WO2004058630A2 - Process and apparatus for hydrogen purification - Google Patents
Process and apparatus for hydrogen purification Download PDFInfo
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- WO2004058630A2 WO2004058630A2 PCT/US2003/040797 US0340797W WO2004058630A2 WO 2004058630 A2 WO2004058630 A2 WO 2004058630A2 US 0340797 W US0340797 W US 0340797W WO 2004058630 A2 WO2004058630 A2 WO 2004058630A2
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Definitions
- This invention relates to a pressure swing adsorption (PSA) system and process for purifying impure gas streams containing more than 50 mole % hydrogen, and more particularly to such a process for the production of high purity hydrogen from various hydrogen-containing feed mixtures such as synthesis gas.
- PSA pressure swing adsorption
- the improved process provides higher hydrogen recovery and lower adsorbent inventory as compared with previously disclosed PSA processes for hydrogen production.
- the H 2 gas being fed to PSA systems can, however, contain several contaminants in widely varying concentrations, (e.g. the feed stream to the PSA from a steam methane reformer (SMR) may contain one or more of C0 2 , CH , CO and N 2 .
- SMR steam methane reformer
- This combination of adsorbates at such widely varying compositions presents a significant challenge to the design of a PSA system, particularly with respect to adsorbent selection and configuration of the adsorber/adsorbent bed.
- Representative prior art PSA processes include Sircar et al . , U.S. Pat. No. 4,077,779; Fuderer et al., U.S. Pat., 4,553,981; Fong et al . , U.S. Pat No. 5,152,975; Wagner, U.S. Pat No. 3,430,418 and Batta, U.S. Pat #3,564,816.
- Bomard et al . in U.S. Pat. # 5,912,422 discloses a PSA process for the separation of hydrogen from a feed gas mixture that contains CO and other impurities such as C0 2 and hydrocarbons.
- the feed mixture is passed into a first adsorbent to remove C0 2 and/or hydrocarbons, and then into a second adsorbent that is a faujasite type zeolite with at least 80 % lithium exchange to remove primarily CO impurity to produce hydrogen.
- N 2 is present in the hydrogen-containing feed mixture then Bomard et al . , introduces a third adsorbent between the first and second adsorbent to remove nitrogen.
- Golden et al . U.S. Pat .# 4,957,514 disclosed the purification of hydrogen using barium exchanged Type X zeolite.
- Golden at - al . US Pat. # 6,027,549, disclose a PSA process to remove C0 2 and CH 4 using activated carbons having bulk densities in the range of approximately 35-38 lb/ft 3 .
- Johnson et al . in US Patent 6,302,943 and in EP 1097746A2, disclose adsorbents for H 2 recovery by pressure and vacuum swing adsorption, wherein the adsorbents at the product end of the bed have Henry' s Law constants between 0.8 and 2.2 mmol/g/atm for CO and between 0.55 to 1.40 mmol/g/atm N 2 .
- the present invention addresses this need through the use of a novel selection and arrangement of adsorbents within the adsorbent bed.
- each adsorber (bed) of the H2-PSA system is divided into four regions .
- the first region comprises an adsorbent for the removal of water from the feed stream.
- the second region functions to reduce high (>10% by vol.) level contaminants (e.g., C0 2 ) in the hydrogen containing feed to less than 10%.
- the third region comprises an adsorbent capable of reducing the concentrations of all impurities entering this layer to less than 1%.
- the fourth region consist of adsorbents having high Henry's Law constants for N 2 (e.g. greater than 1.5mmol/gm bar and preferably greater than 2.3 mmol/gm bar) and CO (e.g. greater than 2.94 mmol/gm bar) to remove the remaining impurities to achieve the desired product (H 2 ) purity.
- the second region may be omitted and/or combined with the third region. Other embodiments are also disclosed.
- FIG. 1 illustrates a schematic of a four layered PSA adsorption column in accordance with a preferred embodiment of the invention.
- Figs. 2a and 2b illustrates delta nitrogen loading and Henry's Law constants, respectively for various adsorbents in Region 4 of an adsorbent bed.
- Fig. 3 shows a correlation between Henry's Law constants and Working Capacity.
- FIG. 4 shows process flow diagram for a four bed PSA system in accordance with the invention.
- Fig. 5 shows comparisons between hydrogen recovery and bed size factor for various processes examples .
