Title of Invention

"A PROCESS FOR PREPARING A HIGH SURFACE AREA (NI, W, CU)/KIESELGUHR CATALYST"

Abstract This invention relates to a process of preparing a high surface area (Ni, W, Cu) / kieselguhr catalyst for hydrogenolysis and hydrogenation reaction for the production of polyols at low temperatures and pressures comprising: step 1- making a slurry of kieselguhr, nickel nitrate and cupric nitrate in water in the ratio 1:0.8 - 5.2: 0.05-0.2: 25 - 35, step 2- heating the said slurry at 60-90°C for diffusing nitrates of nickel and copper into the pores of silica in kieselguhr, step 3- preparing ammonium para & meta - tungstates by mixing 0.4 ml/gm to 17 ml/gm of tungstic acid and concentrated ammonium hydroxide and heating them at 90-110°C, step 4- adding the said ammonium para & meta tungstates to the slurry prepared in step 2 at 60-90 °C for a period of 15-90 minutes, step 5- digesting the resulting mixture of step 4 at 60-90°C for 30-90 minutes for diffusing ammonium para & meta tungstates into the pores of silica in kieselguhr, step 6- adding aqueous solution of sodium carbonate to step 5 and digesting the resulting slurry for 60-120 minutes at 70-110°C to precipitate carbonates and hydroxides of nickel and copper as well as oxides of tungsten, step 7- filtering, washing and drying the said precipitate under vacuum to form the catalyst, and step 8- reducing the said catalyst with hydrogen at temperature 500-700°C to convert carbonates and hydroxides of nickel and copper into nickel and copper and oxides of tungsten into tungsten which partly dissolves in nickel thereby altering its electronic configuration
Full Text This invention relates to a process of preparing a high surface area (Ni, W, Cu) / kieselguhr catalyst for hydrogenolysis and hydrogenation reaction for the production of polyols at low temperatures and pressures.
BACKGROUND
In the preparation of (Ni, W, Cu) / kieselguhr catalyst in US patent nos. 3,691,100 and 3,965,199, ammonium tungstate is used to precipitate tungsten oxide which finely divides metallic nickel and thereby increases the activity of the nickel.
When this catalyst is used for hydrogenolysis for sucrose / glucose, poly-alcohols with lesser number of carbon atoms than in sucrose / glucose are obtained at temperatures and pressures above 180°C and 75 atm. pressure. Further, this catalyst does not produce yield of polyols particularly glycerol more than 25%. This might be due to lower activity of the nickel.
The object of this invention is to improve the catalyst described in US patent numbers 3,691,100 and 3,965,199 by altering the electronic configuration of nickel in addition to finely dividing it by promoting it with tungsten and tungsten oxide. Thus, the activity of nickel is increased substantially for hydrogenolysis of sucrose / glucose at temperatures and pressures lower than 180°C and 75 atm. This increased activity of nickel also results in high polyols' yields particularly glycerol.
To achieve the said objective this invention provides a process of preparing a high surface area (Ni, W, Cu) / kieselguhr catalyst for hydrogenolysis and hydrogenation reaction for the production of polyols at low temperatures and pressures comprising:
Step 1- making a slurry of kieselguhr, nickel nitrate and cupric nitrate in water in the ratio 1:0.8 - 5.2: 0.05-0.2: 25 - 35,
step 2- heating the said slurry at 60-90°C for diffusing nitrates of nickel and copper into the pores of silica in kieselguhr,
step 3- preparing ammonium para & meta - tungstates by mixing 0.4 ml/gm to 17 ml/gm of tungstic acid and concentrated ammonium hydroxide and heating them at 90-110°C,
step 4- adding the said ammonium para & meta tungstates to the slurry prepared in step 2 at 60-90 °C for a period of 15-90 minutes,

step 5- digesting the resulting mixture of step 4 at 60-90°C for 30-90 minutes for diffusing ammonium para & meta tungstates into the pores of silica in kieselguhr,
step 6- adding aqueous solution of sodium carbonate to step 5 and digesting the resulting slurry for 60-120 minutes at 70-110°C to precipitate carbonates and hydroxides of nickel and copper as well as oxides of tungsten,
step 7- filtering, washing and drying the said precipitate under vacuum to form the catalyst, and
step 8- reducing the said catalyst with hydrogen at temperature 500-700°C to convert carbonates and hydroxides of nickel and copper into nickel and copper and oxides of tungsten into tungsten which partly dissolves in nickel to obtain a high surface area (Ni, W, Cu)/ kieselguhr catalyst.
The concentrated ammonium hydroxide in step 3 is preferably 7-10 ml/gm and the said period in step 4 is from 20-90 minutes preferably 25-35 minutes and the digestion in step 5 is for 30-60 minutes preferably at 70-80°C
The aqueous solution of sodium carbonate is added at 60-90°C preferably 70-80°C for a period 15-60 minutes preferably 25-35 minutes.
The ratio of water and sodium carbonate in aqueous solution of sodium carbonate is from 4-8, preferably 4-6 and the second digestion in step 7 is at temperature 80-90°C for 80-90 minutes.
The catalyst is dried under vacuum at 100-120°C for 3-4 hrs and it is reduced with hydrogen preferably at 500 - 600°C.

