CN1528657A - Low-temperature ammonia decomposition hydrogen preparation catalyst and preparing method thereof - Google Patents
Low-temperature ammonia decomposition hydrogen preparation catalyst and preparing method thereof Download PDFInfo
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- CN1528657A CN1528657A CNA03134691XA CN03134691A CN1528657A CN 1528657 A CN1528657 A CN 1528657A CN A03134691X A CNA03134691X A CN A03134691XA CN 03134691 A CN03134691 A CN 03134691A CN 1528657 A CN1528657 A CN 1528657A
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a catalyst preparing zero-COx hydrogen by ammonia decomposition reaction as well as its preparing method. Its components: active component 0.1-30%, carrier 60-99% and assistant 0-20%. The active component is a metal nitride where the metal is selected from the transition metals and has noble metal property, the carrier is a nano crystal metal oxide (crystal particle size 2-200nm); the assistant is selected from alkali metal, alkali earth metal and rare-earth compound. Its preparing method: firstly, dipping the carrier in the solution of the precursor of the active component, and then drying to bake at 300-900 deg.C; then reducing the sample at 300-900 deg.C by hydrogen, adding in the assistant, drying and baking and then activating at 300-900deg.C. It has very high catalysis activity to ammonia decomposition reaction and simple preparing technique. It can be applied to not only the reaction technique of making zero-COx hydrogen by ammonia decomposition, but also the purifying treatment.
Description
Technical field
The present invention relates to class low temperature modification high-activity ommonia decomposition reaction preparation zero CO
xThe Catalysts and its preparation method of hydrogen belongs to catalyzer and preparing technical field thereof.
Background technology
Hydrogen is a kind of clean energy, and its products of combustion is a water.It with hydrogen the concern that the research and development of the Proton Exchange Membrane Fuel Cells (PEMFC) of fuel are subjected to business and government department just day by day.Current, the major cause that hinders hydrogen energy fuel battery acquisition large-scale application is the storage of hydrogen and the inactivation problem of electrode catalyst.The storage of hydrogen comprises material and the liquid hydrogen-containing fuel of using high hydrogen storage.Use the hydrogen of carbonaceous organism production to contain the poisonous substance CO that causes the fuel cell electrode inactivation inevitably.Because the hydrogen richness (17.6%) of amino molecule is higher, and is easy to liquefaction (liquefaction pressure of ammonia in the time of 20 ℃ has only 8 normal atmosphere), be convenient to store and transportation.Before the anti-CO poisoned catalyst of the high hydrogen storage material that can obtain commercial applications and permanence occurs, with the ammonia (NH of carbon atoms not
3) be that raw material production PEMFC fuel hydrogen will be one of technological approaches that has much magnetism.Because the ammonia degradation production has only hydrogen and nitrogen, and nitrogen does not have negative impact to the electrode of PEMFC.Relevant technological economics evaluation shows, with the ammonia be raw material make hydrogen than make hydrogen by methanol recapitalization and have more economic advantages (Metkemeijer and Achard, J.Power Sources 49 (1994) 271; Int.J.Hydrogen Energy 19 (1994) 535).
It is a thermo-negative reaction that ammonia decomposes.When reacting under 400 ℃ and normal pressure, the equilibrium conversion of ammonia can reach 99.1%, therefore, can judge that from the thermodynamics angle ammonia decomposition hydrogen producing catalyst of developing low temperature high activity is fully feasible.Up to now, have only a small amount of document to disclose to produce the ammonia decomposition catalyzer that hydrogen is target, wherein the activity of such catalysts component is mainly single component or polycomponent metals such as Fe, Ni, Ti, Mo, Co, Ru, and carrier is mainly MgO, the SiO of conventional method preparation
2, Al
2O
3And gac (Catal.Lett.72 (2001) 197 for Choudhary, et al.; Jedynak et al., Appl.Catal., 237 (2002) 223; Hinrichsen, Catal Today, 53 (1999) 177; Rarog et al.Appl.Catal.A, 208 (2001) 213; Abasharet al.Appl.Catal.A, 236 (2002) 35; Goetsch and Schmit 2001, WO Patent 0187770A1; Kordeschet al.2002, WO Patent 0208117A1; Bradford et al.J.Catal.172 (1997) 479).But these activity of such catalysts are all lower, are difficult to satisfy efficiently produce hydrogen, the particularly requirement of vehicle-mounted hydrogen production technology.