- FIG. 6 shows comparisons of processes disclosed in the Examples in terms of bed size factor.
- an improved PSA system and process for purifying a gas stream containing more than 50 mol . % hydrogen
- H 2 feed gas to a PSA contains several contaminants, such as H 2 0, C0 2 , CH , CO, and N 2 .
- all gas component percentages are mol . % unless otherwise indicated.
- Such a combination of adsorbates at such widely varying compositions presents significant challenge to efficient adsorbent selection.
- a preferred embodiment of the invention is illustrated with reference to Figure 1.
- the PSA process uses an adsorbent bed comprising four regions of adsorbents.
- the first region is that which is closest to the feed end of the bed as indicated by the arrows indicating the direction of gas flow.
- the first region of the bed comprises adsorbents to remove contaminants like water.
- the adsorbent for the first layer (first region) may be selected from the group consisting of alumina, silica gel, silicalite or zeolites.
- the adsorbent for the second layer/region is utilized for the removal of C0 2 and some CH 4 .
- this layer comprises activated carbon having a bulk density of 38-46 lb/ft 3 (measured by ASTM Standard D-2854) , which may be mixed with a weaker adsorbent (for C0 2 and CH) such as alumina.
- the purpose of the mixture is to minimize the temperature gradient of the layer as well as the thermal swing associated with the heat of adsorption.
- the most preferred activated carbon is G2X activated carbon available from Takeda Chemical Industries, Japan.
- different fractions of alumina and activated carbon may be used.
- the optimum quantity of alumina and carbon for the mixture is dictated by the PSA process operating conditions, feed composition and the local gas phase concentration in the bed. Mixtures of other strong and weak adsorbents may also be used to achieve the desired reduction of thermal gradients in the bed.
- One such mixture could be activated carbon and ZnX zeolite or alumina and ZnX. Additional details on using mixtures of strong and weak adsorbents in PSA processes are disclosed by Ackley et al . , US Patent # 6,027,548. [0025]
- the adsorbent for the third layer is utilized for the removal of residual CH 4 and the bulk of the N 2 and CO in the feed stream.
- a preferred adsorbent for this region is activated carbon having a bulk density greater than or equal to 38 lb/ft 3 '
- G2X activated carbon is the most preferred material .
- Cation exchanged forms of zeolites A, X, Y (e.g. ZnX and ZnY) , chabazites and ) mordenite, and more particularly, X zeolite exchanged with Zn 2+ and Cu 2+ ions at different percentages of exchange may be used.
- the synthesis of Zn 2+ and Cu 2+ exchanged X zeolite is given by Khelifa et al . , Microporous and Mesoporous Materials, Vol. 32, pg 199, 1999 and references therein.
- alternative materials for region 3 of the bed may include impregnated activated carbons having bulk densities in the range of 32-45 lb/ft 3 .
- An example of one such impregnated activated carbon is Sn- activated carbon (Sn-AC) . More specifically, the activated carbon is impregnated with about 35% SnCl 2 .2H 2 0 salt and then dried at 180 °C to produce AC- Sn0 2 . Additional information on the synthesis of Sn- activated carbons (Sn-AC) is given by Iyuke et al . , Chemical Engineering Science, Vol. 55, pg 4745, 2000. Relatively less preferred materials are activated carbons for region 3 of the bed.
- preferred adsorbents to be used in the second and third regions of the bed preferably have a high bulk density, in the range of 38-46 lb. /ft 3 .
- the use of such materials results in higher H 2 recovery (about a 10% improvement) over conventional processes and lower adsorbent inventory for the PSA process.
- adsorbents having bulk density in the preferred range adsorbents having the highest dynamic capacity for the contaminant should be chosen.
- the dynamic loading capacity is defined as is the difference between the loading under adsorption conditions and loading under desorption conditions.
- regions 2 and 3 remove the majority of C0 2 , CO, CH 4 and N 2 present in the H 2 containing feed mixture, the largest thermal gradients and thermal swings are present in those two regions of the bed, with region 2 having greater thermal gradients and thermal swings in the bed than region 3.
- Two mixture combinations of adsorbents were compared for region 2 of the bed.
- a lower density activated carbon (BPL, available from Calgon Carbon Corp. USA) having a density of less than 38 lb/ft 3 was also analyzed for comparison to G2X performance. The results are shown Table 1 below.