The invention will now be described with reference to the following examples. EXAMPLE 1:
Solution of 90g of Ni (NO3)2.6H2O and 5g Cu(NO3)2.3H2O in 300 ml distilled water was mixed with 20g of kieselguhr. A suspension of an ammonium salt of tungsten (prepared by mixing 6.4g tungstic acid with 65 ml concentrated NH4OH and heating them at 95°C) was added uniformly to the above slurry over a period of 30 minutes at 80°C. The slurry is digested with stirring for 1 hr at 80°C. A solution of 37.8g anhydrous sodium carbonate in 94.5 ml water was added uniformly for 30 minutes at 80°C. The slurry is digested for 90 minutes at 90°C and thereafter the catalyst is filtered hot, washed with one liter of hot water and dried under vacuum at 120°C for 4 hrs. The catalyst is then reduced with H2 for 6 hours at 700°C.
Analysis gave 37.3% Ni, 1.25% Cu and 9.8% W. The catalyst area ranges between 700-1200 m2/g
EXAMPLE 2:
A solution of 54g Ni(NO3)2.6H2O and 1.9 Ig Cu(NO3)2.3H2O in 600 ml distilled water was mixed with 20g of kieselguhr. A suspension of an ammonium salt of tungsten (prepared by mixing 6.5g tungstic acid in 5 ml concentrated NH4OH and heating them at 95°C) was added uniformly to the above solution over a period of 30 minutes at 80°C. The slurry is digested with stirring for 1 hour at 20°C. A solution of 15.1g anhydrous sodium carbonate in 75.5 ml water was added uniformly for 30 minutes at 80°C. The slurry is digested for 90 minutes at 90°C and thereafter the catalyst is filtered hot, washed with one liter of hot water and dried under vacuum at 120°C for 4 hrs. The catalyst is then reduced with H2 for 6 hours at 700°C.
Analysis gave 34.86% Ni, 1.07% Cu and 9.95% W. The catalyst area ranges between 700-1200 m2/g


We claim:
1. A process of preparing a high surface area (Ni, W, Cu) / kieselguhr catalyst
for the production of polyols comprising:
step 1- making a slurry of kieselguhr, nickel nitrate and cupric nitrate in water in the ratio 1:0.8 - 5.2: 0.05-0.2: 25 - 35,
step 2- heating the said slurry at 60-90°C for diffusing nitrates of nickel and copper into the pores of silica in kieselguhr,
step 3- preparing ammonium para & meta - tungstates by mixing 0.4 ml/gm to 17 ml/gm of tungstic acid and concentrated ammonium hydroxide and heating them at 90-110°C,
step 4- adding the said ammonium para & meta tungstates to the slurry prepared in step 2 at 60-90 °C for a period of 15-90 minutes,
step 5- digesting the resulting mixture of step 4 at 60-90°C for 30-90 minutes for diffusing ammonium para & meta tungstates into the pores of silica in kieselguhr,
step 6- adding aqueous solution of sodium carbonate to step 5 and digesting the resulting slurry for 60-120 minutes at 70-110°C to precipitate carbonates and hydroxides of nickel and copper as well as oxides of tungsten,
step 7- filtering, washing and drying the said precipitate under vacuum to form the catalyst, and
step 8- reducing the said catalyst with hydrogen at temperature 500-700°C to convert carbonates and hydroxides of nickel and copper into nickel and copper and oxides of tungsten into tungsten which partly dissolves in nickel to obtain a high surface area (Ni, W, Cu)/ kieselguhr catalyst.
2. A process as claimed in claim 1 wherein the preferable amount of
concentrated ammonium hydroxide in step 3 is 7-10 ml/gm and the said
period in step 4 is from 20-90 minutes preferably 25-35 minutes

3. A process as claimed in claim 1 wherein the said period of addition is
ammonium para & meta tungstates in step 4 is 30-60 minutes at 70-85°C.
4. A process as claimed in claim 1 wherein the digestion in step 5 is carried out
for 30-60 minutes preferably at 70-80°C.
5. A process as claimed in claim 1 wherein the aqueous solution of sodium
carbonate is added at 70-80°C for a period 15-60 minutes preferably 25-35
minutes.
6. A process as claimed in claim 1 wherein the ratio of water and sodium
carbonate in aqueous solution of sodium carbonate is from 4-8, preferably
4-6.
7. A process as claimed in claim 1 wherein the catalyst is dried under vacuum
at lOO-120°C for3-4hrs.

8.

A process of preparing a high surface area (Ni, W, Cu) / kieselguhr catalyst for hydrogenolysis and hydrogenation reaction for the production of polyols at low temperatures and pressures substantially as herein described with reference to the fore going examples
reference to the foregoing examples.





Documents:

2019-del-1997-abstract.pdf

2019-del-1997-claims.pdf

2019-del-1997-correspondence-other.pdf

2019-del-1997-correspondence-po.pdf

2019-del-1997-description (complete).pdf

2019-del-1997-form-1.pdf

2019-del-1997-form-2.pdf

2019-del-1997-form-3.pdf

2019-del-1997-form-9.pdf

2019-del-1997-gpa.pdf


Patent Number 199602
Indian Patent Application Number 2019/DEL/1997
PG Journal Number 03/2008
Publication Date 18-Jan-2008
Grant Date 29-Dec-2006
Date of Filing 21-Jul-1997
Name of Patentee SECRETARY, DEPARTMENT OF SCIENCE & TECHNOLOGY
Applicant Address GOVT. OF INDIA, TECHNOLOGY BHAVAN, NEW MEHRAULI ROAD, NEW DELHI-110016, INDIA.
Inventors:
# Inventor's Name Inventor's Address
1 DR. SHEELENDRA RAI VIDYARTHI DEPARTMENT OF CHEMICAL ENGINEERING HARCOURT BUTLER TECHNOLOGICAL INSTITUTE, KANPUR, 208002, U.P.
PCT International Classification Number B01J 21/00
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 NA