Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C68/00—Preparation of esters of carbonic or haloformic acids
  • C07C68/04—Preparation of esters of carbonic or haloformic acids from carbon dioxide or inorganic carbonates
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
  • B01J21/18—Carbon
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C68/00—Preparation of esters of carbonic or haloformic acids
  • C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
  • C07C68/065—Preparation of esters of carbonic or haloformic acids from organic carbonates from alkylene carbonates
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
  • C07C2601/14—The ring being saturated

Definitions

• the invention relates to synthesis of dialkyl carbonates from C0 2 , aliphatic/cyclic aliphatic alcohol and alkylene oxide in presence of renewable catalyst in a single step. Particularly this invention relates to a catalyst prepared directly from biomass used in the synthesis of dialkyl carbonates by single-step preparation.
• C0 2 is a major contributor of climate change and worldwide containment of C0 2 is a major challenge.
• the challenge for decreasing C0 2 in atmosphere needs new ideas and technologies.
• Generating value added chemicals through green chemistry especially by utilizing greenhouse gas carbon dioxide as raw material is a challenging task.
• Present fuel oxygenates like ether compounds methyl tert. butyl ether (MTBE), ethyl tert. butyl ether (ETBE), tert. Amyl methyl ether (TAME) and alcohols like methyl alcohol (CH 3 OH), ethyl alcohol (C 2 H 5 OH) are being used as oxygenates.
• MTBE methyl tert. butyl ether
• ETBE ethyl tert. butyl ether
• TAME tert.
• Alcohols like methyl alcohol (CH 3 OH), ethyl alcohol (C 2 H 5 OH)
• aforementioned oxygenates lead to many problems like corrosiveness, environmental harm, and
• dialkyl carbonates especially dimethyl carbonate (DMC), diethyl carbonate (DEC), and ethyl methyl carbonate (EMC) have been widely accepted as fuel oxygenates because of excellent gasoline blending properties like high blending octane numbers, low blending reid vapour pressures (RVP) and lower amounts of toxic emissions compared to ether oxygenates.
• DMC dimethyl carbonate
• DEC diethyl carbonate
• EMC ethyl methyl carbonate
• RVP reid vapour pressures
• Several other applications of dialkyl carbonates were explored in green chemical industry for the preparation of polycarbonates, isocyanates, synthetic lubricants, pharmaceutical and agricultural intermediates.
• dialkyl carbonates are non-corrosive and highly efficient alkylating agents to replace hazardous phosgene. Due to high volatile value, they are widely used in paint industry.
• the conventional process involves usage of hazardous chemicals like phosgene or carbon monoxide as starting materials.
• the alternative and non-hazardous process involve utilization of C0 2 as raw material, which is eco-friendly and cost-effective process.
• the eco-friendly synthetic route involves reaction of carbon dioxide with alcohol to generate corresponding dialkyl carbonates.
• dialkyl carbonates dimethyl carbonate and diethyl carbonate synthesis has been well recognised and explored.
• number of homogeneous catalysts e.g. tin complexes: distannoxanes
• heterogeneous catalysts e.g. Ce0 2 , modified Zirconia, Zeolites
• Dialkyl carbonates mainly DMC and DEC were prepared in the presence of catalysts NaI/Tl 2 C0 3 , Nal/TIOH, Nal, T1 2 C0 3 , Imidazole, TBAB, TEAB and organic bases like guanidine, DABCO, triethanol amine and etc. Yields of DMC and DEC are high with ethylene oxide compared to propylene oxide, which may be due to sterically more feasible product formation. The main drawback of this work is expensive catalysts and halogen containing catalysts.
• US 5218135 has revealed two step synthesis of dialkyl carbonate from C0 2 , alkylene oxide and alcohol in presence of bifuctional catalysts. Initially cyclic carbonate was prepared from alkylene oxide and C0 2 in presence of bifunctional catalysts then cyclic carbonate was treated with alcohol in presence of bifuctional catalyst to yield corresponding dialkyl carbonate.
• Present invention discloses a preparation methodology of dialkyl carbonates using wood ash catalyst; involving insertion of C0 2 molecule in to an alkylene oxide and transesterification of that intermediate compound with aliphatic alcohol in to dialkyl carbonate in single pot reaction.
• the inherent property of wood ash catalyst of C0 2 insertion along with the property of transestrification was explored for the synthesis of dialkyl carbonates.
