GB2034292A - Production of Ammonia - Google Patents
Production of Ammonia Download PDFInfo
- Publication number
- GB2034292A GB2034292A GB7935046A GB7935046A GB2034292A GB 2034292 A GB2034292 A GB 2034292A GB 7935046 A GB7935046 A GB 7935046A GB 7935046 A GB7935046 A GB 7935046A GB 2034292 A GB2034292 A GB 2034292A
- Authority
- GB
- United Kingdom
- Prior art keywords
- nitrogen
- mol
- process according
- hydrogen
- surface area
- 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.)
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Classifications
-
- 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
-
- 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
-
- 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
- C01C1/0482—Process control; Start-up or cooling-down procedures
-
- 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 process for the production of ammonia comprises passing hydrogen and nitrogen over a catalyst disclosed in 45711/76 comprising a specified 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, at start-up the nitrogen being supplied in stoichiometric excess and thereafter in stoichiometric proportions.
Description
SPECIFICATION
Process for the Production of Ammonia
This invention relates to a process 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 4500--5000C.
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.
Recent 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 1,367,112 to Sagami Chemical Research Centre discloses
a complex catalyst for ammonia synthesis which comprises (a) at least one alkali metal belonging to .Group 1 A 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, 1 961; 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.
Ourcopending 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 on 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.
It is distinguished from the prior art in that it is neither an electron donor-acceptor complex nor is
it an intercalate compound.
It has now been discovered that operating the process with the above catalyst and utilising an excess of nitrogen over the stoichiometric requirements for conversion increases the activity of the catalyst and furthermore that this increased activity is sustained at high feedstock space velocities.
Only an initial excess is necessary. Thereafter the feed is supplied in stoichiometric proportions.
Thus according to the present invention there is provided a continuous process for the production
of ammonia which process comprises passing a feedstock containing hydrogen and nitrogen, at start
up the nitrogen being supplied in stoichiometric excess and thereafter in stoichiometric proportions, over 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, under conditions of temperature, pressure and space velocity such that conversion to ammonia is effected, separating unreacted hydrogen and nitrogen from product ammonia, recycling the unreacted hydrogen and nitrogen with the nitrogen in stoichiometric
excess, and supplying make-up feedstock of hydrogen and nitrogen in stoichiometric proportions.
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.
The graphite-containing carbon may be prepared by the method disclosed in British Patent
Specification 1,468,441 comprising the steps of (1) an initial heat treatment in an inert atmosphere at a temperature between 9000 and 33000C, (2) an oxidation stage at a temperature between 3000 and 1 2000C, and (3) a further heat treatment in an inert atmosphere at a temperature between 1000" and 30000C, preferably between 14000 and 2100 C.
Broad and preferred ranges of process conditions are as follows:- Broad Range Preferred Range
Temperature OC 250-600 300-500 Pressure bars Atmospheric -- 300 20-200 Space velocity v/v/hr 1,000-1 00,000 5,000--30,000 Preferably the initial molar ratio of hydrogen to nitrogen is in the ratio 2 to 1 to 0.67 to 1, most preferably about 1:1, for moderate space velocities.
At high space velocities, e.g., in the range 30,000 to 100,000, even lower initial ratios of hydrogen to nitrogen may be beneficial, e.g., about 0.5:1.
However, as the hydrogen content or the feed drops the maximum conversion to ammonia also decreases. This is because at a given temperature and pressure the maximum percentage of ammonia in the gas cannot exceed the equilibrium concentration and this decreases with the hydrogen content of the gas. As the conversion to ammonia increases, the hydrogen content of the gas drops to the point where equilibrium constraints become too severe in the case of systems with low initial hydrogen contents.
This problem becomes more significant as the initial hydrogen concentration decreases and can be overcome by injecting hydrogen at an intermediate point or points along the reactor.
In a conventional process operating under stoichiometric conditions, a feedstock comprising hydrogen and nitrogen in the molar ratio of 3:1 is passed to a reactor where partial conversion occurs.
the product, ammonia, is removed, and unreacted hydrogen and nitrogen are recycled. Since the feedstock is supplied with a HN2 molar ratio of 3:1 and the product removed has the same molar ratio, the recycle must also contain the same gases in the same ratio and therefore the gas composition at all points in the system has this ratio, i.e., initial feed, feed to reactor, conversion occurs. The product, ammonia, is removed, and unreacted hydrogen and nitrogen are recycled. Since the feedstock is supplied with a HN2 molar ratio of 3:1 and the product removed has the same molar ratio, the recycle must also contain the same gases in the same ratio and therefore the gas composition at all points in the system has this ratio, i.e., initial feed, feed to reactor, product and recycle loop.This is shown diagrammatically in the attached Figure 1.
In a process according to the present invention the system is quite different at start-up. Then an initial feedstock comprising hydrogen and nitrogen with a stoichiometric excess of nitrogen is passed to a reactor where partial conversion occurs. The product, ammonia, is removed and unreacted hydrogen and nitrogen are recycled. Since the feedstock is supplied with a stoichiometric excess of nitrogen and the product is removed in stoichiometric proportions, the recycle therefore contains a stoichiometric excess of nitrogen which provides the stoichiometric excess in the reactor and permits feedstock to be supplied in stoichiometric proportions after the initial period. The gas composition therefore differs at different points in the system. This is shown diagrammatically in the attached Figure 2.
