WO1991009811A1 - Procede de synthese de l'ammoniaque - Google Patents

Procede de synthese de l'ammoniaque Download PDF

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Publication number
WO1991009811A1
WO1991009811A1 PCT/US1990/000075 US9000075W WO9109811A1 WO 1991009811 A1 WO1991009811 A1 WO 1991009811A1 US 9000075 W US9000075 W US 9000075W WO 9109811 A1 WO9109811 A1 WO 9109811A1
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WO
WIPO (PCT)
Prior art keywords
ammonia
ammine
liquid
gas
synthesis
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Application number
PCT/US1990/000075
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English (en)
Inventor
Eugene F. Schwarzenbek
Original Assignee
Schwarzenbek Eugene F
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Schwarzenbek Eugene F filed Critical Schwarzenbek Eugene F
Priority to PCT/US1990/000075 priority Critical patent/WO1991009811A1/fr
Publication of WO1991009811A1 publication Critical patent/WO1991009811A1/fr

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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
    • C01C1/0458—Separation of NH3
    • C01C1/0464—Separation of NH3 by absorption in liquids, e.g. water
    • 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
    • C01C1/0417—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst characterised by the synthesis reactor, e.g. arrangement of catalyst beds and heat exchangers in the reactor
    • 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

Definitions

  • This invention pertains to the field of fertilizer science and technology.
  • the invention pertains, in particular, to the synthesis of ammonia by the catalytic reaction of hydrogen and nitrogen.
  • ammonia is a simple catalytic reaction in which three mols of hydrogen and one mol of nitrogen combine to form two mols of ammonia.
  • the reaction is highly selective in that no byproducts are formed, the only concern being contaminants in the feed which might poison the catalyst, or inerts, such as methane and argon, which have to be purged from the system.
  • inerts such as methane and argon, which have to be purged from the system.
  • the ammonia synthesis reaction is intrinsically limited by thermodynamic equilibrium. The equilibrium studies first carried out by Fritz Haber in the early nineteen hundreds showed that the synthesis reaction required high pressures and low temperatures, but the extent of conversion was limited and considerable recycle of unreacted gas was required.
  • Temperature also has a pronounced effect on the equilibrium ammonia content. For example, at 200 atmospheres pressure with 10% inerts in the feed, the equilibrium ammonia content at 694*F. is 39% and at 925*F. is only 16%.
  • the effect of an increasing temperature to decrease the equilibrium ammonia content is aggravated in the ammonia process by the highly exothermic heat of the synthesis reaction. For example, when producing 10% ammonia in the product gas there is about a 260"F. rise in temperature as the synthesis gas flows from the inlet to the outlet of the catalyst bed. In a typical catalyst bed in an ammonia reactor the inlet temperature is low and the equilibrium ammonia content is high.
  • Catalyst activity is another variable affecting reactor performance. High activity is desirable in that it allows one to decrease operating temperature and thereby increase the thermodynamic equilibrium ammonia content and the extent of conversion to ammonia.
  • the catalytic material utilized in present day ammonia plants is the long established alkalized magnetite catalyst, and an increase in activity has only been obtained by a decrease in its particle size. Utilization of the higher activity of smaller particle size catalyst has introduced process design problems in that the smaller particle size increases catalyst bed pressure drop, which is an important consideration in the overall plant design in that it adversely affects the horsepower required for recycling unconverted synthesis gas. In early fixed bed designs a particle size of 6-10 mm in diameter was preferred, though in some designs a particle size as large as 14-20 mm in diameter was used. Over the years the designers have been using smaller and smaller size catalyst to take advantage of the increased activity. The literature, however, does not report any designer using catalyst below 1.5-3 mm in diameter.
  • This low conversion has a significant affect on other steps in the ammonia plant process scheme. It is apparent from the low conversion to ammonia that considerable recycle of unconverted feed is required. It can be calculated that the recycle rate is 3.6 times the fresh makeup synthesis gas.