• the present invention addresses one or more such problems of the prior art as discussed above. However, it is contemplated that the invention may prove useful in addressing other problems also in a number of technical areas.
• the present invention relates to a single-pot method for preparing dialkyl carbonate, the method comprising dissolving an alkylene oxide in an aliphatic or cyclic aliphatic alcohol, adding a wood ash catalyst, adding C0 2 gas under pressure and heating the reaction mixture, cooling the reaction mixture to about room temperature, and depressurizing to obtain dialkyl carbonate.
• the reaction mixture is filtered to recover the catalyst.
• the aliphatic or cyclic aliphatic alcohols are Ci to C 12 aliphatic alcohols and Ci to C 12 cyclic aliphatic alcohols.
• the aliphatic or cyclic aliphatic alcohol is selected from methanol, ethanol, propanol, butanol, amyl alcohol, hexanol, octanol, cyclohexanol and octahexanol.
• the alkylene oxide is selected from the group comprising ethylene oxide, propylene oxide, 1,2-epoxy butane, 1,2-epoxy pentane and 1,2-epoxy hexane.
• the pressure is about 70-90 bar.
• the heating is carried out at a temperature range of about 100-180°C.
• the filtered catalyst is washed with an aliphatic alcohol and dried at about 120°C for 24 hours for reuse.
• the aliphatic alcohol is methanol or ethanol.
• the catalyst obtained is reused in the process of claim 1.
• the present invention also relates to a method of preparing wood ash catalyst comprising washing wood with deionized water; drying the wood until the wood attains constant weight; dry ashing the wood; and calcining the wood to obtain wood ash catalyst.
• the wood is selected from Azadirachta indica and Acacia nilotica.
• the wood is dried at a temperature of about 60° to 80°C.
• the dry ashing is carried out at a temperature of 525 ⁇ 25°C.
• the calcining is carried out at a temperature of about 300°C to about 1200°C.
• wood ash catalyst BWCsoo as heterogeneous catalyst for the synthesis of dimethyl carbonate from propylene oxide, C0 2 and methanol with good yield of 51.11% which is better than reported in literature.
• Activity of wood ash catalyst BWCsoo was also further evaluated with several alcohols for the synthesis of respective dialkyl carbonates. Amongst, diethyl carbonate was synthesised from propylene oxide, C0 2 and ethanol with highest yield of 53.43%. The following terms are defined as follows:
• BWo Wood ash without calcination. On using BWo as catalyst for the preparation of dialkyl carbonates, the overall yield is 6-7%. The reason for the low yield of dialkyl carbonetes is that wood ash contains primarily carbonates of Ca, Mg along with other metal components and less basic in nature. It also does not contain sintered calcium silica phosphate compound. So, the dialkyl carbonate yield is very less in the reaction with BW 0 .
• BWC500 Wood ash calcined at temperature 500°C.
• the overall yield is 42.46%.
• the reason for the moderate yield is the partial conversion into active catalyst such as some amount of calcium oxide (CaO) and magnesium oxide (MgO) along with small amount of calcium silica phosphates were observed in XRD studies. Accordingly conversion to dialkyl carbonate is not complete and moderate.
• BWCsoo Wood ash calcined at temperature 800°C. On using BWCsoo as catalyst for the preparation of dialkyl carbonates, the overall yield is 53.43%. The reason for the high yield is that catalyst from wood ash at 800°C contains completely converted magnesium oxide (MgO) and calcium oxide (CaO) along with sintered calcium silica phosphates which gave highest dialkyl carbonate yield.
• MgO magnesium oxide
• CaO calcium oxide
• Figure 1 IR spectrum of wood ash catalysts
• Figure 3 TGA analysis of BWCsoo wood ash catalyst.
• the present invention discloses a preparation methodology of dialkyl carbonates (fuel oxygenates) by reacting C0 2 , aliphatic/cyclic aliphatic alcohol and alkylene oxide in presence of renewable catalyst in a single step, the said catalyst being prepared from biomass.
• An aspect of the invention discloses the preparation methodology of the catalyst; said catalyst being prepared directly from the biomass.
• Another aspect of the present invention is the use of the novel renewable catalyst prepared from biomass in a single step reaction to produce dialkyl carbonates from aliphatic & cyclic alcohols and propylene oxide by utilizing C0 2 .
• An aspect of the present invention is that the catalyst prepared from wood ash is novel, economical and eco-friendly.
