Annexure 1
Complete Specification
Abstract:
The present invention deals with separation of mono-ols and polyols from the aqueous stream by reactive extraction technology. In many of the chemical processes, mono-ols and polyols remain in the aqueous phase. Because of their high solubility in water, separation of these compounds is difficult. The conventional method for recovering these compounds is to evaporate water from the solution, distillation or evaporative crystallization. Because of incorporation of distillation or evaporation step, the process of separation of mono-ols and polyols becomes very energy intensive. In this innovation mono-ols and polyols are converted to their corresponding acetals / ketals & are separated from the aqueous stream.

Title: (GRET: Geist's Reactive Extraction Technology)
"Innovative process to separate mono-ols and polyols from the aqueous stream using reactive extraction technology.
Field of the invention:
The present invention provides a Novel Process for separation 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 hydroxy! compounds (e.g. Phenol, Resorcinol, etc.) and their derivatives from their dilute aqueous streams.
Background of the Invention:
In many of mono-ols and polyols utilizing chemical-manufacturing processes, because of high solubility in water, 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, remain in the aqueous phase. The separation process of these mono-ols and polyols involves evaporation of water followed by distillation or crystallization of polyols whichever is applicable. Because of incorporation of water evaporation step, the separation of mono-ols and polyols becomes very energy intensive process. Current invention comprises of the process to separate these mono-ols and polyols from the dilute aqueous solutions.
4
Hereonwards, the term Mono-ol is used to represent organic compounds having single hydroxyl 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.


Object of Invention:
The invention relates to the novel process to recover mono-ols and polyols from the dilute aqueous solution by reactive extraction technology. The objective of this invention is to reduce the separation cost of mono-ols and polyols & devise a non-evaporative method for separation of mono-ols and polyols from the aqueous stream.
Summary of Invention:
The following specification describes the nature of the invention.
The separation of mono-ols and polyols is limited by very high solubility in water
In the invention, an aldehyde / ketone is reacted with the mono-ol / polyol to form its corresponding acetal / ketal & then these acetal / ketal is extracted from, the aqueous phase.
Detailed Description of the invention:
Present invention deals with the Novel Process to recover mono-ols and polyols. The main object of this invention is to reduce the separation cost of mono-ols and polyols & device a methodology to extract mono-ols and polyols from the aqueous stream. This invention deals with the process in which mono-ols «and polyols are reacted with aldehydes / ketones to form their corresponding acetals / ketals in the presence of acid catalyst. Both Alkyl & aryl aldehydes can be selected for preparation of acetals, e.g. Formaldehyde, Acetaldehyde, Propionaldehyde, Butyraldehyde, Benzaldehyde etc. Also for preparation of ketals, aryl or alkyl ketones can be used, e.g. Butanone, Pentanone, Heptanone, Cyclohexanone, Acetophenone etc. In case of water miscible aldehydes / ketones, solvent needs to be added in the mixture e.g. Ethylene Dichloride, Dichloromethane, Toluene, Xylene, Di isopropyl ether etc. The mole ratio of aldehyde to mono-ol or polyol or ketone to mono-ol or polyol can be greater than 0.01 and preferably more than 0.1. The solvent ratio can be in the range of 0.1 to 50 preferably 1 to 10. Acidic catalyst can be selected from the mineral acids such as hydrochloric acid, Sulfuric Acid, Nitric Acid etc or from organic acids such as acetic acid, para-toluene sulfonic acid, butyric acid or acidic ion exchange resins. The operating temperature can be in the range of-15°C to 200 C preferably 5 C to 100°C. The operating pressure can be up to 10 atm. preferably 1 atm. The reaction time can be up to 5 hrs preferably 15 min to 1 hr. The process comprises of addition of acid in the aqueous solution of polyols. Then aldehyde / ketone is added in the solution for the formation of acetal/ ketal. In case of water miscible aldehyde / ketone, solvent is added in the mixture. For aldehyde / ketone with limited water solubility, the aldehyde / ketone itself acts as solvent. The solution is stirred for sufficient time & in number of stages to extract all the acetal / ketal formed. After extraction, the raffinate phase is free from the polyols & extract

