GB2033776A - Catalyst for the production of ammonia - Google Patents
Catalyst for the production of ammonia Download PDFInfo
- Publication number
- GB2033776A GB2033776A GB7936642A GB7936642A GB2033776A GB 2033776 A GB2033776 A GB 2033776A GB 7936642 A GB7936642 A GB 7936642A GB 7936642 A GB7936642 A GB 7936642A GB 2033776 A GB2033776 A GB 2033776A
- Authority
- GB
- United Kingdom
- Prior art keywords
- surface area
- catalyst
- range
- ammonia
- transition metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000003054 catalyst Substances 0.000 title claims abstract description 32
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 13
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 13
- 150000003624 transition metals Chemical class 0.000 claims abstract description 13
- 239000010439 graphite Substances 0.000 claims abstract description 11
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 11
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 7
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 6
- 239000011707 mineral Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 230000000737 periodic effect Effects 0.000 claims description 11
- 229910021645 metal ion Inorganic materials 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 5
- 150000002602 lanthanoids Chemical class 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052768 actinide Inorganic materials 0.000 claims description 3
- 150000001255 actinides Chemical class 0.000 claims description 3
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 3
- 150000001254 actinide compounds Chemical class 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 2
- 229910001414 potassium ion Inorganic materials 0.000 claims 1
- 229910001419 rubidium ion Inorganic materials 0.000 claims 1
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 6
- 150000001340 alkali metals Chemical class 0.000 abstract description 6
- 238000005470 impregnation Methods 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- -1 ruthenium Chemical class 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical class [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052701 rubidium Inorganic materials 0.000 description 2
- 150000003623 transition metal compounds Chemical class 0.000 description 2
- WECIKJKLCDCIMY-UHFFFAOYSA-N 2-chloro-n-(2-cyanoethyl)acetamide Chemical compound ClCC(=O)NCCC#N WECIKJKLCDCIMY-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000009620 Haber process Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 150000001540 azides Chemical class 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 210000004534 cecum Anatomy 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- RTHYXYOJKHGZJT-UHFFFAOYSA-N rubidium nitrate Inorganic materials [Rb+].[O-][N+]([O-])=O RTHYXYOJKHGZJT-UHFFFAOYSA-N 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- KHAUBYTYGDOYRU-IRXASZMISA-N trospectomycin Chemical compound CN[C@H]([C@H]1O2)[C@@H](O)[C@@H](NC)[C@H](O)[C@H]1O[C@H]1[C@]2(O)C(=O)C[C@@H](CCCC)O1 KHAUBYTYGDOYRU-IRXASZMISA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- 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
-
- B01J35/60—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/04—Preparation of ammonia by synthesis in the gas phase
- C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
- C01C1/0411—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst characterised by the catalyst
-
- B01J35/615—
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
A catalyst is prepared which comprises a transition metal, e.g., ruthenium, and a modifying metal, e.g., an alkali metal supported on a graphite-containing carbon support having specified surface area properties which has been washed with a concentrated solution of a strong mineral acid and then with water before impregnation with the other components. It is suitable for use in the production of ammonia.
Description
SPECIFICATION
Catalyst for the production of ammonia
This invention relates to a catalyst suitable for the production of ammonia.
With increased pressure on the world's food resources the demand for nitrogen-containing fertilisers based on ammonia has grown rapidly in recent years. Current Haber processes using nitrogen and hydrogen as feedstock generally use a potassium promoted iron catalyst, usually with other promoters such as alumina. These catalysts are reduced in situ from bulk iron oxides before use and operate under severe conditions, e.g., pressures of up to 300 bars and temperatures of 450'-50O'C.
The reaction N2 + 3H2 = 2NH3 is highly exothermic and thus the equilibrium is moved to the right at lower temperatures. However, present day commercial catalysts are not sufficiently active at lower temperatures to enable the reaction to reach equilibrium within the short time the reactants are in contact with the catalyst. Activity increases with temperature and therefore a compromise has to be reached.
Recently work by Aika et al, Journal of Catalysis, 27, 424-431(1972), on the synthesis of ammonia discloses that synthesis over a ruthenium catalyst is promoted by the addition of an alkali metal, particularly when the ruthenium is supported by active carbon or alumina.