  • the high recycle rate has the effect of increasing the size of the reactor, the horsepower of the synthesis gas compressor, and as well the horsepower requirement of the ammonia refrigeration compresssor.
  • the recycle gas stream is combined with the makeup synthesis gas, and the total stream which contains only about 10% ammonia is cooled by ammonia refrigeration from about 100*F. to about -10*F. for the recovery of ammonia.
  • the cooling load is a combination of the cooling and condensation of ammonia and the cooling of substantial quantities of unconverted synthesis gas.
  • This invention pertains to a new and novel method of carrying out the synthesis of ammonia from hydrogen and nitrogen in which the ammonia product is reacted with a liquid material to form an ammine product, whereby the method of recovery of ammonia from the product gas is improved.
  • two or more fixed beds of catalyst are used in the synthesis step.
  • the ammonia product from each bed is removed by reaction in a separate vessel to form a liquid ammine product before the unconverted portion of the gas is fed to the next catalyst bed.
  • high conversion of the reactant gas to ammonia can be accomplished is each bed as the gas flows from bed to bed without the necessity of cooling, recompressing, and the recycle of large volumes of unreacted synthesis gas.
  • the synthesis of ammonia is carried out in the presence of the synthesis catalyst suspended in a liquid material that reacts with the ammonia as produced to form a liquid ammine.
  • Another embodiment of this invention provides for the decomposition of the liquid ammine product under conditions which allows the recovery of the ammonia as a liquid by heat exchange with cooling water.
  • the horsepower requirement of the synthesis gas compressor and the ammonia refrigeration compressor, the catalyst inventory, the operating temperature, the operating pressure, or combinations of these factors are reduced, having the effect of decreasing equipment and operating costs.
  • FIG. 1 is a schematic diagram, not to scale, of a simplified ammonia synthesis and ammonia recovery flow chart illustrating one embodiment of this invention.
  • this system there are six fixed beds of catalyst, the product gas from each bed being fed to its respective absorber where the ammonia produced is removed by reaction with a liquid material to form a liquid ammine before the unconverted gas is fed to the next catalyst bed.
  • the liquid ammine product from each absorber is decomposed in a common separate step to recover the ammonia as a liquid by heat exchange with cooling water, the decomposed liquid material being recycled as fresh reactant to the absorbers.
  • Figure 2 is another embodiment of this invention in which the synthesis catalyst is suspended in a liquid material which reacts with the ammonia as produced to upset the thermodynamic equilibrium and allow conversion of the reactant gas in excess of 90%.
  • the liquid ammine is decomposed in a manner similar to that presented in Figure 1.
  • Liquid materials that react with ammonia to produce ammines are used in the practice of this invention.
  • Certain inorganic salts react with ammonia to form adducts which are referred to as ammines.
  • This formation of ammonia adducts is similar to the formation of inorganic salt hydrates.
  • Most salts form more than one adduct.
  • Cuprous chloride for example, forms 0.5, 1.5, and 3 mols of ammonia adducts per mol of salt.
  • Lithium bromide forms.1,2,3,4,5, and 6.5 mols of ammonia adducts per mol of salt.
  • the inorganic ammines are similar to inorganic hydrates in that their melting points are much lower than those of their respective inorganic salt.
  • Cuprous chloride has a melting point of 792*F.
  • the corresponding ammines have melting points of 253 to 324'F.
  • lithium bromide has a melting point of 1017 * F.
  • the corresponding mono-ammine has a melting point of only 207*F.
  • Most inorganic ammines are solid at room temperature, but at the temperature levels of the ammonia synthesis process are liquid. Advantage is taken of the reaction of certain inorganic salts with ammonia and the low melting points of the resulting ammines in the development of this invention.
  • My invention pertains to the providing of a liquid material which reacts with ammonia to produce an ammine, which later is decomposed back to a liquid reacting material for recovery of the ammonia product.
  • the requirement of this reacting material is that it have low decomposition or equilibrium pressure at the 650 to 925 * F. operating range of the present day ammonia synthesis alkalized magnetite catalyst, and have a higher decomposition pressure at some reasonable higher temperature which would allow the ammonia to be recovered by heat exchange with cooling water.