- Table 1 Regions 2 and 3 (see Fig. 3) Temperature Swing and Dynamic Loadings of C0 2 and CH 4 on activated carbons (G2X & BPL) , alumina, and mixtures of A201 alumina and G2X activated carbon.
- Table 1 clearly illustrates, that the adverse thermal gradient in region 2 of the bed is reduced significantly by mixing G2X carbon with a weaker adsorbent (e.g., alumina).
- a weaker adsorbent e.g., alumina
- mixtures of G2X carbon and 25% or 50% A201 activated alumina available from UOP, Des Plaines, IL, USA
- the thermal swings were reduced from 25K for the G2X carbon alone to 20K and 16K for the respective mixtures.
- the delta C0 2 and delta CH loadings decreased 14% and 18%, respectively for the 75% carbon mixture.
- the dynamic loadings of the mixtures are higher than the simple weighted average of the adsorbent loadings due to the reduction in the adverse thermal swing, i.e. due to the lower heats of adsorption and the increased heat capacity provided by the higher density, weaker adsorbent .
- a secondary advantage of the use of a mixture in region 2 is the impact upon the base temperature in region 3.
- the delta N 2 and delta CH loadings (not shown in Table 1) are about 10% higher due to the lower temperature in region 2 resulting from the mixture.
- the second region consists of a mixture of a stronger and weaker adsorbents (e.g.
- the most preferred adsorbents for region four have a N 2 Henry' s Law Constant between 2.58 mmol/g.bar and 10 mmol/g.bar, preferably between 2.58 and 4.3 mmol/g.bar.
- Adsorbents having a CO Henry's Law Constant of greater than 2.94 mmol/g.bar is also preferred.
- adsorbents with high Henry's law constant achieve increased dynamic capacity, as well as lower bed pressure during equalization and purge steps in the PSA cycle. Consequently, higher H 2 recovery and lower bed size factor are achieved due to lower bed pressure prior to counter-current (with respect to feed direction) blowdown in the PSA cycle.
- the spreading of the mass transfer zone is suppressed during the co-current pressure changing steps (e.g., bed-to-bed equalization) in the PSA cycle.
- adsorbents having the above Henry's Constant include CaEMT, CaMOR and LiMOR and absorbents with Henry's constant ⁇ l .5 mmol/g.
- Alternative materials for region 4 include naturally occurring crystalline zeolite molecular sieves such as chabazite, erionite, clinoptilolite, and faujasite, and suitable synthetic zeolite molecular sieves such as ZSM-2, ZSM-3, EMC-2 (containing hexagonal faujasite possessing structure code EMT) , beta, mordenite, heulandite,A, D, R, T, X, Y, and L.
- naturally occurring crystalline zeolite molecular sieves such as chabazite, erionite, clinoptilolite, and faujasite
- suitable synthetic zeolite molecular sieves such as ZSM-2, ZSM-3, EMC-2 (containing hexagonal faujasite possessing structure code EMT) , beta, mordenite, heulandite,A, D, R, T, X, Y, and L.
- zeolites containing cations selected from group I e.g., Li, Na, K, Rb, Cs
- group II e.g., Mg, Ca, Sr, and Ba
- zeolites A and X having at least 50% of its A10 2 elements associated with cations chosen from the group formed by calcium, lithium, zinc, copper, manganese, magnesium, nickel, strontium and barium could be used in region 4 of the bed.
- mordenites exchanged with Li or Ca cations, EMT, FAU, MOR, and CaX could also be used the in the purification zone (region 4) of the bed to remove impurities such as N 2 and traces of CH 4 , and CO to produce high purity H 2 .
- the three letter codes identifying the tetrahedral frameworks are structure type codes assigned by the international Zeolite Association in accordance with rules set up by the IUPAC Commission on Zeolite Structure Types, W.M. Meier et al . , 4 th Revised Edition, 1996.
- zeolite containing lithium/alkaline earth metal A and X zeolites (Chao et al . , U.S. Pat Nos. 5,413,625; 5,174,979; 5,698,013; 5,454,857 and 4,859,217) may also be used in region 4 of this invention.
- Figure 4 shows four adsorbent beds (Bl, B2 , B3 and B4) and associated valves and conduits that will be used to illustrate the enhanced PSA process performance of this invention.
- adsorbent beds Bl, B2 , B3 and B4
- FIG. 1 and 4 one embodiment of this invention is disclosed over one complete PSA cycle, and the PSA valve switching and steps are given in Tables 2 and 3, respectively.