Similarly, British Patent Specification 1367112 to Sagami Chemical Research Centre discloses a complex catalyst for ammonia synthesis which comprises (a) at least one alkali metal belonging to Group 1A of the Periodic Table, (b) at least one compound, preferably a halide, oxide or sulphide, of a transition metal selected from the group consisting of Group 4B, Group 5B, Group 6B, Group 7B and Group 8 of the Periodic Table and graphite. The Periodic Table referred to by Sagami is that given in the "Handbook of Chemistry", edited by Norbert Adolf
Lange; McGraw-Hill, 1961; pages 56 to 57.
The complex comprises an alkali metal as the electron donor, graphite as the electron acceptor and a transition metal compound. The alkali metal and the transition metal compound are present as intercalates in the graphite lattice. Aika and Sagami both disclose the use of free alkali metal or precursors thereof, such as azides, as electron donors.
Our copending British Patent Application No. 45711/76 discloses a catalyst comprising (i) as support a graphite-containing carbon having (a) a basal plane surface area of at least 100 m2/g, (b) a ratio of BET surface area to basal plane surface area of not more than 8:1, preferably not more than 5:1 and (c) a ratio of basal plane surface area to edge surface area of at least 2:1 and preferably at least 5::1 and (ii) as active component (a) 0.1 to 50% preferably 1-30%, most preferably 5-1 0% by weight of a transition metal of the 4th, 5th and 6th horizontal Periods of
Groups VB, VIB, VIIB and VIII of the Periodic Table expressed as % by weight of total catalyst and (b) 0.1 to 4 times by weight of (a) of a modifying metal ion selected from Groups IA or IIA of the Periodic Table or the lanthanides or actinides, the modifying metal ion being actively associated with the transition metal rather than the support.
Unless otherwise indicated the Periodic Table referred to in the present specification is the
Periodic Table published on page B-4 of the Handbook of Chemistry and Physics, 57th Edition, 1976-1977, published by CRC Press, Cleveland, Ohio.
Such a catalyst is suitable for the production of ammonia from hydrogen and nitrogen and the
Fischer-Tropsch reaction.
It is distinguished from the prior art in that it is neither an electron donor-acceptor complex nor is it an intercalate compound.
The graphite-containing carbon may be prepared by the method disclosed in British Patent
Specification 1468441 comprising the steps of (1) an initial heat treatment in an inert atmosphere at a temperature between 900 and 3300"C, (2) an oxidation stage at a temperature between 300 and 1200"C, and (3) a further heat treatment in an inert atmosphere at a temperature between 1000 and 3000"C, preferably between 1400 and 2100"C.
The activated carbons used in the preparation of the support invariably contain significant levels of impurities that can be deposited in the pore mouths during heat treatment resulting in a reduction in the accessible surface area. During or after the preparation the support may also become contaminated with sulphur compounds which subsequently have a deactivating effect.
We have now discovered that washing the support with acid either during the carbon preparation or prior to the addition of the catalytically active substances both removed the sulphur and improves the surface properties of the carbon, thus resulting in a more active catalyst.
Thus according to the present invention there is provided a method for the preparation of a catalyst comprising (i) as support a graphite-containing carbon having (a) a basal plane surface area of at least 100 m2/g, (b) a ratio of BET surface area to basal plane surface area of not more than 8: 1, preferably not more than 5:1 and (c) a ratio of basal plane surface area to edge surface area of at least 2:1 and preferably, at least 5::1 and (ii) as active component (a) 0.1 to 50% preferably -1-30%, most preferably 510% by weight of a transition metal of the 4th,
5th and 6th horizontal Periods of Groups VB, VIB, VIIB and VIII of the Periodic Table, expressed as % by weight of total catalyst and (b) 0.1 to 4 times by weight of (a) of a modifying metal ion selected from Groups IA or IIA of the Periodic Table or the lanthanides or actinides, the modifying metal ion being actively associated with the transition metal rather than the support, which method includes the steps of washing the carbon with a concentrated solution of a strong mineral acid, washing the acid treated carbon with water to remove the acid, then impregnating with a solution of a compound of the transition metal to give the desired concentration and adding a solution of the Groups 1 A, 2A, lanthanide or actinide compound to give the desired concentration of the modifying metal ion.