phase contains essentially all the acetal / ketal. Evaporation of solvent gives acetal / ketal in the concentrated form.
Advantages of Reactive extraction process are
1. Complete recovery of mono-ols and polyols from the aqueous stream.
2. Ease of separation of mono-ols and polyols from the extract phase.
3. Amenable to presence of organic & inorganic impurities.
4. Highly Energy efficient process
The process is as follows:
Reaction:
H+
Mono-ol/Polyol + Aldehyde/Ketone + Water (Acetal / Ketal + Water)
Extraction:
Solvent / Aldehyde / Ketone
(Acetal / Ketal + Water) ¾® (Acetal / Ketal in extract phase) + Water
Solvent Recovery
Heat
(Acetal / Ketal in extract phase Acetal / Ketal
+
Solvent / Aldehyde / ketone
Where,
Aldehyde - Alkyl or Aryl Aldehyde
Ketones - Alkyl or Aryl
Solvent - Suitable solvent which can extract acetal / ketal
The process of the invention is described in detail in the following examples.
Example 1:
This example illustrates use of n-Butyraldehyde for the extraction of glycerol. .
The extraction of glycerol from aqueous solution obtained after fat splitting process containing Sodium Sulfate is carried out in stirred vessel, having pitched blade downward flow impeller, and fitted with variable speed motor, thermo pocket with thermometer for monitoring temperature.
250 gms of fat splitting resultant aqueous solution containing 10% glycerol & 10% Sodium Sulfate was charged in the extraction vessel. The pH of the solution was adjusted to 4 using Sulfuric Acid. 60 gms of n-Butyraldehyde was charged to


the vessel. Excess of butyraldehyde acts as solvent for extraction of acetal. The solution was stirred for 30 min at a pre-decided RPM. After extraction, the layers were separated. Similar operations were conducted for five stages. The analysis of the aqueous phase shows 0.2% residual concentration of glycerol, which corresponds to 98% extraction.
Example 2:
This example illustrates effect of acid concentration on the extraction.
Hardware details are similar to the example no I.
250 gms of aqueous solution containing 10% glycerol was charged in the extraction vessel. The pH of the solution was adjusted to 1.5 using Sulfuric acid. The extraction was carried out for two stages using 60 gms of butyraldehyde. The analysis of the aqueous phase shows 0.4% residual concentration of glycerol, which corresponds to 96% extraction.
Example 3:
This example illustrates the use of solvent for extraction.
Hardware details are similar to the example no. 1
500 gms of aqueous solution containing 15% ethylene glycol was taken for extraction. The pH of the solution was adjusted to 2 using hydrochloric acid. 170 gms of aqueous acetaldehyde solution (35%) was added in the solution. The solution was stirred for 15 min. 1000 gms of Dichloromethane was added in- the solution & solution was again stirred for 4 hrs. After 5 stages of extraction with Dichloromethane the analysis of aqueous phase shows 1% residual concentration of ethylene glycol.
Example 4:
This example illustrates the use of ion exchange resin for acidification.
Hardware details are similar to the example no 1
500 gms of aqueous solution containing 5% glycerol was taken in the extraction vessel. 10 gms of ion exchange resin (H+ form) having 4 m.eq. Of H+ ions per gram of resin was added in the solution followed by 20 gms Butyraldehyde. The solution was stirred for 60 min. After 5 stages of contact the residual concentration of glycerol in the water was 0.2%

Example 5:
This example illustrates effect of operating temperature on the extraction of polyols
Hardware details are similar to the example no 1
500 gms of aqueous solution containing 5% glycerol was taken in the extraction vessel. 10 gms of ion exchange resin (H+ form) having 4 m.eq. Of H+ ions per gram of resin was added in the solution followed by 20 gms Butyraldehyde. The solution was heated to 50°C. After 3 stages of extraction the concentration of glycerol in the aqueous reduces to 0.5%.
Example 6:
This example illustrates extraction of sorbitol from aqueous solution.
Hardware details are similar to the example no 1
100 gms of aqueous solution containing 4% sorbitol was taken in the extraction vessel. The pH of the solution was adjusted to 2 using hydrochloric acid. 40 gms Butyraldehyde was added to the solution and stirred at room temperature for 60 min. After single stage extraction, concentration of sorbitol in the aqueous reduces to 0.01%.
Example 7:
This example illustrates extraction of D-mannitol from aqueous solution.
Hardware details are similar to the example no 1
100 gms of aqueous solution containing 4% D-mannitol was taken in the extraction vessel. The pH of the solution was adjusted to 2 using hydrochloric acid. 40 gms Butyraldehyde was added to the solution and stirred at room temperature for 60 min. After single extraction, concentration of D-mannitol in the aqueous reduces to 0.05%.
Example 8:
This example illustrates extraction of D-fructose from aqueous solution.
Hardware details are similar to the example no 1
100 gms of aqueous solution containing 4% D-fructose was taken in the extraction vessel. The pH of the solution was adjusted to 2 using hydrochloric acid. 40 gms Butyraldehyde was added to the solution and stirred at room