- region 1 contains alumina
- region 2 contains a mixture of 50 % each of A201 alumina and Takeda G2X activated carbon
- region 3 contains G2X activated carbon
- region 4 contains CaX(2.0) .
- Step 1 (AD1) Bed 1 (Bl) is in the first adsorption step (AD1) at 232 psig, while Bed 2 (B2) is undergoing countercurrent blowdown (BD) , Bed 3 (B3) is undergoing the first equalization falling step (EQIDN) , and bed 4 (B4) is undergoing the second pressure equalization rising step (EQ2UP) .
- Step 2 Bed 1 is in the second adsorption step (AD2) and is also supplying product gas to bed 4 that is undergoing the first product pressurization (PP1) step. During the same time, beds
- Step 3 Bed 1 is in the third adsorption step (AD3) , and is also supplying product gas to Bed 4 that is undergoing the second product pressurization (PP2) step.
- beds 2, 3, and 4 are undergoing the first equalization rising step (EQ1UP) , second equalization falling (EQ2DN) , and second product pressurization step
- Step 4 (EQIDN) : Bed 1 is undergoing the first equalization falling step (EQIDN) , while bed 2 receives the gas from bed 1 and is undergoing the second equalization rising step (EQ2UP) . Beds 3 and 4 are now undergoing blowdown (BD) and the first adsorption step
- Step 5 PPG: Bed 1 is undergoing cocurrent depressurization step to provide purge gas (PPG) to bed
- Step 6 Bed 1 undergoes a second equalization falling step (EQ2DN) by sending low pressure equalization gas to bed 3 that is undergoing the first equalization rising (EQIUP) step. Beds 2 and 4 are undergoing the second product pressurization (PP2) and third adsorption step, respectively.
- Step 7 Beds 1 and 2 undergo the countercurrent blowdown (BD) and first adsorption (ADl) step, respectively. During this time Beds 3 and 4 are undergoing bed-to-bed equalization, i.e., Beds 3 and 4 are undergoing the second equalization rising (Eq2UP) and first equalization falling (EQIDN) steps, respectively.
- Step 8 or PG (time units 340-425 sec) : Bed 1 is now receiving purge gas (PG) from Bed 4, and Beds 2 and 3 are undergoing the second adsorption step and first product pressurization (PP1) step, respectively.
- Step 9 (EQIUP) : Bed 1 is undergoing the first equalization rising step (EQIUP) by receiving low pressure equalization gas from bed 4 that is undergoing the second equalization falling step (EQ2DN) .
- EQ2DN second equalization falling step
- beds 2 and 3 is undergoing the third adsorption step (AD3) and the second product pressurization (PP2) , respectively.
- Step 10 Bed 1 is undergoing the second equalization rising step (EQ2UP) by receiving high pressure equalization gas from bed 2 that is undergoing the first equalization falling step (EQIDN) .
- Steps 3 and 4 are undergoing the first adsorption (ADl) step and countercurrent blowdown step, respectively.
- Step 11 (PP1) Bed 1 is receiving first product pressurization (PP1) gas from bed 3 that is also in the second adsorption step (AD2) , while Bed 2 is undergoing cocurrent depressurization step to provide purge gas (PPG) to bed 4.
- PP1 first product pressurization
- AD2 second adsorption step
- PPG purge gas
- Step 12 Bed 1 is receiving second product pressurization (PP2) gas from bed 3 that is also in the third adsorption step (AD3) .
- PP2 second product pressurization
- AD3 third adsorption step
- Bed 2 undergoes a second equalization falling step (EQ2DN) by sending low pressure • equalization gas to bed 4 that is undergoing the first equalization rising (EQIUP) step.
- EQ2DN second equalization falling step
- Tables 2 and 3 summarize the valve sequence over one complete cycle for the four bed PSA process shown in Figure 4, and Table 5 gives the respective time intervals and the corresponding status of each bed during one complete PSA cycle. Note from Tables 2 and 3 that the four beds operate in parallel, and during ⁇ of the total cycle time one of the beds is in the adsorption step, while the other beds are either undergoing pressure equalization, purge, blowdown, or product pressurization.