Recently, we have invented a kind of Catalysts and its preparation method (Chinese patent application number: 03143112.7) that ammonia decomposition reaction is had higher catalytic activity and stability.This catalyzer is a carrier with the carbon nanotube, and cost is relatively costly; And the bulk density of carbon nanotube is less, may also can increase the cost of catalyzer aspect shaping of catalyst.
It is carrier that the present invention selects the nanocrystal metal oxide of unorthodox method preparation for use, has obtained better performances and cheap catalyzer.We select for use auxiliary agents such as alkalimetal oxide that this class catalyzer is modified, the activity of its ammonia decomposition reaction has been brought up to the level of the KRu/CNTs catalyzer that we invent in earlier stage, but the cost of catalyzer of the present invention reduces (annotate: the magnesian price of 500 grams is 42 yuan, and the price of 500 gram multi-walled carbon nano-tubes about 25000 yuan) significantly.
Summary of the invention
The purpose of this invention is to provide a class low temperature high activity (activity is represented with the transformation efficiency of ammonia and the generating rate of hydrogen in the literary composition) and be used for ammonia decomposition reaction preparation zero CO
xThe simple method for preparing catalyst of the catalyzer of hydrogen and preparation technology.
Low temperature high activity ammonia decomposition reaction preparation zero CO provided by the invention
xThe catalyst pack of hydrogen contains active ingredient, auxiliary agent and carrier.It is characterized in that: the composition of described catalyzer comprises active ingredient 0.1-30%, carrier 60-99%, auxiliary agent 0-20%.Described active ingredient is the metal nitride that is selected from transition metal and has precious metal character, preferred Ru, Rh, Ni and MoN; Described carrier is nanocrystal metal oxide (grain-size 2-200nm), preferred Al
2O
3, MgO, ZrO
2Be selected from basic metal, alkaline-earth metal and rare earth compound with the described auxiliary agent of ZnO, preferred KOH, NaOH, Ba (OH)
2And La (NO
3)
3
Preparation of catalysts method of the present invention, it is characterized in that: the nanocrystal metal oxide (grain-size 2-200nm) with the unorthodox method preparation is a carrier, " nano composite/oxide catalyst " notion that proposes with Tsing-Hua University is design basis (Bo-Qing Xu, et al., J.Phys Chem B., 107 (2003) 5203), the nanocrystalline size of nano-oxide carrier and reactive metal is complementary.The Preparation of catalysts steps in sequence comprises:
(1) prepares metal hydroxides with hydrolysis or sedimentary method, wash with alcohol then or these oxyhydroxide of alcohol reflux; If amphoteric oxyhydroxide, can also be with they reflux digestions in Glass Containers.
(2) with these oxyhydroxide after super-dry or roasting, flood the precursor solution of active ingredient again, 20-120 ℃ of dry back in 300-900 ℃ of roasting;
(3) again sample is used hydrogen reducing at 300-900 ℃, add auxiliary agent then, dry back at 20-120 ℃ in 300-900 ℃ of roasting;
(4) the reaction procatalyst need be 300-900 ℃ of activation.
In above-mentioned Preparation of catalysts method, the presoma of the described active ingredient of step (2) is any in soluble metal muriate, nitrate, the organic salt.
In above-mentioned Preparation of catalysts method, when active ingredient was transition metal (as Ru, Rh, Ni), the solvent that is used for lytic activity component presoma was organic compound, preferred alcohol and acetone.
In above-mentioned Preparation of catalysts method, when active ingredient was transition metal, catalyzer was at 300-900 ℃ of logical H
2Reduction activation; When active ingredient is when having the metal nitride of precious metal character, catalyzer is at 600-900 ℃ of logical ammonia activation.
In above-mentioned Preparation of catalysts method, be ZrO as step (1) carrier
2, can also be with its presoma ZrO (OH)
2Reflux digestion in Glass Containers.