  • the preferred embodiment of my invention is that the reacting material at all times be a liquid, since this provides for ready flow of the reacting material between the synthesis and decomposition sections of the process, and also provides readily for heat removal in the ammonia synthesis section and heat input in the decomposition. section.
  • an attractive operating system would involve the reaction of ammonia with the liquid mono- am ine to form a di-ammine, and flow of the di-ammine to the decomposition section to produce ammonia and the mono-ammine for recycling to the synthesis section.
  • the operating conditions are such that at all times the decomposition equilibrium pressure is above that of the mono-ammine.
  • ammines react with ammonia to form ammines. They may include chlorides, bromides, iodides, nitrates, sulfates and other compounds.
  • the metal components may include zinc, cadium, copper, nickel, magnesium, barium, iron, manganese, lithium, sodium, potassium, calcium, aluminum, titanium, and others.
  • These ammines vary considerably in their stability.
  • the di- ammine of lithium bromide has an ammonia decomposition or equilibrium pressure of 1 atmosphere at 190 • F.
  • the di-ammine of calcium chloride at 329*F.
  • di- ammine of zinc bromide at 712*F.
  • the advantageous application of a particular ammine will depend on the operating temperature and pressure of the system.
  • inorganic ammines which have application in the present day synthetic ammonia process. They include, for example, the mono- and di-am ines of the bromides of nickel, iron, cobalt, magnesium, and zinc, and the chlorides of cobalt and zinc. This invention, however, is not restrictive to the use of these particular materials. In this invention the following reaction is used to illustrate the use of the inorganic ammines in a synthetic ammonia process.
  • Example 1 The above reaction proceeds in the forward or reverse direction depending on the temperature and pressure of the system.
  • zinc bromide mono- and di- ammine system is used to illustrate the examples below, any liquid ammine with the equilibrium or decomposition pressure and temperature relationship similar to that indicated above will perform in a similar manner.
  • the catalyst in a 3000 psia unit is divided into six equal compartments, though more or less compartments can be used, and more or less catalyst can be used in one compartment compared to another compartment.
  • the exit gas from each catalyst bed is fed to an absorber where essentially all the ammonia is removed from the gas before feeding to the next catalyst bed. This procedure is followed for all catalyst beds with the result that the first pass conversion through the reaction system is much higher than in a conventional fixed bed unit.
  • the amount of unconverted recycle gas is markedly reduced.
  • the temperature of the outlet gas from each absorber is set at about 655'F. by the decomposed liquid ammine feed, at which temperature the equilibrium or decomposition pressure of ammonia is only 0.5 atmospheres.
  • the ammonia contents of the exit gas from each catalyst bed is 11.2 - 12 mol%, the removal of the ammonia produced in each bed resulting in a high conversion of the reactant gas as it flows through the six beds.
  • the decomposed liquid ammine is fed at a rate sufficient to react with the ammonia produced and as well to absorb the exothermic heat of the synthesis reaction and the exothermic heat of the ammonia with the liquid reactant material without obtaining excessively high temperatures in the absorber.
  • the exit temperature of the liquid from the bottom of the absorbers is in the range of 950 to 975*F. Higher or lower inlet and outlet temperatures can be used depending on the particular reactant material used, the activity of the synthesis catalyst, and the amount of ammonia in the product gas from each catalyst bed.
  • liquid ammine system the ammonia can be recovered as a liquid by heat exchange with cooling water.
  • Liquid ammonia has a vapor pressure of 212 psia at 100*F.
  • the ammonia product is recovered by decomposing the liquid ammine at a temperature of 1014*F. and a pressure of about 242 psia.
  • the synthesis gas feed 1 produced, for example, in a reformer - purification section [not shown] is joined with unconverted recycle gas 22 and increased to reaction pressure by compressor 2.
  • the total feed 3 is increased to reaction temperature by flow through heat exchangers 4 and 5, and fed to the reaction system.
  • the reaction system contains six catalyst beds, 6,8,10,12,14, and 16, and six absorbers 7,9,11,13,15, and 17.
  • the total feed 3 flows downward through the first fixed catalyst bed 6.
  • the product gas 18 from catalyst bed 6 flows to the bottom of absorber 7 where the product ammonia is reacted with the liquid reactant material 24.