• the wood ash used in accordance with this invention can be obtained from biomass, including but not necessarily limited to, wood of trees such as Azadirachta indica, Acacia nilotica.
• Another aspect of the invention discloses the production of alkylene glycol as by-product during synthesis of dialkyl carbonates in presence of renewable catalyst.
• the wood ash catalyst is basic in nature. Composition of wood ash catalyst is mixture of oxides of Ca and Mg along with sintered material calcium silica phosphates. Wood ash also contains potassium and small quantities of other metal derivatives. The typical combination of all these compounds in wood ash catalyst makes it a suitable catalyst for various organic transformations.
• wood ash catalyst catalyses C0 2 insertion in to alkylene oxide to form cyclic carbonate which is further converted in situ to dialkyl carbonates in the presence of alcohols. Therefore, wood ash catalyst helps to convert C0 2 to dialkyl carbonates in the presence of alcohols in a single pot reaction conditions in comparison to prior art claim of dialkyl carbonates synthesis from C0 2 mostly carried out in two separate steps by using two different types of catalysts.
• the advantage of this invention is wood ash catalyst able to perform synthesis of dialkyl carbonates from C0 2 in a single pot reaction conditions.
• the preparation methodology according to the present invention involves washing the wood with deionised water and then drying until the wood attains constant weight.
• the wood was dry ashed separately and calcined.
• One-pot synthesis of dialkyl carbonates from aliphatic/cyclic aliphatic alcohol, C0 2 and alkylene oxide was carried out in a controlled heating system.
• the preparation of dialkyl carbonate involves washing the wood with deionised water and then drying at about 60°-80°C until the wood attains constant weight.
• the wood was dry ashed separately and calcined, at temperature ranges of about 300°C to about 1200°C.
• One-pot synthesis of dialkyl carbonates from aliphatic/cyclic aliphatic alcohol, C0 2 and alkylene oxide was carried out in an autoclave vessel fixed to stirrer and controlled heating system.
• drying step the wood is heated at a temperature range of 60 to 80°C for 24 hours to remove moisture and impurities present in the wood after washing with deionised water.
• the dry ashing step the wood is burned in a furnace at 525°C ⁇ 25°C (Ref. TAPPI, Ash in wood, pulp, paper and paperboard: combustion at 525°C, T211 om-93, 1993).
• the aliphatic alcohols/cyclic alcohols used according to the present invention include C 1 to C 12 aliphatic alcohols, Ci to C 12 cyclic aliphatic alcohols like cyclic pentanol, cyclic hexanol, more preferably methanol, ethanol, propanol, butanol, amyl alcohol, hexanol, ocyanol, cyclohexanol, octahexanol.
• the alkylene oxides used according to the present invention include ethylene oxide, propylene oxide, 1,2-epoxy butane, 1,2-epoxy pentane, 1,2-epoxy hexane.
• the single-pot method for preparing dialkyl carbonate comprises dissolving alkylene oxide in an aliphatic/cyclic aliphatic alcohol, adding wood ash catalyst, adding C0 2 gas at a workable pressure range and heating the reaction mixture, cooling the reaction mixture to about room temperature, and depressurizing to obtain dialkyl carbonate.
• the reaction mixture is filtered to remove the catalyst.
• the filtered catalyst was washed with an aliphatic alcohol, preferably methanol or ethanol and dried for reuse.
• the single-pot method for preparing dialkyl carbonate comprises dissolving alkylene oxide in an aliphatic/cyclic aliphatic alcohol, adding wood ash catalyst in the autoclave vessel.
• the autoclave vessel was pressurised with C0 2 gas.
• C0 2 gas At the workable pressure range of about 70-90 bar and temperature range of about 100-180°C, the reaction mixture was stirred constantly for about 24 hours.
• reaction mixture was cooled to room temperature, depressurised and filtered to remove the catalyst.
• the filtered catalyst was washed with an aliphatic alcohol, preferably methanol or ethanol and dried at about 120°C for about 24 hours for reuse.
• the identification and quantification of the components in the reaction mixtures were performed with GC and GC-MS analysis.
• Catalyst prepared from wood ash is novel, economical and eco-friendly compared to catalysts reported in literature for the synthesis of dialkyl carbonates.
• the developed process methodology is single step reaction to produce dialkyl carbonates from aliphatic/cyclic alcohols and propylene oxide by utilizing C0 2 . Separation and regeneration of catalyst is performed by low cost techniques.