Catalyzer of the present invention has very high catalytic activity to ammonia decomposition reaction, and preparation technology is simple.This class catalyzer is not only applicable to ammonia and decomposes the reaction process of making hydrogen, but also can be used for the various purifying treatment that contain ammonia gas.
It can accomplish the end in view evidence.
Description of drawings
Fig. 1 is the stability diagram of the catalyzer of embodiment 5 preparations.
Embodiment
The present invention will be further described below in conjunction with the embodiment of the invention and comparative example:
Embodiment 1
Get 0.1081g RuCl
3Be dissolved in the 10ml acetone and be configured to solution, then with 1g MgO[MgO according to the described method preparation of CN 1280882A (2001), grain-size and the specific surface of sample behind 600 ℃ of roasting 5h is respectively 11nm and 150m
2/ g] mix, at 55 ℃ of dry 5h, be warmed up to 600 ℃ with 10 ℃/min again, behind the stirring 1h at this roasting temperature 10h.This catalyzer is after 500 ℃ of reduction, and the Ru particle size is 4-10nm.Get 0.1g catalyzer (content of Ru is 5%) and be put in the quartz reactor, at 25%H
2Be warming up to 550 ℃ with 5 ℃/min in the-Ar atmosphere (80ml/min), and activate 2h under this temperature, be cooled to 500 ℃ then, and the high-purity ammonia of feeding reacts under this temperature, the flow velocity of ammonia is 50ml/min.Reaction result: the transformation efficiency of ammonia is 76.9%, and the generating rate of hydrogen is 25.7mmol/ (ming-cat).
Embodiment 2
Prepare the Ru/MgO catalyzer according to embodiment 1 described step,, obtain Ru and Na atomic ratio after drying and the roasting and be 1: 2 NaRu/MgO catalyzer then with the aqueous solution of its saturated dipping NaOH.Get the 0.1g catalyzer and be put in the quartz reactor, at 25%H
2Be warming up to 550 ℃ with 5 ℃/min in the-Ar atmosphere (80ml/min), and activate 2h under this temperature, be cooled to 520 ℃ then, and the high-purity ammonia of feeding reacts under this temperature, the flow velocity of ammonia is 50ml/min.Reaction result: the transformation efficiency of ammonia is 100%, and the generating rate of hydrogen is 33.4mmol/ (ming-cat).
Embodiment 3
Get 0.2162g RuCl
3Be dissolved in the 10ml acetone and be configured to solution, then with 1g ZrO
2[ZrO
2According to the described method preparation of CN 1260324A (2000), grain-size and the specific surface of sample behind 600 ℃ of roasting 5h is respectively 10nm and 70m
2/ g] mix, at 55 ℃ of dry 5h, be warmed up to 500 ℃ with 10 ℃/min again, behind the stirring 1h at this roasting temperature 10h.This catalyzer is after 500 ℃ of reduction, and the Ru particle size is 4-20nm.Get 0.1g catalyzer (content of Ru is 9.8%) and be put in the quartz reactor, at 25%H
2Be warming up to 550 ℃ with 5 ℃/min in the-Ar atmosphere (80ml/min), and activate 2h under this temperature, be cooled to 500 ℃ then, and the high-purity ammonia of feeding reacts under this temperature, the flow velocity of ammonia is 50ml/min.Reaction result: the transformation efficiency of ammonia is 92.8%, and the generating rate of hydrogen is 31.0mmol/ (ming-cat).
Embodiment 4
Get 0.2162g RuCl
3Be dissolved in the 10ml acetone and be configured to solution, then with 1.15g ZrO (OH)
2[ZrO (OH)
2According to the described method preparation of CN 1260324A (2000)] mix, at 55 ℃ of dry 5h, be warmed up to 500 ℃ with 10 ℃/min again, behind the stirring 1h at this roasting temperature 10h.Get 0.1g catalyzer (content of Ru is 9.8%) and be put in the quartz reactor, at 25%H
2Be warming up to 550 ℃ with 5 ℃/min in the-Ar atmosphere (80ml/min), and activate 2h under this temperature, be cooled to 500 ℃ then, and the high-purity ammonia of feeding reacts under this temperature, the flow velocity of ammonia is 50ml/min.Reaction result: the transformation efficiency of ammonia is 92.1%, and the generating rate of hydrogen is 30.8mmol/ (ming-cat).
