Title of Invention	A PROCESS FOR THE PREPARATION OF AN IMPROVED IRON CATALYST Fe.Cu.MnO.K2O BETONITE USEFUL FOR THE PRODUCTION OF WAX FROM SYNTHESIS GAS.
Abstract	The present invention relates to a process for the preparation of an improved iron catalyst Fe.Cu.MnO.K20 bentonite useful for the production of wax from synthesis gas. More particularly this invention relates to a process for the preparation of an iron catalyst useful for the production of wax from synthesis gas a mixture of carbon monoxide and hydrogen which can be obtained from any carbonaceous source such as coal natural gas, associated gas, refinery off gas or biogas. The iron catalyst is developed by incorporating salts of iron ,Cu ,Ca ,Mg ,Cr ,A1 or Mn of group I,II,III,VI or VII either alone or in combination thereof by using freshly prepared silica gel or bentonite as support.; 1

Title of Invention

A PROCESS FOR THE PREPARATION OF AN IMPROVED IRON CATALYST Fe.Cu.MnO.K2O BETONITE USEFUL FOR THE PRODUCTION OF WAX FROM SYNTHESIS GAS.

Abstract

The present invention relates to a process for the preparation of an improved iron catalyst Fe.Cu.MnO.K20 bentonite useful for the production of wax from synthesis gas. More particularly this invention relates to a process for the preparation of an iron catalyst useful for the production of wax from synthesis gas a mixture of carbon monoxide and hydrogen which can be obtained from any carbonaceous source such as coal natural gas, associated gas, refinery off gas or biogas. The iron catalyst is developed by incorporating salts of iron ,Cu ,Ca ,Mg ,Cr ,A1 or Mn of group I,II,III,VI or VII either alone or in combination thereof by using freshly prepared silica gel or bentonite as support.; 1