• Wood ash catalyst has combination of the above properties due to presence of metal oxides, mixed metal oxides along with alkali earth metal halides. Both alcohol and C0 2 are equally capable to insert into epoxide ring but catalyst should be selective for C0 2 insertion. Wood ash catalyst showed typical interaction with C0 2 and activated it successfully towards epoxide insertion reaction.
• the prepared catalysts were evaluated for their alkalinity (pH), particle size and surface area, results are shown in Table 1.
• the alkalinity of BW 0 (wood ash without calcination), BWC 50 o (wood ash calcined at 500°C) and BWCsoo (wood ash calcined at 800°C) catalysts were found to be 11.28, 11.68 and 12.02 respectively. It was observed that the calcination temperature affects the alkalinity of the catalysts.
• the results showed that BWCsoo catalyst calcined at 800°C temperatures has highest alkalinity may be due to thermal decomposition of CaC0 3 to CaO which is having higher soluble alkalinity.
• the surface area of wood ash catalysts decreases with increase of calcination temperature.
• the surface areas of BWo, BWC500 and BWCsoo catalysts were 2.0, 1.6 and ⁇ 1 m 2 /gm respectively.
• Lower surface area of BWC 80 o catalyst than BWC 50 o catalyst is due to conversion of CaC0 3 into CaO which results in sintering by the formation of calcium phosphate silicate.
• the observation was further confirmed by XRD study of the catalyst structure ( Figure 2).
• BWo, BWC500 and BWC 8 oo were determined as 20.76, 25.65 and 36.26 ⁇ respectively.
• the result reveals that particle size of the catalysts has increased with increasing calcination temperature [Biomass Bioenergy 4 (1993) 103-106].
• the possible reason may be the increase of sintering with increase of temperature, leads to increase in particle size as reported in earlier study [Biomass and Bioenergy 41 (2012) 94-106].
• Recovered BWC 80 o catalyst particle size is 56.77 ⁇ may be due to the formation of some amounts of calcium hydroxide and carbonates however this does not has any effect on catalyst performance on subsequent reuse.
• the FTIR spectra of wood ash catalysts are given in Figure 1.
• the spectra of BWo catalyst shows the presence of carbonates, C0 3 "2 ( the peaks at 1795, 1427, 875 and 71 1 cm _1 ) and phosphates, P0 4 "3 components (peaks at 1 1 12, 1047 and 617 cm “1 ), confirms the presence of metal carbonates (mainly CaC0 3 ) and metal phosphates.
• the IR spectrum of BWC 500 catalyst shows similar spectral features.
• BWC 80 o catalyst After calcination at 800°C, BWC 80 o catalyst indicates the presence of metal oxides (peak at 3425, 2960, 1462, 1408, 921 and 516 cm “1 ) along with the calcium phosphates silicate (peak at 2856, 1388 and 1 1 18 cm “1 ). The results reveal that the calcination at higher temperature results in carbonates decomposition to metal oxides.
• BW 0 The XRD pattern of BW 0 , BWC 50 o, BWC 80 o and recovered BWC 80 o catalyst is shown in Figure 2.
• the results indicate that BWo catalyst is mainly composed of CaC0 3 along with small amount of KC1 and Si0 2 .
• the pattern of crystalline phases remains same in BWC 500 catalyst with additional appearance of CaO crystalline phase.
• BWC 8 oo catalyst shows the presence of metal oxides mainly CaO and MgO along with KC1 and mixed metal phosphates Ca 2 SiO 4 .0.05Ca 3 (PO 4 ) 2 . These results were further confirmed by elemental analysis.
• XRD analysis of recovered BWC 80 o catalyst show same structure as of fresh BWC 80 o catalyst. However some decreasing intensity of crystalline phases of CaO, MgO and mixed metal phosphates is due to formation of calcium hydroxide is confirmed by increasing of pH value and IR analysis.
• BWC 8 oo catalyst shows the presence of Ca, K and Mg in higher amounts as 32.30, 10.91 and 5.79 mass fraction percentage respectively. While the Na, P and Al are in notable amounts as 1.42, 1.40 and 1.90 mass fraction percentage respectively, the transition metals present in BWCsoo are mainly Fe, Mn and Zn in trace quantities. The presence of the minor quantities of Silicon was also confirmed by XRF analysis. TGA Analysis
• BWCsoo catalyst stability was measured by TG analysis carried out on TG model 2950 Hi Resolution modulated TGA, with heating rates 10°C/min, temperature ramp up to 800°C.
