Annexure 1
Complete Specification
Abstract:
The present invention deals with recovery of mono-ols and polyols of aliphatic and water-soluble aromatic compounds from their corresponding acetals / ketals. Recovery of mono-ols and polyols from the acetals / ketals A is considered to be difficult because of possibility of polymerization of aldehydes / ketones during the course of reaction. In this innovation mono-ols and polyols are recovered from acetals / ketals by improved hydrolysis technology.


Title: (GMPRT: Geist's Mono-ol & Polyol Recovery Technology)
"Innovative process to recover mono-ols and polyols from corresponding acetals / ketals".
Field of the invention:
The present invention provides a Novel Process for recovery of mono-ols (e.g. methanol, ethanol, etc.) and their derivatives, various diols (e.g. butanediol, propanediol, etc.) and their derivatives, glycols (e.g. Propylene glycol, Ethylene glycol, etc.) and their derivatives, polyols such as Glycerol and their derivatives, Sugars (e.g. Sorbitol, Adonitol, Dulcitol, Mannitol, Sorbose, Mannose, Fructose, Arabinose, Glucose, Rhamnose, Galactose etc.) and their derivatives, water soluble aromatic hydroxyl compounds (e.g. Phenol, Resorcinol, etc.) and their derivatives from their corresponding acetals / ketals.
Background of the Invention:
Acetals / ketals are prepared by reacting mono-ols and/or polyols with aldehydes / ketones. Mono-ols are the organic compounds containing single hydroxyl group (-OH) and Polyols are the organic compounds having more than one hydroxyl (-OH) group. Mono-ols and Polyols are separated from the dilute aqueous streams by converting them to corresponding acetals / ketals. Acidified water can be used to recover the mono-ols and polyols from corresponding acetals / ketals. But in that case, the conversion of acetal / ketal is never complete. Also the output of the process is again dilute mono-ols or polyol, which needs to be concentrated by evaporation of excess water or distillation. Current invention comprises of the process to separate these mono-ols and polyols from corresponding acetals / ketals.
Object of Invention:
The invention relates to a novel process to recover mono-ols (e.g. methanol, ethanol, etc.) and their derivatives, various diols (e.g. butanediol, propanediol, etc.) and their derivatives, glycols (e.g. Propylene glycol, Ethylene glycol, etc.) and their derivatives, polyols such as Glycerol and their derivatives, Sugars (e.g. Sorbitol, Adonitol, Dulcitol, Mannitol, Sorbose, Mannose, Fructose, Arabinose, Glucose, Rhamnose, Galactose etc.) and their derivatives, water soluble aromatic hydroxyl compounds (e.g. Phenol, Resorcinol, etc.) and fheir derivatives from their corresponding acetals / ketals by improved hydrolysis technology. The objective of this invention is to recover concentrated mono-ols or polyols from corresponding acetals / ketals.


Hereonwards, the term Mono-ol is used to represent organic compounds having single hydroxy! group (-OH) such as methanol, ethanol, phenol etc. and their derivatives. Term Polyol is used to represent organic compounds having more than one hydroxyl group (-OH) such as various diols (e.g. butanediol, propanediol, etc.) and their derivatives, glycols (e.g. Propylene glycol, Ethylene glycol, etc.) and their derivatives, polyols such as Glycerol and their derivatives, Sugars (e.g. Sorbitol, Adonitol, Dulcitol, Mannitol, Sorbose, Mannose, Fructose, Arabinose, Glucose, Rhamnose, Galactose etc.) and their derivatives, water soluble polyhydroxy aromatic compounds such as resorcinol and their derivatives.
Summary of Invention:
The following specification describes the nature of the invention. The separation of polyols is limited by
1) Less Conversion (typically less than 30 - 40%)
2) Low concentration in the aqueous stream (around 10%)
In the invention, the acetal / ketal is hydrolyzed in presence of acid catalyst & the aldehyde / ketone thus formed is recovered continuously.
Detailed Description of the invention:
Present invention deals with the Novel Process to recover mono-ols / polyols form their corresponding acetals / ketals. The main object of this invention is to separate concentrated mono-ols / polyols from their corresponding acetals / ketals. This invention deals with the process in which acetals / ketals are hydrolyzed in presence of acidic catalyst & aldehydes / ketones formed are continuously removed. Any acid, which can give H+ ions, can be used as a catalyst. Examples of acid catalyst are mineral acids such as hydrochloric acid, Sulfuric Acid, Nitric Acid etc and/or organic acids such as acetic acid, para-toluene sulfonic acid, butyric acid and/or acidic ion exchange resins. The H+ concentration can be in the range of 0.0001 to l000 milimoles per gram of water. The mole ratio of water to acetal / ketal for hydrolysis can be greater than 0.01 preferably 1 to 10. The operating temperature can be in the range of -20°C to 400°C preferably 30°C to 200°C. The operating pressure can be upto 50 atm, preferably between 5 torrto 1 atm. The reaction time depends on the rate of separation of released aldehyde /ketone from the reaction mixture. The process comprises of addition of water & acid catalyst to the acetal / ketal and heating the mixture to cause vaporization of aldehyde / ketone which is condensed and collected separately.