Full Text	The present invention relates to a process for the preparation of an improved iron catalyst useful for the production of wax from synthesis gas. More particularly this invention relates to a process for the preparation of iron catalyst useful for production of wax from synthesis gas a mixture of carbon monoxide and hydrogen which can be obtained from any carbonaceous source such as coal, natural gas, associated gas, refinery off gas or biogas. The studies on synthetic hydrocarbons production from synthesis gas have been initiated from 1902. The process is known as Fischer-Tropsch synthesis and first patent on this process was taken in 1913. The investigations are still continuing on global basis to improve the productivity and selectivity of the catalyst necessary for the process. Mainly metals form group VIII of the periodic table viz. iron, cobalt nickel, platinum, ruthenium are used to prepare catalyst for the process. Out of all these metals mentioned to prepare catalyst suitable for the production of hydrocarbons with high yield of wax fraction from the synthesis gas, iron is cheapest has flexibility with respect to the t-VCO ratio in the feed synthesis gas and available abundantly. In the literature it has been mentioned that iron metal in combination with one or more elements like copper, calcium, magnesium, potassium are used in the preparation of the catalyst for the production of hydrocarbons containing wax fraction. Such catalysts additionally incorporate silica or kieselghur, a naturally occurring silicious material as catalyst support. Thus, earlier such a catalyst e.g. iron incorporating copper and potassium used to be prepared from the nitrate solution of iron and copper and then co-precipitating them with sodium/potassium carbonate over silica or kieselghur. The important ingredients silica/kieselghur have certain limitations. Silica preparation is a laborious method and kieselghur being a naturally occurring siliceous material is not available everywhere. The main objective of the present invention is to provide a process for the preparation of an improved iron catalyst using alternative naturally occurring siliceous material bentonite as support in place of silica and kieselghur to obtain wax from the synthesis gas The yield of wax from the synthesis gas using silica or kieselghur supported iron catalyst in the fixed bed reactor system has been mentioned in the literature as 71.7 weight percent of C$++ hydrocarbons.The "conversion of synthesis gas obtained from carbonaceous source like coal, natural gas, associated gas, refinery off gas, biogas to synthetic hydrocarbons is a versatile process. By using group VIII metals in combination with elements from certain other groups as Catalyst and wide range of operating conditions such as Temperature 100-400° C, pressure 1-1000 Kg/sq.cm, space velocity 100-30000 h"1 and H2/CO ratio 0.5 - 3.5 a wide variety of end products like methane, iso-paraffins, synthetic liquid fuels, wax, rnethanol, higher alcohols can be obtained. Processes based on synthesis gas therefore, prima-facie may appear similar. But each process differs in catalyst composition and in the end product. As an example in our co-pending application No. 773/D/89 we have described a process for the preparation of iron catalyst The product to be obtained from synthesis gas using this catalyst is middle distillate which have been discussed in our application bearing No.933/Del/90, a distinctly different product from that of wax. The present invention provides a process for the preparation of a new catalyst which converts synthesis gas to synthetic hydrocarbons with high yield ofwax The present invention lies in the development of an iron catalyst incorporating elements like Cu, Ca, Mg, Cr, Al, Mn of gr. 1,11,111, Vi, VII either atone or in combination of some of them using freshly prepared silica gel or bentonite as support The preformed catalyst may have the composition: 100 parts by weight of iron; 10-30 parts by weight of copper, 5-45 parts by weight of oxides like Ca, Mg, Cr, Mn ; 0.5-10 parts by weight of Na or K and 20-100 parts by weight of freshly prepared silica gel or bentonite support Thus a promoted iron catalyst with composition Fe Cu-MnO-KaO Bentonite within the ranges can be prepared by co-precipitation method from metal nitrate solution. The solution may be maintained at 70-85° C using hot alkaline solution such as potassium/sodium carbonate solution, previously heated to 80-90° C as precipitant. The precipitation may be effected within the pH range of 8.0 -9.5, to which bentonite or silica salt is added. The precipitated mass is filtered, washed to make it free from alkali and nitrate tons. Required amount of potassium salt is then added to the filtered mass. The whole mass is then extruded, dried and made to size. The sized catalyst is pnetneated with H2/(20-30)N2 + (70-80}H2 mixture at 225-350° C for 4-12 hours and with synthesis gas at 140-250° for 40-55 hours and then employed "for the production of synthetic hydrocarbons mixture with high yield of wax fraction that is subject matter of our co-pending application details of the process for the production of synthetic hydrocarbons mixture with high yield of wax using the invented catalyst have been described and claimed in our copending patent application No.1731/DEL/94. According to the said process tine purified synthesis gas is compressed to a pressure of 12-30 kg/sq.cm and after passing through a high pressure final purification tower to remove taace nnpurities is metered through a high pressure rotameterAnass-flow meter and then fed to the synthesis reactor via gas preheater where the feed synthesis gas is pre- heated to a temperature of 150-200° C. The reactor contains catalyst bed on which syntfiesis gas is reacted at a temperature of 180-250° C and space velocity 300-1650 h . The syntfiesis gas is converted to syntiietic hydrocarbon mixture witfi high yield of wax.. The production of wax has been accomplished by using a high pressure-fixed bed catalyst testing unit of 150 ml. catalyst capacity having provisions for maintaining isothermal condition of tfie catalyst bed which is the subject matter of a copending application N0.447/DEL/93. EXAMPLE Results obtained in a tvpicai once through run 1. Feed ; Syntfiesis gas, H/CO = 1.4 2. Temperature : 200° C 3. Pressure :16kg/sq.cm-1 4. Space velocity :4(X)h 5. Conversion of Synthesis gas :84.5 vol% 6. Yield of hydrocarbon: gm/N cu.m wt% products CO + H2 (on C5++) i)C1-C4 14.6 10.5 ii)OI(IBP-320C) 16.0 11.5 fraction Hi) Wax (>320 C fraction) 108.0 78.0 7. Yield of wax on C5++ 60-87 wt% Accordingly, the present invention relates to a process for the preparation of an improved iron catalyst useful for the production of wax from synthesis gas which comprises: i) preparing an aqueous solution of salts of iron ,Cu ,Ca ,Mg ,Cr ,A1 or Mn in an amount ranging from 10 to 30 parts by weight of Cu,5 to 45 parts by wt of oxides of Ca, Mg ,Cr, & Mn of group I,II,III,VI or VII either alone or in combination thereof; ii) heating the resulting solution simultaneously while adding weak alkali solution such as herein described till the resulting solution attains a pH in the range of 8 to 9.5; iii) adding bentonite or freshly prepared silica gel in an amount ranging from 20 to 100 parts by weight and silica gel is pretreated by heating to a temperature in the range of 210 to 550°C for a period of 1 to 8 hrs, iv) filtering and washing the precipitate formed till it is free from alkali, v) adding potassium oxide to the precipitate, vi) drying the resultant mass by conventional methods to obtain iron catalyst. In a preferred embodiment of the invention the bentonite or silica gel is pretreated by heating to a temperature in the range of 210 to 550 degree C. The heating may be done preferably for a period of 1 to 8 hrs, most preferably at a temperature in the range 210 ti 250 degree C for a period in the range of 1 to 4 hrs.The support may be crushed to the size of-72 BS size before heating. The salts of the elements used may be oxides and the amount may be range from 10 to 30 parts by weight of Cu,5 to 45 parts by wt of oxides of Ca, Mg ,Cr, & Mn .The alkali used may be sodium or potassium carbonate ,the amount may range from 0.5 to 10 parts by weight. hours and then employed gel or bentonite used may range from 20 to 100 parts by weight. We Claim: 1. A process for the preparation of an improved iron catalyst Fe.Cu.MnO.K20 bentonite useful for the production of wax from synthesis gas which comprises: i) characterized in that preparing an aqueous solution of salts of iron ,Cu ,Ca ,Mg ,Cr ,A1 or Mn in an amount ranging from 10 to 30 parts by weight of Cu,5 to 45 parts by wt of oxides of Ca, Mg ,Cr, & Mn of group I,II,III,VI or VII either alone or in combination thereof; ii) heating for a period in the range of 1 to 4 hrs. the resulting solution simultaneously while adding weak alkali solution such as herein described till the resulting solution attains a pH in the range of 8 to 9.5; iii) adding bentonite or freshly prepared silica gel in an amount ranging from 20 to 100 parts by weight and silica gel is pretreated by heating to a temperature in the range of 210 to 550°C for a period of 1 to 8 hrs, iv) filtering and washing the precipitate formed till it is free from alkali, v) adding potassium oxide to the precipitate, vi) drying the resultant mass by conventional methods to obtain iron catalyst. 2. A process as claimed in claim 1 , wherein the silica gel /bentonite is added to the solution maintaining the pH of the solution preferably at 6.5 to 7.5. 3. A process as claimed in claims 1 & 2, wherein weak alkali solution employed is sodium or potassium carbonate. 4. A process as claimed in claims 1 to 3, wherein the alkali solution is preheated to a temperature in the range of 80 to 90°C. 5. A process for the preparation of an improved iron catalyst Fe.Cu.MnO.K20 bentonite useful for the production of wax from synthesis gas substantially as herein described with references to the examples.