Embodiment 5
Prepare Ru/ZrO according to embodiment 3 described steps
2Catalyzer then with the aqueous solution of its saturated dipping KOH, obtains Ru and K atomic ratio and is 1: 3 KRu/ZrO after drying and the roasting
2Catalyzer.Get the 0.1g catalyzer and be put in the quartz reactor, at 25%H
2Be warming up to 550 ℃ with 5 ℃/min in the-Ar atmosphere (80ml/min), and activate 2h under this temperature, be cooled to 480 ℃ then, and the high-purity ammonia of feeding reacts under this temperature, the flow velocity of ammonia is 50ml/min.Reaction result: the transformation efficiency of ammonia is 100.0%, and the generating rate of hydrogen is 33.5mmol/ (ming-cat), and the stability of catalyzer is seen accompanying drawing 1.
Embodiment 6
Get 0.2081g RuCl
3Be dissolved in the 10ml acetone and be configured to solution, then and 1gAl
2O
3[Al
2O
3According to implementing the preparation ZrO described in 3
2Method preparation, grain-size and the specific surface of sample behind 600 ℃ of roasting 5h is respectively 8nm and 268m
2/ g] mix, at 55 ℃ of dry 5h, be warmed up to 500 ℃ with 10 ℃/min again, behind the stirring 1h at this roasting temperature 10h.This catalyzer is after 500 ℃ of reduction, and the Ru particle size is 3-10nm.Get the 0.1g catalyzer and be put in the quartz reactor, at 25%H
2Be warming up to 500 ℃ with 5 ℃/min in the-Ar atmosphere (80ml/min), and activate 2h under this temperature, be cooled to 500 ℃ then, and the high-purity ammonia of feeding reacts under this temperature, the flow velocity of ammonia is 50ml/min.Reaction result: the transformation efficiency of ammonia is 86.9%, and the generating rate of hydrogen is 29.1mmol/ (ming-cat).
Embodiment 7
Prepare Ru/Al according to embodiment 6 described steps
2O
3Catalyzer is then with its saturated dipping Ba (NO
3)
2The aqueous solution, obtain Ru and Ba atomic ratio after drying and the roasting and be 1: 2 BaRu/Al
2O
3Catalyzer.Get the 0.1g catalyzer and be put in the quartz reactor, at 25%H
2Be warming up to 500 ℃ with 5 ℃/min in the-Ar atmosphere (80ml/min), and activate 2h under this temperature, be cooled to 500 ℃ then, and the high-purity ammonia of feeding reacts under this temperature, the flow velocity of ammonia is 50ml/min.Reaction result: the transformation efficiency of ammonia is 98.9%, and the generating rate of hydrogen is 33.1mmol/ (ming-cat).
Embodiment 8
Get 0.4081g Ni (NO
3)
2Be dissolved in the 10ml acetone and be configured to solution, then with 1g ZrO
2[ZrO
2According to the described method preparation of CN1267568 (2000), sample is at 600 ℃ of roasting 5h] mix, at 55 ℃ of dry 5h, be warmed up to 500 ℃ with 10 ℃/min again, behind the stirring 1h at this roasting temperature 10h.Get 0.1g catalyzer (content of Ni is 22.1%) and be put in the quartz reactor, at 25%H
2Be warming up to 700 ℃ with 5 ℃/min in the-Ar atmosphere (80ml/min), and activate 2h under this temperature, be cooled to 550 ℃ then, and the high-purity ammonia of feeding reacts under this temperature, the flow velocity of ammonia is 25ml/min.Reaction result: the transformation efficiency of ammonia is 88.9%, and the generating rate of hydrogen is 14.9mmol/ (ming-cat).