Advantages of process are
I Complete conversion of acetal / ketal to corresponding aldehyde / ketone.
2. Recovery of mono-ol / polyol with high concentration.
3. Amenable to presence of organic & inorganic impurities.
4. Ease of operation
The process is as follows:
Reaction:
Acetal / Ketal + Water *• Aldehyde / Ketone + Polyol/ Mono-ol
Where,
Aldehyde - Alkyl or Aryl
Ketones - Alkyl or Aryl
The process of the invention is described in detail in the following examples. ,
Example 1:
This example illustrates the use of hydrochloric acid for the recovery of glycerol.
The reaction was carried out in stirred vessel, having pitched blade downward flow impeller, and fitted with variable speed motor, thermo pocket with thermometer for monitoring temperature. The condenser was attached to, the reactor, which was connected to condensate receiver.
100 gms of butyraldehyde phase containing 40% Butyraldehyde- Glycerol acetal which is obtained from extraction of aqueous phase of fat splitting origin was charged in the reaction vessel. 10 gms of water followed by 0.1 gms hydrochloric acid was charged in the solution. The mixture was gradually heated to 90 C. The butyraldehyde was collected separately. 30.37 gms pale yellow colored reaction residue was obtained. The analysis shows 83% glycerol in it.
Example 2:
This example illustrates effect of acid concentration.
Hardware details are similar to the example no 1.
250 gms of butyraldehyde phase containing 35% Butyraldehyde-Glycerol acetal was charged in the reaction vessel. 2 gms of Hydrochloric acid dissolved in 20 gms of water was charged in the vessel. The mixture was heated to 90 C. The butyraldehyde evaporated from the vessel was condensed & collected separately.


After 2 hrs, the residual mass was cooled. The output of the process was 64.10 gms of glycerol phase. The analysis of the phase shows 86% glycerol in it.
Example 3:
This example illustrates effect of pressure & temperature.
Hardware details are similar to the example no. 1
250 gms of butyraldehyde phase containing 35% Butyraldehyde-Glycerol aCetal was charged in the reaction vessel. 2gms of hydrochloric acid dissolved in 15 gms of water was charged in the vessel. The pressure of the system was reduced to 100 torr. The reaction mass was heated gradually to 50°C. The butyraldehyde evaporated from the reaction mixture at 40°C, which was condensed & collected. After 1 hr, the reaction residue was cooled. The weight of the reaction residue was 59.30 gms. The analysis of the residual phase shows 93% glycerol in it.
Example 4:
This example illustrates the use of ion exchange resin.
Hardware details are similar to the example no 1
100 gms of Butyraldehyde-Glycerol acetal was charged in the reaction vessel. Igms of ion exchange resin having 4 m. eq. Of H+ per gram of dry resin was charged in the vessel along with 30 gms of water. The reaction mass was heated gradually to 100°C. Butyraldehyde & some part of water evaporated from the reaction mixture was condensed & collected. After 8 hrs, the reaction residue was cooled. The weight of the reaction residue was 67.75 gms. The analysis of the residual phase shows 93% glycerol in it.
Example 5:
This example illustrates hydrolysis of acetal of sucrose and butyraldehyde
Hardware details are similar to the example no 1
100 gms of Butyraldehyde-sucrose acetal was charged in the reaction vessel. Igms of ion exchange resin having 4 m. eq. Of H+ per gram of dry resin was charged in the vessel along with 26 gms of water. The reaction mass was heated gradually to 100°C. Butyraldehyde & some part of water evaporated from the reaction mixture was condensed & collected. After 8 hrs, the reaction residue was cooled. The weight of the reaction residue was 74.3Igms. The analysis of the residual phase shows 82.5% sucrose in it.