Full Text

The present invention relates to a process for the preparation of an improved iron catalyst useful for the production of wax from synthesis gas. More particularly this invention relates to a process for the preparation of iron catalyst useful for production of wax from synthesis gas a mixture of carbon monoxide and hydrogen which can be obtained from any carbonaceous source such as coal, natural gas, associated gas, refinery off gas or biogas.
The studies on synthetic hydrocarbons production from synthesis gas have been initiated from 1902. The process is known as Fischer-Tropsch synthesis and first patent on this process was taken in 1913. The investigations are still continuing on global basis to improve the productivity and selectivity of the catalyst necessary for the process. Mainly metals form group VIII of the periodic table viz. iron, cobalt nickel, platinum, ruthenium are used to prepare catalyst for the process.
Out of all these metals mentioned to prepare catalyst suitable for the production of hydrocarbons with high yield of wax fraction from the synthesis gas, iron is cheapest has flexibility with respect to the t-VCO ratio in the feed synthesis gas and available abundantly.
In the literature it has been mentioned that iron metal in combination with one or more elements like copper, calcium, magnesium, potassium are used in the preparation of the catalyst for the production of hydrocarbons containing wax fraction. Such catalysts additionally incorporate silica or kieselghur, a naturally occurring silicious material as catalyst support. Thus, earlier such a catalyst e.g. iron incorporating copper and potassium used to be prepared from the nitrate

solution of iron and copper and then co-precipitating them with sodium/potassium
carbonate over silica or kieselghur. The important ingredients silica/kieselghur have certain limitations. Silica preparation is a laborious method and kieselghur being a naturally occurring siliceous material is not available everywhere.
The main objective of the present invention is to provide a process for the preparation of an improved iron catalyst using alternative naturally occurring siliceous material bentonite as support in place of silica and kieselghur to obtain wax from the synthesis gas
The yield of wax from the synthesis gas using silica or kieselghur supported iron catalyst in the fixed bed reactor system has been mentioned in the
literature as 71.7 weight percent of C$++ hydrocarbons.The "conversion of synthesis gas obtained from carbonaceous source like coal, natural gas, associated gas, refinery off gas, biogas to synthetic hydrocarbons is a versatile process. By using group VIII metals in combination with elements from certain other groups as Catalyst and wide range of operating conditions such as Temperature 100-400° C, pressure 1-1000 Kg/sq.cm, space velocity 100-30000 h"1 and H2/CO ratio 0.5 - 3.5 a wide variety of end products like methane, iso-paraffins, synthetic liquid fuels, wax, rnethanol, higher alcohols can be obtained.
Processes based on synthesis gas therefore, prima-facie may appear similar. But each process differs in catalyst composition and in the end product. As an example in our co-pending application No. 773/D/89 we have described a