If the graphite containing carbon is prepared by the method of 1468441, then the acid wash may take place either before the first heat treatment, between the first and second heat treatments or after the final heat treatment.
The preferred transition metals are cobalt, ruthenium and rhodium. Ruthenium is the most preferred.
Preferred components (b) are the alkali and alkaline earth metal ions. The most preferred are rubidium and potassium.
Suitable strong mineral acids include hydrochloric, nitric and sulphuric acids, preferably the first.
Suitable concentrations lie in the range 10% to 80% by volume.
According to another aspect of the present invention, there is provided a process for the production of ammonia which process comprises passing a feedstock containing nitrogen and hydrogen over a catalyst prepared as herein before described under conditions of temperature, pressure and space velocity such that conversion to ammonia is effected.
Synthesis gas is a suitable feedstock.
The Catalyst has a high tolerance of poisons which are normally harmful to conventional catalysts, such as water and carbon monoxide.
Broad and preferred ranges of process conditions are as follows:
Broad Range Preferred Range
Temperature "C 250-600 300-500
Pressure bars Atmospheric-300 20-200
Space Velocity v/v/h 1,000-100,000 5,000--30,000 The invention is illustrated by the following example and the accompanying drawing.
Example
Activated carbon AC 40 supplied by CECA Limited was heat treated to 900"C in nitrogen and the heat treatment continued to 1500"C in argon. It was then oxidised in air at 450"C to 20% weight loss. Portions of the oxidised material were then heat treated in argon at various temperatures ranging from 1 500 to 2100"C to form graphite-containing carbon catalyst supports.
Samples of the latter were then boiled in 40% HCI and subsequently Soxhlet extracted with distilled water until free from chloride ions.
Catalysts were prepared by adding 7.5% ruthenium to the supports by impregnation from an aqueous solution of ruthenium chloride. After reduction at 500"C in hydrogen for 2 hours 15% rubidium was added from an aqueous solution of rubidium nitrate. After a further heat treatment at 500"C in nitrogen the catalysts were ready for use.
The catalysts were then tested in a 2 ml microreactor at a GHSV of 1000 and a pressure of 5.14 bar. In each test the temperature was programmed over the range 350"--450"C and the maximum ammonia yield noted.
The results obtained are plotted on the accompanying drawing which is a graph in which the temperature of the second heat treatment of the support is plotted against the maximum ammonia yield expressed as a per cent.
The graph clearly shows the improved performance of catalysts based on acid treated and washed supports.
Claims (14)
1. A method for the preparation of a catalyst comprising (i) as support a graphite-containing carbon having (a) a basal plane surface area of at least 100 m2/g, (b) a ratio of BET surface area to basal plane surface area of not more than 8:1, and (c) a ratio of basal plane surface area to edge surface area of at least 2::1 and (ii) as active component (a) 0.1 to 50% by weight of a transition metal of the 4th, 5th and 6th horizontal Periods of Groups VB, VIB, VIIB and VIII of the Periodic Table, expressed as % by weight of total catalyst and (b) 0.1 to 4 times by weight of (a) of a modifying metal ion selected from Groups IA or IIA of the Periodic Table or the lanthanides or actinides, the modifying metal ion being actively associated with the transition metal rather than the support, which method includes the steps of washing the carbon with a concentrated solution of a strong mineral acid, washing the acid treated carbon with water to remove the acid, then impregnating with a solution of a compound of the transition metal to give the desired concentration and adding a solution of the Groups IA, IIA, lanthanide or actinide compounds to give the desired concentration of the modifying metal ion.
2. A method according to Claim 1 wherein the graphite-containing carbon has a ratio of BET surface area to basal plane surface area of not more than 5:1 and a ratio of basal plane surface area to edge surface area of at least 5:1.
3. A method according to either of Claims 1 or 2 wherein the transition metal is present in amount 1 to 30% by weight expressed as % by weight of total catalyst.
4. A method according to any of the preceding claims wherein the transition metal is ruthenium.
5. A method according to any of the preceding claims wherein the modifying metal ions are rubidium or potassium ions.
6. A method according to any of the preceding claims wherein the strong mineral acid is hydrochloric acid.
7. A method according to any of the preceding claims wherein the concentration of the strong mineral acid lies in the range 10 to 80% by volume.