Synthesis gas is a suitable source of hydrogen and the atmosphere of nitrogen.
It is not, however, necessary to use highly pure nitrogen and hydrogen in a process according to the present invention since the catalyst has a high tolerance of poisons which are normally harmful to conventional catalysts, such as water and carbon monoxide.
If impurities are present, such as inert gases in nitrogen derived from the atmosphere, these will tend to concentrate in the system unless steps are taken to remove them.
Preferably to achieve this a purge stream is withdrawn from the recycle stream. If this is done, however, the quantity of hydrogen and nitrogen recycled will be altered and therefore the molar ratio of total feedstock to the reactor (i.e., recycle and make-up feed) will also be altered. To compensate for this, a make-up stream to re-establish the desired ratio should be supplied to the reactor This is shown diagrammatically in the attached Figure 3.
With reference to Figure 1.
Feedstock enters the system through line 1 and is mixed with unreacted nitrogen and hydrogen before entering a reactor 2. Product and unreacted feedstock leave by line 3 and pass to a separator 4 from which ammonia product is withdrawn by line 5 and unreacted nitrogen and hydrogen are recycled by line 6.
Typical throughput ratios at various points are given below:-
Point Composition #1.5 mol H2 A 2 mol #0.5 mol N2
Point Composition mol H2 B 6 mol # 1.5 mol N2 # 1 mol NH3 C 5 mol 3 mol H2 mol N2 D 1 mol NH3 #3 mol H2 E 4 mol #1 mol N2 The molar ratio of H2:N2 at all points is 3:1.
With reference to Figure 2.
The system of Figure 2 is similar to that of Figure 1 with the addition of a feed line 7 for supplying additional nitrogen at start-up.
Typical throughput ratios at various points are given below:
Point Composition #3 mol H2 A Initially 6 mol #3 mol N2 A Subsequently 2 mol 1.5 mol H2 #3 mol H2 B 6 mol #3 mol N2 #1 mol NH3 #1.5 mol H2 2.5 mol N2 D 1 mol NH3 E 4 mol #1.5 mol H2 In this system the ratio of H2:N2 changes from 1:1 H2:N2 at the reactor inlet to 1.5::2.5 at the outlet.
With reference to Figure 3.
The system of Figure 3 is similar to that of Figure 1 with the addition of a purge line 8.
Typical throughput ratios at various points are given below:
Point Compositions #3 mol H2 A Initially 6 mol 1.575 mol H2 A Subsequently 2.1 mol 3 mol H2 3 mol N2 1 mol NH3 C 5 mol 1.5 mol H2 2.5 mol N2 D 1 mol NH3 1.425 mol H2 E 3.8 mol 2.375 mol N2 3.0 mol H2 F 5.9 mol 2.9 mol N2 G 0.1 mol N2 0.075 mol H2 H 0.2 mol 0.125 mol N2 In the system according to Figure 3, because the molar ratio of H2:N2 is displaced to 1.5:2.5 in the recycle line 6, purging by line 8 results in the removal of a disproportionate volume of nitrogen. This is made up by the continuous injection of extra nitrogen through line 7.
Assuming a purge of 5% of total flow, the gas removed in the purge would contain 0.075 mol H2 and 0.125 mol N2 leaving a recycle gas flow of 1.425 mol H2 and 2.375 mol N2. This in turn would give a gas mixture at the reactor inlet, after addition of feed gas, of 2.925 mol H2 and 2.875 mol N2. To compensate for this it would be necessary to increase the feed to 1.575 mol H2 and 0.525 mol N2 giving a gas ratio of 3.0 mol H2 and 2.9 mol N2 at F. Therefore to retain the 1:1 ratio at the reactor inlet the continuous injection of 0.1 mol N2 would be required.
Reverting to the system described with reference to Figure 2, the feedstock entering the reactor has the desired molar ratio of H2:N2 of 1 :1. However, since the reaction consumes more hydrogen than nitrogen, the molar ratio of hydrogen to nitrogen will progressively decrease along the length of the reactor. In order to compensate for this, additional hydrogen may be injected at points along the reactor to maintain the desired ratio.
This will affect the composition of the recycle gas and additional adjustments to the composition of the make-up feed may be necessary.
This system is schematically set out in Figure 4 wherein intermediate hydrogen injection takes place through lines 9 and 10.
Typical throughputs at various points are given below.
0.4995 mol N2 A 1.332 mol 0.8325 mol H2 6 mol N2 B 12 mol 6 mol H2 5.5005 N2 C 11.668 mol 5.1675 H2 1 mol NH3 D 1 mol 1 mol NH3 E 10.668mol [ 5 005 N2 5.8335 mol N N 11.667 mol 5.5005 mol H2 0.333 mol NH3 5.8335 mol N2 0 12 mol 5.8335 mol H2 - 0.333 mol NH3 mol N2 P 11.667 mol | mol H2 mol NH3 ~ 5.667 mol N2 Q 12 mol 5.667 mol H2 ~ 0.666 mol NH3 0.333 mol Hydrogen injected at 9 10.