- AD2/PP1 Second Adsorption Step/First product pressurization
- AD3/PP2 Third Adsorption Step/Second product pressurization
- Table 4 gives an example of the operating conditions and the PSA process performance using alumina in region 1, a mixture of 50% each of A201 alumina and G2X activated carbon in region 2, G2X in region 3, and CaX(2.0) in the region 4 in the bed. This example is hereafter referred to as IV2.
- Table 5 gives an example of the operating conditions and the PSA process performance using alumina in region 1, high bulk density ( >38 lb/ft 3 ) G2X activated carbon in regions 2&3, and VSA6 in the fourth region in the bed. This example is hereafter referred to as IV1.
- Table 6 (Prior Art) gives an example of the operating conditions and the PSA process performance using alumina in region 1, low bulk density ( ⁇ 38 lb/ft 3 ) activated carbon in regions 2&3, and 5A zeolite in the fourth region in the bed. This example is hereafter referred to as PA.
- TPD ton (2000 lb) per day of hydrogen
- kPa 1000
- s time unit in seconds .
- Table 4 (IV2) Four Bed PSA process performance (SMR feed) using alumina in the first region in the bed, a mixture of 50% A201 alumina and G2X activated carbon in the second region, G2X activated carbon in the third region, and CaX(2.0) in the fourth region (top) .
- the results shown below correspond to PSA process modeling using a feed mixture of 75.83% H 2 , 0.72% N 2 , 3.35 % CH 4 , 2.96% CO, and 17.14% C0 2 .
- the adsorption pressure is 232 psig
- the desorption pressure is 4.4 psig
- twelve steps see Tables 2 and 3) are used in the four bed PSA cycle. Further details of the four bed PSA process are given below.
- Adsorbent region 1 : Alumina Bulk Density (Alumina) 49.0 lb/ft 3 Amount of Alumina : 74.65 lb m /TPD H 2
- Adsorbent region 2 : Mixture ( 50% each of A201 alumina and G2X)
- Adsorbent (region 3) : Takeda G2X activated carbon Bulk Density: 39.0 lb/ft 3 '
- Adsorbent region 4: CaX(2.0) Bulk Density (CaX(2.0): 41.33 lb/ft 3 Amount of CaX(2.0) : 137.38 lb m /TPD H 2
- Table 5 (IV1) Four Bed PSA process performance (SMR feed) using alumina in the first region in the bed, high bulk density (> 38 lb m /ft 3 ) G2X activated carbon in the regions 2 &3 , and VSA6 zeolite in the fourth region (top) .
- SMR feed Bed PSA process performance
- the results shown below correspond to PSA process modeling using a feed mixture of 75.83% H 2 , 0.72% N 2 , 3.35 % CH 4 , 2.96% CO, and 17.14% C0 2 .
- the adsorption pressure is 232 psig
- the desorption pressure is 4.4 psig
- twelve steps see Table 2 and 3) are used in the four bed PSA cycle. Further details of the six bed PSA process are given below.
- Adsorbent region 1 : Alumina Bulk Density (Alumina): 49.0 lb/ft 3 Amount of Alumina: 78.26 lb m /TPD H 2
- Adsorbent (regions 2&3) : Takeda G2X activated carbon
- Adsorbent region 4) : VSA6
- VSA6 Bulk Density
- Table 6 (Prior Art, i.e. PA) : An example of the operating conditions and the PSA process performance using alumina, activated carbon and 5A zeolite in the three layer bed and the four bed PSA process of Figure 4. The results shown below were obtained from PSA simulation results using a feed mixture on a dry basis: 75.83% H 2 , 17.14% C0 2 , 2.96% CO, 3.35% CH 4 and 0.72% N 2 . Also, in the table, total bed size factor is the total quantity of adsorbents per ton per day of H 2 produced.
- Adsorbent regions 2 &3 : activated carbon
- Adsorbent in (region 4) 5A zeolite Amount of 5A zeolite (lb/TPD H 2 ) : 293.93
- FIG. 5 compares the PSA process performance, obtained via computer simulations, using the PSA processes of Tables 4-6. Note that in the upper drawing of Fig. 5, that for about the same H 2 purity (99.99%), the H 2 recovery using 5A zeolite (PA) is about 76% (Table 6) .
- the H 2 recovery is about 80% (Table 5, i.e., IV1) , and 84% (Table 4, i.e., IV2), respectively.
- the lower diagram of Figure 5 shows the total bed size factor (BSF, lb/TPDH 2 ) obtained using each of the aforementioned adsorbents and the PSA processes of Tables 4-6.