temperature for 60 min. After single stage extraction, concentration of D-fructose in the aqueous reduces to 0.75%.
Example 9:
This example illustrates use of cyclohexanone for the extraction of D-fructose from aqueous solution.
Hardware details are similar to the example no 1
100 gms of aqueous solution containing 4% D-fructose was taken in the extraction vessel. The pH of the solution was adjusted to 2 using hydrochloric acid. 40 gms cyclohexanone was added to the solution and stirred at room temperature for 60 min. After single stage extraction, concentration of D-fructose in the aqueous reduces to 2.35% giving 41.25% extraction.
Example 10:
This example illustrates use of benzaldehyde for the extraction of D-fructose from aqueous solution.
Hardware details are similar to the example no 1
100 gms of aqueous solution containing 4% D-fructose was taken in the extraction vessel. The pH of the solution was adjusted to 2 using hydrochloric acid. 40 gms benzaldehyde was added to the solution and stirred at room temperature for 60 min. After single stage extraction, concentration of D-fructose in the aqueous reduces to 3.25% giving 18.75% extraction.
Example 11:
This example illustrates use of acetaldehyde for the extraction of methanol from aqueous solution.
Hardware details are similar to the example no 1.
100 gms of aqueous solution containing 5% methanol was taken in the extraction vessel. The pH of the solution was adjusted to 2 using hydrochloric acid. 15 gms acetaldehyde solution was added to the solution and stirred at 15°C for 2 hrs. After reaction was complete, acetal was extracted from aqueous phase by toluene. In single stage extraction, concentration of methanol in the aqueous reduces to 1% giving 80% extraction.

Example 12:
This example illustrates use of butyraldehyde for the extraction of phenol from aqueous solution.
Hardware details are similar to the example no 1.
100 gms of aqueous solution containing 5% phenol was taken in the extraction vessel. The pH of the solution was adjusted to 2 using hydrochloric acid. 30 gms butyraldehyde was added to the solution and stirred at room temperature for 2 hrs. In single stage extraction, concentration of phenol in the aqueous reduces to 2% giving 60% extraction.

Claims:
We claims the following
1. The GRET process for separation of polyols from the dilute aqueous stream by non-evaporative method comprises of reacting polyols with aldehydes / ketones to form their corresponding acetals / ketals in the presence of an acid & then extracting them from the aqueous stream by suitable solvents.
2. A process claimed in claim 1 wherein the input aqueous stream can be obtained from various processes such as fat splitting, biodiesel synthesis etc.
3. A process claimed in claim 1 wherein aldehyde is selected from alkyl or aryl aldehydes such as Formaldehyde, Acetaldehyde, Propionaldehyde, Butyraldehyde, Benzaldehyde etc. and ketone is selected from alkyl or aryl ketones such as Butanone, Pentanone, Heptanone, Cyclohexanone, Acetophenone etc.
4. A process is claimed in claim 1 wherein solvent means aldehyde or ketone itself if it has limited solubility. In case of complete water solubility additional solvent such as Ethylene Dichloride, Dichloromethane, Toluene, Xylene, Di isopropyl ether etc needs to be added which can extract acetal / ketal.
5. A process is claimed in claim 1 wherein the mole ratio of aldehyde / ketone to mono-ol/ polyol should be greater than 0.01 and preferably more than 0.1.
6. A process is claimed in claim 1 wherein the solvent ratio can be in the range of 0.1 to 50 preferably 1 to 10.
7. A process is claimed in claim 1 wherein the operating temperature can be adjusted in the range of-15°C to 200°C preferably 5°C to 100°C.
8. A process is claimed in claim 1 wherein the operating pressure can be up to 10 atm. preferably 1 atm.
9. A process is claimed in claim 1 wherein the reaction time can be up to 5 hrs preferably 15 min to 1 hr.
10. A process is claimed in claim 1 wherein the acidification can be done using mineral acids such as hydrochloric acid, Sulfuric Acid, Nitric Acid etc or from organic acids such as acetic acid, para-toluene sulfonic acid, butyric acid or acidic ion exchange resins.

Annexurc 1
Complete Specification
Abstract:
The present invention deals with separation of mono-ols and polyols from the aqueous stream by reactive extraction technology. In many of the chemical processes, mono-ols and polyols remain in the aqueous phase. Because of their high solubility in water, separation of these compounds is difficult. The conventional method for recovering these compounds is to evaporate water from the solution, distillation or evaporative crystallization. Because of incorporation of distillation or evaporation step, the process of separation of mono-ols and polyols becomes very energy intensive. In this innovation mono-ols and polyols are converted to their corresponding acetals / ketals & are separated from the aqueous stream.
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