• the results given in the Figure 3 shows the weight loss of 2.19 wt. % is observed at 198°C corresponding to the removal of loosely absorbed water on the surface of catalyst.
• the stability of BWC 80 o catalyst is confirmed by metal analysis of carbonate product produced with XRF technique and found all the metal ⁇ 1 mg/Kg. Above findings also confirm the non-leaching behaviour of the catalyst and are in agreement with the earlier study [Biomass and Bioenergy 41 (2012) 94-106].
• dialkyl carbonates are extensively studied as fuel oxygenates in the literature (Energy & Fuels 1997, 11, 2-29). The octane number, RVP and toxic emissions from dialkyl carbonates are compared with ether oxygenates and reported in the literature (Energy Fuels 2010, 24, 4812-4819). However, synthesis of these dialkyl carbonates reported through phosgene route which is corrosive and environmentally not favourable. We have developed environmentally safe method for preparation of dialkyl carbonates from C0 2 as feed stock and carrying out the preparation in single pot in presence of wood ash as novel catalyst.
• Blending carried out to keep overall oxygen content in gasoline to 2.7% by mass as per IS 2796-2008 motor gasoline BS IV specifications.
• dialkyl carbonates are extensively studied as fuel oxygenates in the literature (Energy & Fuels 1997, 11, 2-29).
• the octane number, RVP and toxic emissions from dialkyl carbonates were compared with ether oxygenates and reported in the literature (Energy Fuels 2010, 24, 4812-4819).
• the synthesis of these dialkyl carbonates through phosgene route is corrosive and environmentally not favourable.
• Example 1 explains that reaction mixture was cooled to room temperature after 24 hours, depressurised and filtered to remove the catalyst. The filtered catalyst was washed with methanol (20 ml) dried at 120°C for 24 hours for reuse.
• Example 2 Synthesis of DEC from Ethanol, C0 2 and Propylene oxide using BWC 500 as catalyst
• Example 3 Synthesis of DEC from Ethanol, C0 2 and Propylene oxide using 10 wt % BWCsoo as catalyst
• First fraction contains mixture of excess ethanol and DEC and second fraction contains mixture of propylene glycol and propylene carbonate.
• identification and quantification of the components in the fractions were performed with GC and GC-MS analysis.
• the quantitative analysis of ethanol fraction reveals that formation of DEC is 11.06 gm (93.67 mmol).
• the calculated yield of DEC from propylene oxide is measured as 53.43%.
• Example 4 Synthesis of DEC from Ethanol, C0 2 and Propylene oxide using BWC 80 o as catalyst at 70 bar C0 2 pressure
• Example 5 Synthesis of DEC from Ethanol, C0 2 and Propylene oxide using BWCsoo as catalyst at 90 bar C0 2 pressure
• Example 6 Synthesis of DEC from Ethanol, C0 2 and Propylene oxide using BWCsoo as catalyst at 80 bar C0 2 pressure and 120 °C temperature.
• Propylene oxide (10.17 gm, 0.175 mol), ethanol (64.70 gm, 1.40 mol) and wood ash catalyst BWCsoo (7.0 gm, 10% wt/wt) were charged in to 700 ml autoclave vessel.
• the autoclave vessel was pressurised with C0 2 pressure, heated to reach 120°C temperature and 80 bar pressure under constant stirring during the reaction for 24 hours.
• Reaction mixture work up was carried out as described in example 3.
• Analytical analysis of ethanol fraction reveals that formation of DEC is 5.08 gm (43.05 mmol).
• the calculated yield of DEC corresponding to propylene oxide is 24.54%.
• Example 7 Synthesis of DEC from Ethanol, C0 2 and Propylene oxide using 5 wt % BWCsoo as catalyst
• Example 8 Synthesis of DEC from Ethanol, C0 2 and Propylene oxide using 15 wt % BWCsoo as catalyst
• Example 9 Synthesis of DEC from Ethanol, C0 2 and Propylene oxide using 10 wt % of recovered BWCsoo from example 3 as catalyst
• Propylene oxide (10.17 gm, 0.175 mol), ethanol (64.70 gm, 1.40 mol) and wood ash recovered catalyst BWCsoo from example 3 (10.5 gm, 15% wt/wt) were charged into 700 ml autoclave vessel.