- FIG. 6 shows the total bed size factor (BSF, lb/TPDH 2 ) obtained using each of the aforementioned adsorbents and the PSA processes of Tables 4-6.
- the lower diagram shows the percentage reduction in bed size factor of this invention (IV1 & IV2) relative to the prior art (PA) .
- IV1 gives about 35% reduction over the prior art (PA)
- IV2 gives about 50% reduction in the bed size factor relative to the prior art (PA) .
- the 50 % reduction in bed size factor in IV2 implies that IV2 needs only half the adsorbent inventory relative to the prior art (PA) process .
- the region/layer of each bed could be replaced with multiple layers of different adsorbents.
- the adsorbent layer could be substituted by a composite adsorbent layer containing different adsorbent materials positioned in separate zones in which temperature conditions favor adsorption performance of the particular adsorbent material under applicable processing conditions in each zone. Further details on composite adsorbent layer design is given by Notaro et al . , U.S. Pat. #5,674,311. [0062] Further, consideration of the dynamic or rate effects may achieve enhanced PSA process performance.
- the adsorbents selected for regions 2-4 of the bed could be improved by using higher rate adsorbents in those regions.
- higher surface area/higher porosity adsorbent and/or smaller particles would provide higher adsorption/desorption kinetics.
- a higher rate material such as binderless LiX (2.0) would be desirable. This material could be placed in the entire zone (region 4) or on top of region 4.
- the adsorbent used in region 4 of the bed e.g., CaX
- CaX caustically digested
- smaller particles may also be employed here as well to improve rate.
- Adsorbents having diameters in the range of 0.5- 2.0 mm are preferred in regions 2-4 of the bed in the practice of this invention.
Abstract
Description
Claims
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US10/540,506 US7537742B2 (en) | 2002-12-24 | 2003-12-22 | Process and adsorbent for hydrogen purification |
CA002511660A CA2511660A1 (en) | 2002-12-24 | 2003-12-22 | Process and apparatus for hydrogen purification |
ES03800049.3T ES2455992T3 (en) | 2002-12-24 | 2003-12-22 | Procedure and apparatus for hydrogen purification |
EP03800049.3A EP1590079B1 (en) | 2002-12-24 | 2003-12-22 | Process and apparatus for hydrogen purification |
AU2003299775A AU2003299775A1 (en) | 2002-12-24 | 2003-12-22 | Process and apparatus for hydrogen purification |
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EP (1) | EP1590079B1 (en) |
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EP1874438A4 (en) * | 2005-04-26 | 2010-09-22 | Uop Llc | Gas purification process |
EP1826176A2 (en) * | 2006-02-22 | 2007-08-29 | Linde Aktiengesellschaft | Pressure swing adsorption method and device |
EP1826176A3 (en) * | 2006-02-22 | 2008-03-12 | Linde Aktiengesellschaft | Pressure swing adsorption method and device |
EP2134446B1 (en) * | 2007-03-20 | 2015-09-02 | PT Biogas Technology Limited | Biogas upgrading |
WO2010111049A1 (en) * | 2009-03-25 | 2010-09-30 | Praxair Technology, Inc. | Cyclic adsorption control method and controller |
US8016914B2 (en) | 2009-03-25 | 2011-09-13 | Praxair Technology, Inc. | Adsorption control method and controller |
CN102834159A (en) * | 2009-03-25 | 2012-12-19 | 普莱克斯技术有限公司 | Cyclic adsorption control method and controller |
RU2597920C2 (en) * | 2009-10-27 | 2016-09-20 | Касале Са | Method for production of ammonia |
Also Published As
Publication number | Publication date |
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ES2455992T3 (en) | 2014-04-21 |
EP1590079B1 (en) | 2014-03-26 |
US7537742B2 (en) | 2009-05-26 |
CA2511660A1 (en) | 2004-07-15 |
EP1590079A4 (en) | 2008-04-09 |
WO2004058630A3 (en) | 2005-01-27 |
CN1758957A (en) | 2006-04-12 |
AU2003299775A8 (en) | 2004-07-22 |
EP1590079A2 (en) | 2005-11-02 |
CN100581645C (en) | 2010-01-20 |
US20060254425A1 (en) | 2006-11-16 |
AU2003299775A1 (en) | 2004-07-22 |
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