  • the exit gas 19 from absorber 7 flows directly to the top of catalyst bed 8.
  • the exit gas 20 from catalyst bed 8 flows to the bottom of absorber 9.
  • the exit gas 21 from the top of absorber 9 flows directly to the top of catalyst bed 10.
  • the synthesis gas thus flows progressively through catalyst bed 10 and absorber 11, catalyst bed 12 and absorber 13, catalyst bed 14 and absorber 15, and finally through catalyst bed 16 and absorber 17.
  • the exit or recycle gas 22 from absorber 17 is cooled via heat exchanger 4 and water cooler 23, joins synthesis makeup gas 1, is compressed, and flows to the first catalyst bed 6 and absorber 7.
  • the liquid reactant material 24 to absorber 7 flows countercurrent to the exit gas 18 from catalyst bed 6, and exits as the ammonia rich liquid ammine in line 25, through pressure control valve 26 to line 27 which feeds the ammine rich product from the various absorbers to the ammonia recovery system.
  • liquid reactant material feed 28 to absorber 9 exits from the absorber in line 29 through pressure control valve 30 to join line 27.
  • the ammonia rich liquid ammine flows through hydraulic turbine 43 for recovery of power from the pressure release from the synthesis section to the ammonia recovery section.
  • the liquid ammine 44 flows through furnace 45 to separator
  • Liquid ammonia 60 is withdrawn from separator 57 and flows through line 61 to an ammonia refrigeration system [not shown] for cooling and storage of the product at about -28*F. if so desired.
  • an ammonia refrigeration system [not shown] for cooling and storage of the product at about -28*F. if so desired.
  • Table 1 The advantage of the liquid ammine system over conventional fixed bed operation is illustrated in Table 1.
  • the catalyst for the synthesis of ammonia from hydrogen and nitrogen is suspended in the liquid reactant material.
  • synthesis gas 2 in the ratio of 3 parts of hydrogen to 1 part of nitrogen is fed to the bottom of reaction vessel 1.
  • Ammonia produced from the catalytic reaction is reacted with the liquid reactant material.
  • the pressure is 1000 psia and the optimum temperature is 750*F.
  • the equilibrium or decomposition pressure of the liquid di-ammine formed from the reaction is 1.58 atmospheres of ammonia pressure, or 23.3 psia equivalent to 2.3 mol% of ammonia in the vapor phase at the 1000 psia operating pressure.
  • the equilibrium ammonia content at the inlet of the reactor under these operating conditions is 19.5 mol%. This equilibrium ammonia content changes only slightly due to a buildup of inerts as the gas flows from the bottom to the top of the reaction vessel. Since the ammonia content in the vapor phase is at all times low, there is a large driving force for the synthesis reaction to proceed.
  • the liquid ammine produced from the reaction with ammonia is withdrawn from the top of the reactor. A portion is cooled and returned to the bottom of the reaction vessel to aid in removing the exothermic heat of the synthesis reaction and the reaction of the ammonia with the liquid reactant material. The balance of the liquid ammine withdrawn is fed to the ammonia recovery system.
  • a further advantage of this invention is that it is possible to recover the ammonia product as a liquid by heat exchange with cooling water. If the ammonia product collected at about 100*F. can be used directly for further processing to produce, for example, urea, the expensive ammonia refrigeration system of conventional ammonia plants can be completely eliminated. If ammonia product is cooled to -28*F. for storage, the ammonia refrigeration requirement is only to cool the liquid from 100*F. to -28'F. In conventional ammonia processing additional ammonia refrigeration is required to condense the ammonia and to cool the large volumes of unreacted recycle gas to about -10 ⁇ F. In this invention the refrigeration horsepower load is only 23% of that in a conventional present day plant.
  • FIG. 2 is a schematic diagram, not to scale, of a simplified ammonia synthesis flow chart illustrating this embodiment of the present invention.
  • the reaction vessel 1 is provided with an inlet conduit 2 for introduction of the synthesis gas feed comprising the hydrogen and nitrogen reactants for the ammonia synthesis.
  • a feed gas distributor 3 is provided near the bottom portion of the vessel 1 to facilitate distribution of the feed gas across substantially the entire cross section of the vessel.
  • the feed gas flows upward through the reaction vessel 1 which contains a liquid suspension 4 of synthesis catalyst in a liquid reactant material.
  • the product gas leaves the reaction vessel 1 through conduit 5, is cooled in heat exchanger 6, and flows through conduit 7 to a gas - liquid separator where condensed liquid ammine is separated from the purge gas.