Total feed=A+9+10=2.0 mol.
Claims (13)
1. A continuous process for the production of ammonia which process comprises passing a feedstock containing hydrogen and nitrogen, at start-up the nitrogen being supplied in stoichiometric excess and thereafter in stoichiometric proportions, over a catalyst comprising (i) as support a graphitecontaining 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 IA of the Periodic Table or the lanthanides or actinides, the modifying metal ion being actively associated with the transition metal rather than the support, under conditions of temperature, pressure and space velocity such that conversion to ammonia is effected, separating unreacted hydrogen and nitrogen from product ammonia, recycling the unreacted hydrogen and nitrogen with the nitrogen in stoichiometric excess, and supplying make-up feedstock of hydrogen and nitrogen in stoichiometric proportions.
2. A process 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 process according to either of the preceding claims, wherein the transition metal is present in amount 1 to 30% by weight, expressed as % by weight of total catalyst.
4. A process according to any of the preceding claims, wherein the transition metal is ruthenium.
5. A process according to any of the preceding claims, wherein the modifying metal ions are rubidium or potassium ions.
6. A process according to any of the preceding claims, wherein the feedstock is passed over the catalyst at a temperature in the range 2500 to 6000C, a pressure in the range atmospheric to 300 bars and a space velocity in the range 1,000 to 100,000 v/v/hr.
7. A process according to Claim 6, wherein the feedstock is passed over the catalyst at a temperature in the range 300 to 5000C, a pressure in the range 20 to 200 bars and a space velocity in the range 5,000 to 30,000 v/v/hr.
8. A process according to any of the preceding claims, wherein the molar ratio of hydrogen to nitrogen at the entrance to the reactor is in the range 2:1 to 0.67:1.
9. A process according to Claim 8, wherein the molar ratio of hydrogen to nitrogen at the entrance to the reactor is 1:1.
10. A process according to any of the preceding claims, wherein a purge stream is withdrawn from the recycle stream and a compensating make-up stream is supplied to the reactor to re-establish the desired ratio of hydrogen to nitrogen.
11. A process according to any of the preceding claims, wherein hydrogen is injected at an intermediate point or points along the reactor.
12. A process according to Claim 1 as hereinbefore described with reference to the Examples.
13. Ammonia whenever prepared by a process according to any of the preceding claims.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB7935046A GB2034292B (en) | 1978-10-12 | 1979-10-09 | Production of ammonia |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB7840384 | 1978-10-12 | ||
GB7935046A GB2034292B (en) | 1978-10-12 | 1979-10-09 | Production of ammonia |
Publications (2)
Publication Number | Publication Date |
---|---|
GB2034292A true GB2034292A (en) | 1980-06-04 |
GB2034292B GB2034292B (en) | 1982-11-10 |
Family
ID=26269179
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB7935046A Expired GB2034292B (en) | 1978-10-12 | 1979-10-09 | Production of ammonia |
Country Status (1)
Country | Link |
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GB (1) | GB2034292B (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0179392A2 (en) * | 1984-10-16 | 1986-04-30 | The M. W. Kellogg Company | Ammonia synthesis process |
EP0553815A1 (en) * | 1992-01-31 | 1993-08-04 | MONTECATINI TECNOLOGIE S.r.l. | A method for producing lower polyhydric alcohols and a new ruthenium-based catalyst used in this method |
-
1979
- 1979-10-09 GB GB7935046A patent/GB2034292B/en not_active Expired
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0179392A2 (en) * | 1984-10-16 | 1986-04-30 | The M. W. Kellogg Company | Ammonia synthesis process |
EP0179392A3 (en) * | 1984-10-16 | 1989-01-04 | The M. W. Kellogg Company | Ammonia synthesis process |
EP0553815A1 (en) * | 1992-01-31 | 1993-08-04 | MONTECATINI TECNOLOGIE S.r.l. | A method for producing lower polyhydric alcohols and a new ruthenium-based catalyst used in this method |
US5403805A (en) * | 1992-01-31 | 1995-04-04 | Montecatini Tecnologie S.R.L. | Ruthenium-based catalyst for producing lower polyhydric alcohols |
US5600028A (en) * | 1992-01-31 | 1997-02-04 | Montecatini Technologie S.R.L. | Method for producing lower polyhydric alcohols and a new ruthenium-based catalyst used in this method |
USRE37329E1 (en) * | 1992-01-31 | 2001-08-14 | Giuseppe Gubitosa | Ruthenium-based catalyst for producing lower polyhydric alcohols |
Also Published As
Publication number | Publication date |
---|---|
GB2034292B (en) | 1982-11-10 |
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Legal Events
Date | Code | Title | Description |
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PCNP | Patent ceased through non-payment of renewal fee |