Embodiment 9
Prepare Ni/ZrO according to embodiment 8 described steps
2Catalyzer is then with its saturated dipping CsNO
3The aqueous solution, obtain Ni and Cs atomic ratio after drying and the roasting and be 1: 2 CsNi/ZrO
2Catalyzer.Get the 0.1g catalyzer and be put in the quartz reactor, at 25%H
2Be warming up to 700 ℃ with 5 ℃/min in the-Ar atmosphere (80ml/min), and activate 2h under this temperature, be cooled to 500 ℃ then, and the high-purity ammonia of feeding reacts under this temperature, the flow velocity of ammonia is 50ml/min.Reaction result: the transformation efficiency of ammonia is 94.3%, and the generating rate of hydrogen is 31.6mmol/ (ming-cat).
Embodiment 10
Get 0.2092g RhCl
3Be dissolved in the 10ml acetone and be configured to solution, with these solution and 1g ZrO
2[ZrO
2According to the described method preparation of CN1267568 A (2000), sample is at 600 ℃ of roasting 5h] mix, at 100 ℃ of dry 2h, be warmed up to 500 ℃ with 2 ℃/min again behind the stirring 1h, constant temperature calcining 5h under this temperature, cooling feeds 25%H then
2-Ar (60ml/min) is in 600 ℃ of activation 2h.Get 0.4018g Ba (NO
3)
2Be dissolved in 10ml water wiring solution-forming, and with these activatory catalyst mix, behind 55 ℃ of dry 10h, make catalyzer in 400 ℃ of roasting 2h.Getting the 0.1g catalyzer is put in the quartzy system reactor, at 25%H
2Be warming up to 550 ℃ with 2 ℃/min in the-Ar atmosphere (80ml/min), and activate 2h under this temperature, feed high-purity ammonia then and react at 520 ℃, the ammonia flow velocity is 30ml/min.Reaction result: the transformation efficiency of ammonia is 98.1%, and the generating rate of hydrogen is 21.9mmol/ (ming-cat).
Embodiment 11
Get 0.3471g ammonium molybdate and 0.4411g nickelous nitrate and be dissolved in the 10ml water and be configured to solution, then with 1g ZrO
2[ZrO
2According to the described method preparation of 1267568A (2000), sample is at 600 ℃ of roasting 5h] mix, at 55 ℃ of dry 10h, be warmed up to 600 ℃ with 2 ℃/min again, behind the stirring 1h at this roasting temperature 5h.Get 0.1g catalyzer (content of Mo is 14.1%, and the content of Ni is 10.6%) and be put in the quartz reactor, at NH
3Be warming up to 900 ℃ with 5 ℃/min in the stream, and under this temperature nitrogenize 2h, under nitrogen protection, be quickly cooled to room temperature then, be warming up to 550 ℃ then, and under this temperature, carry out ammonia decomposition reaction, the flow velocity of ammonia is 25ml/min.Reaction result: the transformation efficiency of ammonia is 98.1%, and the generating rate of hydrogen is 1 6.4mmol/ (ming-cat).
In order to further specify the superiority of catalyzer of the present invention, select following catalyzer for use as a comparison case.
Comparative example 1
Get 0.1081g RuCl
3Be dissolved in the 10ml acetone and be configured to solution, mix with the commercial MgO of 1g (analytical pure, the Beijing Chemical Plant produces) then, stir behind the 1h, be warmed up to 500 ℃ with 2 ℃/min again, at this roasting temperature 2h at 55 ℃ of dry 2h.Get 0.1g catalyzer (content of Ru is 5.0%) and be put in the quartz reactor, at 25%H
2Be warming up to 500 ℃ with 5 ℃/min in the-Ar atmosphere (80ml/min), and activate 2h under this temperature, feed high-purity ammonia then and react at 500 ℃, the flow velocity of ammonia is 50ml/min.Reaction result is: the transformation efficiency of ammonia is 43.7%, and the generating rate of hydrogen is 14.6mmol/ (ming-cat).