  • Product gas from separator 8 flows through conduit 9 and through a pressure control valve 10 to outlet line 11 where the purge gas flows to fuel.
  • Liquid ammine separated in vessel 8 flows through conduit 12 to pump 13 and returned via conduit 14 to the reaction vessel 1.
  • Liquid ammine in vessel 1 is removed via conduit 15 to pump 16 and pump outlet line 17.
  • a portion of the liquid ammine is recirculated to the reaction vessel 1 via conduit 18, through heat exchanger 19, and through conduits 20 and 21.
  • the other portion of the liquid ammine from pump outlet line 17 is diverted to conduit 22 for ammonia recovery.
  • This liquid flows through pressure control valve 23 to conduit 24, through hydraulic turbine 25 to conduit 26 for heating in furnace 27.
  • the effluent from furnace 27 flows via conduit 28 to liquid - gas separator 29.
  • the decomposed reactant material flows from separator 29 through conduit 30, heat exchanger 31 and conduit 32 to pump 33.
  • the product from pump 33 flows through conduit 34 and joins recycle liquid ammine from conduit 20 in conduit 21 for feed to the bottom of reaction vessel 1.
  • the gaseous effluent from separator 29, consisting essentially of ammonia flows through conduit 35 through heat exchanger 36, and through conduit 37 to gas - liquid separator 38.
  • Ammine material condensed in heat exchanger 36 and collected in gas - liquid separator 38 is returned via conduit 39 and pump 40 to the inlet of pump 33.
  • the gaseous ammonia product from gas - liquid separator 38 flows through conduit 41 to water cooler 42 where the ammonia product is condensed and collected in gas - liquid separator 43.
  • the pressure in the ammonia condensation step is controlled by valve 44 through which any unreacted gas is vented to fuel.
  • the liquid ammonia collected in gas - liquid separator 43 is withdrawn through conduit 45 and fed to a conventional ammonia refrigeration system [not shown] if product at about -28*F. is desired for storage.
  • Example 2 of this invention The comparison of pertinent process conditions of Example 2 of this invention and the 3000 psia M. W. Kellogg designed unit with a horizontal fixed bed reactor previously described is presented in Table 2.
  • the pressure in this example was decreased from 3000 to 1000 psia and the catalyst requirement was actually less than in a conventional fixed bed system.
  • the synthesis gas feed is converted to the extent of 94.6% on a once through basis, no recycle of unconverted synthesis gas being required.
  • the conversion on a once through basis is only 23.9%, considerable recycle of unconverted gas being required to arrive at an ultimate conversion of 93.9%.
  • the improved reaction kinetics of this example of the invention has the effect of decreasing the synthesis gas compressor horsepower from 32,160 for the conventional fixed bed unit to 12,810 for this example of this invention.
  • Example l one of the major advantages of this invention is that the ammonia in Example 2 is also recovered as a liquid at about 100*F. by heat exchange with cooling water. Use of the 100 ⁇ F. liquid product in subsequent processing would result in elimination of the refrigeration compressor.
  • the refrigeration horsepower is only 3,905 for this invention compared to 16,737 for a conventional fixed bed unit.
  • refrigeration horsepower is required to cool the large amounts of unreacted recycle gas as well as to cool and liquify the gaseous ammonia.
  • the heavy heat load of liquefaction is carried out with cooling water with the result that the only need for ammonia refrigeration is to cool the liquid ammonia to a low temperature for storage.
  • Example 2 illustrated that operating pressure was decreased from 3000 to 1000 psia by utilizing only about two thirds the amount of catalyst used in the conventional fixed bed unit.
  • This invention covers an operating pressure range of about 10 to 500 atmospheres and an operating temperature range of about 300 to 1000'F. in the synthesis section.
  • the decomposition of the liquid ammine to obtain the ammonia product is carried out at an operating pressure range of about 1 to 50 atmospheres and an operating temperature range of about 500 to 1500*F.
  • Examples 1 and 2 illustrated the advantages of this invention utilizing the reaction of the zinc bromide mono-ammine with ammonia to form the di-ammine. These advantages are attributable to the equilibrium or decomposition pressure - temperature relationship of these two materials. Other compounds that are liquid, will react with ammonia, and have similar decomposition pressure - temperature relationship will give similar results.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