Example 6:
This example illustrates hydrolysis of ketal of sorbitol and cyclohexanone.
Hardware details are similar to the example no 1
100 gms of cyclohexanone-sorbitol ketal was charged in the reaction vessel. Igms of ion exchange resin having 4 m. eq. Of H+ per gram of dry resin was charged in the vessel along with 25.56 gms of water. The reaction mass was heated gradually to 90 C. After 10 hrs, the reaction residue was cooled. The weight of the reaction residue was 55.89gms. The analysis of the residual phase shows 77.13% sorbitol in it.
Example 7:
This example illustrates hydrolysis of acetal of mannitol and benzaldehyde.
Hardware details are similar to the example no 1
100 gms of benzaldehyde-mannitol acetal was charged in the reaction vessel. 3gms HCI was mixed with 25 gms of water and charged in the vessel. The reaction mass was heated gradually to 90°C. After 10 hrs, the reaction residue was cooled. The weight of the reaction residue was 52.88gms. The analysis of the residual phase shows 77.13% mannitol in it.
Example 8:
This example illustrates hydrolysis of acetal of methanol and acetaldehyde.
Hardware details are similar to the example no 1
100 gms of dimethyl acetal of acetaldehyde was charged in the reaction vessel. 3gms HCI was mixed with 25 gms of water and charged in the vessel. The reaction mass was heated gradually to 50°C. After 8 hrs, the reaction residue was cooled. The weight of the reaction residue was 71.1 Igms. The analysis of the residual phase shows 90% methanol in it.
Example 9: This example illustrates hydrolysis of acetal of phenol and butyraldehyde.
Hardware details are similar to the example no 1
100 gms of acetal of phenol and butryaldehyde was charged in the reaction vessel. 3gms HCI was mixed with 25 gms of water and charged in the vessel. The reaction mass was heated gradually to 90°C. After 12 hrs, the reaction residue was cooled. The weight of the reaction residue was 77.68gms. The analysis of the residual phase shows 79% phenol in it.


Claims:
We claims the following
1. The GPRT process consists of recovery of mono-ols and polyols from acetal / ketal in presence of acid catalyst & continuously removing aldehyde / ketone from the reaction mass to get complete conversion of acetal / ketal & concentrated mono-ols and polyols.
2. A process claimed in claim 1 wherein the acetal/ Ketal phase can be obtained by extraction of various aqueous streams containing mono-ols/ polyols resulting from fat splitting, biodiesel synthesis etc.
3. A process claimed in claim 1 wherein acid means any species, which can donate H+ ions e.g. Mineral acid such as hydrochloric acid, Sulfuric Acid, Nitric Acid etc and/or organic acids such as acetic acid, para-toluene sulfonic acid, butyric acid and/or acidic ion exchange resins.
4. A process is claimed in claim 1 wherein the concentration of H+ can be in the range of 0.0001 to 1000 milimoles per gram of water.
5. A process is claimed in claim 1 wherein the mole ratio of water for hydrolysis can be greater than 0.01 preferably 1 to 10.
6. A process is claimed in claim 1 wherein the operating temperature can be in the range of-20°C to 400°C preferably 30°C to 200X.
7. A process is claimed in claim 1 wherein the operating pressure can be upto 50 atm, preferably between 5 torr to 1 atm.
8. A process is claimed in claim 1 wherein the reaction time is dependent on the operating temperature & pressure.