Comparative example 2
Get 0.1081g RuCl
3Be dissolved in the 10ml acetone and be configured to solution, mix with the 1g carbon nanotube then, stir behind the 1h, be warmed up to 500 ℃ with 2 ℃/min again, at this roasting temperature 2h at 55 ℃ of dry 2h.Get 0.1g catalyzer (content of Ru is 5.0%) and be put in the quartz reactor, at 25%H
2Be warming up to 500 ℃ with 5 ℃/min in the-Ar atmosphere (80ml/min), and activate 2h under this temperature, feed high-purity ammonia then and react at 500 ℃, the flow velocity of ammonia is 50ml/min.Reaction result is: the transformation efficiency of ammonia is 43.7%, and the generating rate of hydrogen is 14.6mmol/ (ming-cat); The stability of catalyzer is seen accompanying drawing 1.
Claims (10)
1, low temperature modification ammonia decomposes the catalyzer of preparation hydrogen, and it contains active ingredient, auxiliary agent and carrier, it is characterized in that: described catalyzer is formed and is comprised: active ingredient 0.1-30%, carrier 60-99%, auxiliary agent 0-20%.
2, catalyzer according to claim 1 is characterized in that: described active ingredient is the metal nitride that is selected from transition metal and has precious metal character, preferred Ru, Rh, Ni and MoN.
3, catalyzer according to claim 1 is characterized in that: described carrier is a nanocrystal metal oxide, preferred Al
2O
3, MgO, ZrO
2And ZnO.
4, catalyzer according to claim 1 is characterized in that: described auxiliary agent is selected from basic metal, alkaline-earth metal and rare earth compound, preferred KOH, NaOH, Ba (OH)
2And La (NO
3)
3
5, a kind of method for preparing the catalyzer of low temperature modification ammonia decomposition preparation hydrogen as claimed in claim 1, it is characterized in that: described method is that the nanocrystal metal oxide for preparing with unorthodox method is a carrier, its grain-size is 2-200nm, the nanocrystalline size of nano-oxide carrier and reactive metal is complementary, and the Preparation of catalysts steps in sequence comprises:
(1) prepares the presoma oxyhydroxide of carrier by hydrolysis or sedimentary method, wash with alcohol then or these oxyhydroxide of alcohol reflux;
(2) with above-mentioned oxyhydroxide after super-dry or roasting, flood the solution of the presoma of active ingredient again, 20-120 ℃ of dry back in 300-900 ℃ of roasting;
(3) sample that again step (2) is obtained is used hydrogen reducing at 300-900 ℃, adds auxiliary agent then, and is dry back in 300-900 ℃ of roasting at 20-120 ℃;
(4) with above-mentioned reaction procatalyst 300-900 ℃ of activation.
6, Preparation of catalysts method according to claim 5 is characterized in that: active ingredient precursor described in the step (2) is any in the metal chloride, nitrate, organic salt of solubility.
7, according to claim 5 or 6 described Preparation of catalysts methods, it is characterized in that: the solvent that is used for lytic activity component presoma is organic compound, preferred alcohol and acetone.
8, according to claim 5 or 6 or 7 described Preparation of catalysts methods, it is characterized in that: when active ingredient was precious metal and transition metal, catalyzer was at 300-900 ℃ of logical H
2Reduction activation.
9, Preparation of catalysts method according to claim 5 is characterized in that: when active ingredient is when having the metal nitride of precious metal character, catalyzer is at 600-900 ℃ of logical ammonia activation, and the volume space velocity of ammonia is not less than 500h
-1
10, Preparation of catalysts method according to claim 5 is characterized in that: as step (1) carrier is ZrO
2, can also be with its presoma ZrO (OH)
2Reflux digestion in Glass Containers.
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| CN1318134C (en) * | 2004-11-11 | 2007-05-30 | 中国科学院大连化学物理研究所 | Prepn of nickel-base catalyst for decomposing ammonia |
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| KR101595963B1 (en) * | 2008-09-17 | 2016-02-19 | 가부시기가이샤 닛뽕쇼꾸바이 | Catalyst for ammonia decomposition, process for producing same, and method of treating ammonia |
| KR20110055722A (en) * | 2008-09-17 | 2011-05-25 | 니폰 쇼쿠바이 컴파니 리미티드 | Catalyst for ammonia decomposition, process for producing same, and method of treating ammonia |
| CN102356043A (en) * | 2009-04-07 | 2012-02-15 | 丰田自动车株式会社 | Hydrogen generating apparatus and hydrogen generating method |
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