process for the preparation of iron catalyst The product to be obtained from synthesis gas using this catalyst is middle distillate which have been discussed in our application bearing No.933/Del/90, a distinctly different product from that of wax. The present invention provides a process for the preparation of a new catalyst which converts synthesis gas to synthetic hydrocarbons with high yield ofwax
The present invention lies in the development of an iron catalyst incorporating elements like Cu, Ca, Mg, Cr, Al, Mn of gr. 1,11,111, Vi, VII either atone or in combination of some of them using freshly prepared silica gel or bentonite as support The preformed catalyst may have the composition: 100 parts by weight of iron; 10-30 parts by weight of copper, 5-45 parts by weight of oxides like Ca, Mg, Cr, Mn ; 0.5-10 parts by weight of Na or K and 20-100 parts by weight of freshly prepared silica gel or bentonite support
Thus a promoted iron catalyst with composition Fe Cu-MnO-KaO Bentonite within the ranges can be prepared by co-precipitation method from metal nitrate solution. The solution may be maintained at 70-85° C using hot alkaline solution such as potassium/sodium carbonate solution, previously heated to 80-90° C as precipitant.
The precipitation may be effected within the pH range of 8.0 -9.5, to which bentonite or silica salt is added. The precipitated mass is filtered, washed to make it free from alkali and nitrate tons. Required amount of potassium salt is then added to the filtered mass. The whole mass is then extruded, dried and made to size.

The sized catalyst is pnetneated with H2/(20-30)N2 + (70-80}H2 mixture at 225-350° C for 4-12 hours and with synthesis gas at 140-250° for 40-55 hours and then employed "for the production of synthetic hydrocarbons mixture with high yield of wax fraction that is subject matter of our co-pending application details of the process for the production of synthetic hydrocarbons mixture with high yield of wax using the invented catalyst have been described and claimed in our copending patent application No.1731/DEL/94. According to the said process tine purified synthesis gas is compressed to a pressure of 12-30 kg/sq.cm and after passing through a high pressure final purification tower to remove taace nnpurities is metered through a high pressure rotameterAnass-flow meter and then fed to the synthesis reactor via gas preheater where the feed synthesis gas is pre- heated to a temperature of 150-200° C. The reactor contains catalyst bed on which syntfiesis gas is reacted at a temperature of 180-250° C and space velocity 300-1650 h . The syntfiesis gas is converted to syntiietic hydrocarbon mixture witfi high yield of wax..
The production of wax has been accomplished by using a high pressure-fixed bed catalyst testing unit of 150 ml. catalyst capacity having provisions for maintaining isothermal condition of tfie catalyst bed which is the subject matter of a
copending application N0.447/DEL/93.
EXAMPLE
Results obtained in a tvpicai once through run
1. Feed ; Syntfiesis gas, H/CO = 1.4
2. Temperature : 200° C

3. Pressure :16kg/sq.cm-1
4. Space velocity :4(X)h
5. Conversion of Synthesis gas :84.5 vol%
6. Yield of hydrocarbon: gm/N cu.m wt% products CO + H2 (on C5++)
i)C1-C4 14.6 10.5
ii)OI(IBP-320C) 16.0 11.5
fraction
Hi) Wax (>320 C fraction) 108.0 78.0
7. Yield of wax on C5++ 60-87 wt%
Accordingly, the present invention relates to a process for the preparation of an improved iron catalyst useful for the production of wax from synthesis gas which comprises:
i) preparing an aqueous solution of salts of iron ,Cu ,Ca ,Mg ,Cr ,A1 or Mn in an amount ranging from 10 to 30 parts by weight of Cu,5 to 45 parts by wt of oxides of Ca, Mg ,Cr, & Mn of group I,II,III,VI or VII either alone or in combination thereof;
ii) heating the resulting solution simultaneously while adding weak alkali solution such as herein described till the resulting solution attains a pH in the range of 8 to 9.5;

iii) adding bentonite or freshly prepared silica gel in an amount ranging from 20 to 100
parts by weight and silica gel is pretreated by heating to a temperature in the range of
210 to 550°C for a period of 1 to 8 hrs,
iv) filtering and washing the precipitate formed till it is free from alkali,
v) adding potassium oxide to the precipitate,
vi) drying the resultant mass by conventional methods to obtain iron catalyst.
In a preferred embodiment of the invention the bentonite or silica gel is pretreated by heating to a temperature in the range of 210 to 550 degree C. The heating may be done preferably for a period of 1 to 8 hrs, most preferably at a temperature in the range 210 ti 250 degree C for a period in the range of 1 to 4 hrs.The support may be crushed to the size of-72 BS size before heating.
The salts of the elements used may be oxides and the amount may be range from 10 to 30 parts by weight of Cu,5 to 45 parts by wt of oxides of Ca, Mg ,Cr, & Mn .The alkali used may be sodium or potassium carbonate ,the amount may range from 0.5 to 10 parts by weight. hours and then employed gel or bentonite used may range from 20 to 100 parts by weight.