La synthèse de l'ammoniaque à partir de l'hydrogène et de l'azote s'effectue au moyen d'un procédé dans lequel une matière liquide est amenée en réaction avec l'ammoniac pour former un ammoniacate pour, soit améliorer le procédé de récupération de l'ammoniac à partir d'un débit gazeux du produit, soit renverser l'équilibre thermodynamique du système H2-N2-NH3 pour effectuer une meilleure conversion de première passe du gaz réactif en ammoniaque. L'invention permet de réduire la puissance du compresseur de gaz de synthèse, l'inventaire catalytique, la température et la pression opérationnelles, ou tous ces facteurs combinés, ce qui entraîne une diminution des coûts d'équipement et d'exploitation. De plus, l'ammoniacate liquide est décomposé dans des conditions permettant de récupérer l'ammoniaque sous forme liquide par échange thermique avec de l'eau de réfrigération. Ceci diminue considérablement la demande en puissance de réfrigération.
PCT/US1990/000075 1990-01-04 1990-01-04 Procede de synthese de l'ammoniaque WO1991009811A1 (fr)

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Application Number Priority Date Filing Date Title
PCT/US1990/000075 WO1991009811A1 (fr) 1990-01-04 1990-01-04 Procede de synthese de l'ammoniaque

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PCT/US1990/000075 WO1991009811A1 (fr) 1990-01-04 1990-01-04 Procede de synthese de l'ammoniaque

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104150508A (zh) * 2014-08-10 2014-11-19 山东省舜天化工集团有限公司 一种氨合成催化剂低压升温的方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2954272A (en) * 1954-03-23 1960-09-27 Chemical Construction Corp Method of separating ammonia from a gas containing ammonia and carbon dioxide
US4744966A (en) * 1986-11-20 1988-05-17 Santa Fe Braun Inc. Process for synthesizing ammonia

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2954272A (en) * 1954-03-23 1960-09-27 Chemical Construction Corp Method of separating ammonia from a gas containing ammonia and carbon dioxide
US4744966A (en) * 1986-11-20 1988-05-17 Santa Fe Braun Inc. Process for synthesizing ammonia

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104150508A (zh) * 2014-08-10 2014-11-19 山东省舜天化工集团有限公司 一种氨合成催化剂低压升温的方法
CN104150508B (zh) * 2014-08-10 2016-02-24 山东省舜天化工集团有限公司 一种氨合成催化剂低压升温的方法

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