• the autoclave vessel was pressurised with C0 2 pressure, heated to reach 150°C temperature and 80 bar pressure under constant stirring during the reaction for 24 hours.
• Reaction mixture work up was carried out as described in example 3.
• the analytical analysis of ethanol fraction reveals that formation of DEC is 9.85 gm (83.50 mmol).
• the measured yield of DEC from propylene oxide is 47.6%.
• Example 9 shows the recovered catalyst used second time for the monitoring DEC synthesis under standardised reaction conditions.
• the DEC yield with second time recovered catalyst is slightly lower 47.6% than the previous results.
• Third cycle usage of wood ash catalyst gave 46.5% of DEC yield.
• Example 10 Synthesis of DEC from Ethanol, C0 2 and Propylene oxide using BWC 80 o as catalyst at 80 bar C0 2 pressure and 180°C temperature
• Example 11 Synthesis of DEC from Ethanol, C0 2 and Ethylene oxide using BWCsoo as catalyst at 80 bar C0 2 pressure and 150°C temperature
• Example 12 Synthesis of DMC from Methanol, C0 2 and Ethylene oxide using BWCsoo as catalyst at 80 bar C0 2 pressure and 150°C temperature
• Ethylene oxide (7.7 gm, 0.175 mol), methanol (44.80 gm, 1.40 mol) and wood ash catalyst BWC 8 oo (5.5 gm, 10% wt/wt) were taken in to 700 ml autoclave vessel and closed tightly.
• the autoclave vessel was pressurised with C0 2 pressure, heated to reach 150°C temperature and 80 bar pressure under constant stirring during the reaction for 24 hours.
• Reaction mixture work up was carried out as described in example 1.
• the quantitative analysis of methanol fraction reveals that formation of dimethyl carbonate is 8.20 gm (91.11 mmol).
• the calculated yield of dimethyl carbonate from ethylene oxide is measured as 52.13%.
• Example 13 Synthesis of DEC from Ethanol, C0 2 and 1,2-epoxyhexane using BWCsoo as catalyst at 80 bar C0 2 pressure and 150°C temperature
• 1,2-epoxyhexane (17.53 gm, 0.175 mol), methanol (44.80 gm, 1.40 mol) and wood ash catalyst BWC 80 o (6.23 gm, 10% wt/wt) were charged into 700 ml autoclave vessel and tightly closed.
• the autoclave vessel was pressurised with C0 2 pressure, heated to reach 150°C temperature and 80 bar pressure under constant stirring during the reaction for 24 hours.
• Reaction mixture work up was carried out as described in example 1.
• the quantitative analysis of methanol fraction reveals that formation of dimethyl carbonate is 4.42 gm (49.00 mmol).
• the calculated yield of dimethyl carbonate from epoxyhexane is measured as 28.06%.
• Example 15 Synthesis of Dicyclohexyl Carbonate from cyclohexanol, C0 2 and 1,2- epoxyhexane using BWCsoo as catalyst at 80 bar C0 2 pressure and 150°C temperature
• Example 16 Synthesis of DMC from methanol, C0 2 and propylene oxide using BWC 80 o as catalyst at 80 bar C0 2 pressure and 150°C temperature
• the mixture of propylene oxide (10.17 gm, 0.175 mol), methanol (44.80 gm, 1.40 mol) and wood ash catalyst BWCsoo (5.5 gm, 10% wt/wt) was taken into 700 ml autoclave vessel and closed with lid.
• the autoclave vessel was pressurised with C0 2 pressure, heated to reach 150°C temperature and 80 bar pressure under constant stirring during the reaction for 24 hours.
• Reaction mixture work up was carried out as described in example 1.
• the quantitative analysis of methanol fraction reveals that formation of dimethyl carbonate is 8.05 gm (89.5 mmol).
• the calculated yield of dimethyl carbonate from propylene oxide is measured as 51.11%.
• Example 17 Synthesis of didecyl carbonate from n-decanol, C0 2 and propylene oxide using BWCsoo as catalyst at 80 bar C0 2 pressure and 150°C temperature
• Example 18 Synthesis of dicyclohexyl carbonate from cyclohexanol, C0 2 and propylene oxide using BWCsoo as catalyst at 80 bar C0 2 pressure and 150°C temperature

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