We Claim:
1. A process for the preparation of an improved iron catalyst Fe.Cu.MnO.K20 bentonite
useful for the production of wax from synthesis gas which comprises:
i) characterized in that preparing an aqueous solution of salts of iron ,Cu ,Ca ,Mg ,Cr ,A1
or Mn in an amount ranging from 10 to 30 parts by weight of Cu,5 to 45 parts by wt of
oxides of Ca, Mg ,Cr, & Mn of group I,II,III,VI or VII either alone or in combination
thereof;
ii) heating for a period in the range of 1 to 4 hrs. the resulting solution simultaneously
while adding weak alkali solution such as herein described till the resulting solution
attains a pH in the range of 8 to 9.5;
iii) adding bentonite or freshly prepared silica gel in an amount ranging from 20 to 100
parts by weight and silica gel is pretreated by heating to a temperature in the range of
210 to 550°C for a period of 1 to 8 hrs,
iv) filtering and washing the precipitate formed till it is free from alkali,
v) adding potassium oxide to the precipitate,
vi) drying the resultant mass by conventional methods to obtain iron catalyst.
2. A process as claimed in claim 1 , wherein the silica gel /bentonite is added to the
solution maintaining the pH of the solution preferably at 6.5 to 7.5.
3. A process as claimed in claims 1 & 2, wherein weak alkali solution employed is sodium or potassium carbonate.
4. A process as claimed in claims 1 to 3, wherein the alkali solution is preheated to a temperature in the range of 80 to 90°C.
5. A process for the preparation of an improved iron catalyst Fe.Cu.MnO.K20 bentonite useful for the production of wax from synthesis gas substantially as herein described with references to the examples.

Documents:

1123-DEL-2002-Abstract-(10-07-2009).pdf

1123-DEL-2002-Abstract-(23-04-2009).pdf

1123-del-2002-abstract.pdf

1123-DEL-2002-Claims-(10-07-2009).pdf

1123-DEL-2002-Claims-(23-04-2009).pdf

1123-del-2002-claims.pdf

1123-DEL-2002-Correspondence-Others (25-09-2009).pdf

1123-DEL-2002-Correspondence-Others-(09-07-2009).pdf

1123-DEL-2002-Correspondence-Others-(10-07-2009).pdf

1123-DEL-2002-Correspondence-Others-(23-04-2009).pdf

1123-del-2002-correspondence-others.pdf

1123-del-2002-correspondence-po.pdf

1123-DEL-2002-Description (Complete)-(10-07-2009).pdf

1123-DEL-2002-Description (Complete)-(23-04-2009).pdf

1123-del-2002-description (complete).pdf

1123-DEL-2002-Form-1 (25-09-2009).pdf

1123-DEL-2002-Form-1-(10-07-2009).pdf

1123-DEL-2002-Form-1-(23-04-2009).pdf

1123-del-2002-form-1.pdf

1123-del-2002-form-13-(25-05-2009).pdf

1123-del-2002-form-18.pdf

1123-DEL-2002-Form-2-(10-07-2009).pdf

1123-del-2002-form-2.pdf

1123-DEL-2002-Form-3-(23-04-2009).pdf

1123-del-2002-form-3.pdf

1123-del-2002-gpa.pdf

1123-DEL-2002-Petition-137-(09-07-2009).pdf

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Patent Number

237506

Indian Patent Application Number

1123/DEL/2002

PG Journal Number

01/2010

Publication Date

01-Jan-2010

Grant Date

23-Dec-2009

Date of Filing

08-Nov-2002

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	SAMIRAN BASU	CENTRAL FUEL RESEARCH INSTITUTE, DHANBAD.
2	SATYA BRATA BASU	CENTRAL FUEL RESEARCH INSTITUTE, DHANBAD.
3	PRADIP KUMAR BASU	CENTRAL FUEL RESEARCH INSTITUTE, DHANBAD.
4	UJJAL BHATTACHARJEE	CENTRAL FUEL RESEARCH INSTITUTE, DHANBAD.
5	GORA CHAND NANDI	CENTRAL FUEL RESEARCH INSTITUTE, DHANBAD.

PCT International Classification Number

B01J 23/745

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1			NA