8. A process for the production of ammonia which process comprises passing a feedstock containing nitrogen and hydrogen over a catalyst prepared as hereinbefore described under conditions of temperature, pressure and space velocity such that conversion to ammonia is effected.
9. A process according to Claim 8 wherein the feedstock is passed over the catalyst at a temperature in the range 250 to 600"C, a pressure in the range atmospheric to 300 bars and a space velocity in the range 1 ,000 to 100,000 v/v/hr.
10. A process according to Claim 9 wherein the feedstock is passed over the catalyst at a temperature in the range 300 to 500"C, a pressure in the range 20 to 200 bars and a space velocity in the range 5,000 to 30,000 v/v/hr.
11. A method for the preparation of a catalyst according to Claim 1 as hereinbefore described with reference to the Example.
1 2. A process for the production of ammonia as hereinbefore described with reference to the
Example.
1 3. Catalysts whenever prepared by a method according to any of Claims 1 to 7 or 11.
14. Ammonia whenever prepared by a process according to any of Claims 8 to 10 or 1 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB7936642A GB2033776B (en) | 1978-10-24 | 1979-10-23 | Catalyst for the production of ammonia |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB7841708 | 1978-10-24 | ||
| GB7936642A GB2033776B (en) | 1978-10-24 | 1979-10-23 | Catalyst for the production of ammonia |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2033776A true GB2033776A (en) | 1980-05-29 |
| GB2033776B GB2033776B (en) | 1983-02-09 |
Family
ID=26269302
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB7936642A Expired GB2033776B (en) | 1978-10-24 | 1979-10-23 | Catalyst for the production of ammonia |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2033776B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4753913A (en) * | 1985-07-08 | 1988-06-28 | Basf Aktiengesellschaft | Gas-phase alkylation of phenols, and a catalyst for this purpose |
| WO1998007512A1 (en) * | 1996-08-22 | 1998-02-26 | Rhodia Chimie | Wet oxidation processing of a solution or suspension of organic compounds |
| US6235676B1 (en) | 1999-03-15 | 2001-05-22 | Haldor Topsoe A/S | Process for the preparation of ammonia and ammonia synthesis catalyst |
| US6479027B1 (en) | 1999-10-29 | 2002-11-12 | Haldor Topsoe A/S | Process for the preparation of ammonia and ammonia synthesis gas |
| EP1391428A1 (en) * | 2002-07-11 | 2004-02-25 | Haldor Topsoe A/S | Process for the preparation of ammonia and catalyst therefore |
-
1979
- 1979-10-23 GB GB7936642A patent/GB2033776B/en not_active Expired
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4753913A (en) * | 1985-07-08 | 1988-06-28 | Basf Aktiengesellschaft | Gas-phase alkylation of phenols, and a catalyst for this purpose |
| WO1998007512A1 (en) * | 1996-08-22 | 1998-02-26 | Rhodia Chimie | Wet oxidation processing of a solution or suspension of organic compounds |
| FR2752534A1 (en) * | 1996-08-22 | 1998-02-27 | Rhone Poulenc Chimie | PROCESS FOR TREATING SOLUTION OR SUSPENSION OF ORGANIC COMPOUNDS BY WET-OXIDATION |
| US6235676B1 (en) | 1999-03-15 | 2001-05-22 | Haldor Topsoe A/S | Process for the preparation of ammonia and ammonia synthesis catalyst |
| US6479027B1 (en) | 1999-10-29 | 2002-11-12 | Haldor Topsoe A/S | Process for the preparation of ammonia and ammonia synthesis gas |
| US6764668B2 (en) | 1999-10-29 | 2004-07-20 | Haldor Topsoe A/S | Process for the preparation of ammonia and ammonia synthesis gas |
| EP1391428A1 (en) * | 2002-07-11 | 2004-02-25 | Haldor Topsoe A/S | Process for the preparation of ammonia and catalyst therefore |
| US7025944B2 (en) | 2002-07-11 | 2006-04-11 | Häldor Topsoe A/S | Process for the preparation of ammonia |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2033776B (en) | 1983-02-09 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |