CN101875016A - Catalyst for preparing methane by low-temperature oxidization of methane and preparation method and application thereof - Google Patents
Catalyst for preparing methane by low-temperature oxidization of methane and preparation method and application thereof Download PDFInfo
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- CN101875016A CN101875016A CN2009102377938A CN200910237793A CN101875016A CN 101875016 A CN101875016 A CN 101875016A CN 2009102377938 A CN2009102377938 A CN 2009102377938A CN 200910237793 A CN200910237793 A CN 200910237793A CN 101875016 A CN101875016 A CN 101875016A
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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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- 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
The invention discloses a catalyst for preparing methane by low-temperature oxidization of methane and a preparation method and application thereof. The catalyst consists of a molecular sieve carrier and an active ingredient supported on the carrier; and the active ingredient comprises copper oxide or copper oxide and noble metal compound active ingredient, wherein the mass ratio of the molecular sieve to the copper in the copper oxide to the noble metal is 100:1-5:0-1. The molecular sieve serves as the carrier, and the preparation method for the catalyst comprises the following steps of: mixing a precursor copper acetate of the basic active ingredient or/and a metal precursor of the noble metal active ingredient in a certain ratio to prepare solution; and soaking the molecular sieve in the solution to allow the metals of the active ingredient to be supported on the carrier, and washing, drying and baking to prepare the catalyst. The catalyst can catalyze the methane oxidation at low temperature to prepare the methanol; a catalytic reaction system is simple; and the yield and selectivity of the target product methanol are high.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method and application that is used for preparing methane by low-temperature oxidization of methane.
Background technology
China South Sea is one of four big oil-gas accumulation ground, the world, and its natural gas resource is very abundant.Along with the continuous increase of the gas field depth of water, the offshore distance also constantly increases.This will mean longer natural-gas transfer pipeline, longer hydrate inhibitor for natural gas (as methyl alcohol) transportation range, thereby cause the significantly increase of submarine pipeline construction cost, and the hydrate inhibitor cost of transportation also can roll up.On the other hand, thermodynamics injectings such as methyl alcohol are the necessitys of gas hydrates chemistry extraction system, if depend on the mode from land transport, then the cost of chemical injecting will significantly improve along with the increase of deep water gas field offshore distance.Therefore, on the job facilities of deep water gas field, methane in-situ is converted into methyl alcohol with significant.
At first, natural gas is the major product in deep water gas field, is methyl alcohol with the natural gas converted in-situ and is used for hydrate and suppresses, and can effectively reduce the acquisition cost and the freight of chemical agent.On the other hand, the methyl alcohol that the natural gas converted in-situ is obtained is applied to following exploitation of gas hydrates as the thermodynamics injecting, also can save the purchase cost and the cost of transportation of chemistry exploitation injecting, can avoid laying in a large amount of chemical reagent at the scene simultaneously, help exploiting on-the-spot safety.In addition, with respect to pipe pressurizing transportation and natural gas liquefaction technology, with the natural gas converted in-situ liquid fuel such as methyl alcohol and by failing outside the oil tanker at the natural gas resource enrichment region, also be one of cost-effective transportation resources.
For many years, methane oxidation prepares methyl alcohol and has received many researchers' concern and launched extensive studies.What present industrial methane system methyl alcohol adopted is two-step method, promptly prepares synthesis gas by methane, then by synthesis gas preparation methyl alcohol.In addition, document and patent report many directly oxidizing methanes prepare the method for methyl alcohol.No matter be industrial two-step method or the direct method of being reported, because have the reaction temperature height, energy consumption is big, reactant system is complicated, methanol product yield and problem such as selectivity is low, complex process, equipment are huge, all be not suitable for the on-the-spot methane in-situ of ocean natural gas exploitation and transform system methyl alcohol.For example: E.D.Park etc. (Catal.Comm., 2001,2,187-190) add Cu (CH with Pd/C
3COO)
2Be catalyst, H
2O
2Oxidizing of methylene system methyl alcohol.L.C.Kao etc. (J.Am.Chem.Soc., 1991,113,700-701) with Pd (O
2CC
2H
5)
2Be catalyst, at H
2O
2With catalytic methane in the trifluoroacetic acid system.Patent US5585515, WO2004069784, US2007149832 and WO2007073533 have reported methyl hydride catalyzed oxidation reaction in the trifluoroacetic acid system, and methane conversion is about 10%.B.Michalkiewcz etc. (Appl.Catal.A:, 2004,277,147-153) adopt the Fe-HSAM-5 catalyst, the methane conversion of acquisition is 31.51%, the selectivity of methyl alcohol is 10.79%.Patent CN101199939A adopts mesoporous molecular sieve carried Mo, the V catalyst, and methane conversion is 8-15%, the selectivity of methyl alcohol is 40-80%.Patent CN101209956A is catalyst with the iodine substance, is oxidant with potassium permanganate or potassium peroxydisulfate, and adds acetic acid and the alternative traditional sulfuric acid of heteropoly acid in reaction system, and methane conversion can reach 36.8%, and the yield of methyl alcohol is up to 32.8%.As seen, above reaction system complexity, need reaction raw materials such as strong oxidizer and acid, and reaction needed carries out under high temperature (greater than 300 ℃) condition, conversion ratio and selectivity are all undesirable.Patent US2004116752 and WO2004024280 utilize plasma oxidation methane system methyl alcohol, and methane conversion is 55%, and the yield of methyl alcohol is 9%.In addition, patent reports such as US6156211, DE3101021A1 and US5720858 photocatalysis methane system methyl alcohol at a lower temperature, but this method needs ultraviolet source, and methane conversion is less than 9%.
In sum, be suitable for the catalyst of ocean natural gas converted in-situ system methyl alcohol, must possess characteristics such as catalytic oxidation methane process is efficient, product is single, selectivity is high, reaction temperature is low, reaction system is simple, thereby reach that catalytic reaction technology is simple, energy consumption is little, efficient is high, requirement such as small investment and production cost are low.
Summary of the invention
The purpose of this invention is to provide a kind of Catalysts and its preparation method that methane oxidation prepares methyl alcohol that is used for.
Catalyst provided by the present invention is made up of molecular sieve carrier and the active component that loads on the described carrier; Described active component comprises cupric oxide, and wherein, the mass ratio of copper is 100 in described molecular sieve and the described cupric oxide: 1-5.
Described active component can be a cupric oxide only also; This moment, described catalyst was made up of molecular sieve carrier and load cupric oxide thereon.
Described active component also can be by at least a composition the in cupric oxide and the following noble metal: Au, Pt, Pd, Rh, Ru and Ir; Wherein, the copper in described molecular sieve, the described cupric oxide and the mass ratio of described noble metal are followed successively by 100: 1-5: 0-1, but do not comprise 100: 1-5: 0.
Molecular sieve described in the present invention can be micro porous molecular sieve or mesopore molecular sieve; Described micro porous molecular sieve can be ZSM type molecular sieve, preferred ZSM-5 molecular sieve, and described mesopore molecular sieve can be SBA molecular sieve or MCM molecular sieve, the preferred SBA-15 molecular sieve of described SBA molecular sieve, the preferred MCM-41 molecular sieve of described MCM molecular sieve.
Active component in the catalyst of the present invention all loads on the described molecular sieve with the form of particle, and described particle grain size distribution scope is 1-20nm, is preferably 1-8nm.
Preparation of catalysts method provided by the present invention comprises the steps:
1) aqueous solution of the metal precursor of the described active component of preparation;
When described active component was cupric oxide, described metal precursor was Schweinfurt green, copper nitrate, copper chloride or other soluble copper salt, and the concentration of copper ion is 0.5 * 10 in the described aqueous solution
-2Mol/L-2.5 * 10
-2Mol/L; When described active component was cupric oxide and noble metal, described metal precursor was the precursor and the noble metal precursor of cupric oxide, and the concentration of copper ion is 0.5 * 10 in the described aqueous solution
-2Mol/L-2.5 * 10
-2Mol/L, the concentration of precious metal ion is 0-2.7 * 10
-2Mol/L;
2) described molecular sieve carrier be impregnated in the aqueous solution of step 1) preparation, after stirring at room 24-36 hour, filter washing; Repeating step 2) operation at least twice loads to the metal in the described aqueous solution on the molecular sieve, obtains the precursor of described catalyst; Can be in the preparation process by the concentration of adjusting slaine mixed aqueous solution and the consumption of molecular sieve, the molecular sieve catalyst precursor that obtains having the different metal load capacity;
3) with the precursor drying of described catalyst 100-500 ℃ of roasting 24 hours, obtain described catalyst;
Above-mentioned noble metal precursor comprises the precursor of following at least a metal: Au, Pt, Pd, Rh, Ru, Ir metal precursor, for example gold chloride and chloroaurate, chloroplatinic acid and chloroplatinate, acid of chlorine palladium and palladium, radium chloride, ruthenic chloride, inorganic metallic precursors such as chloro-iridic acid and chloroiridate, and nitrotrimethylolmethane Phenylphosphine alloy, nitroso amino close platinum, oxalic acid closes platinum potassium and dicarbapentaborane closes organometallic complex precursors such as ruthenium.
Another object of the present invention provides described Application of Catalyst.
To be described catalyst prepare application in the methyl alcohol at methane oxidation in application provided by the present invention.
The method that described methane oxidation prepares methyl alcohol is: react after reactant and the described catalyst mix, described reactant is methane (or natural gas) and Air mixing gas, the reaction temperature of described reaction is 60-200 ℃, reaction pressure is 0.5-10.0MPa, catalyst amount can be 0.1g-1g, and the volume of reacting gas is 5-100L.
Described methane (or natural gas) and described reactant volume ratio be≤4% or 〉=50%.
The oxidation product that above-mentioned reaction obtains is single, almost has only methyl alcohol in the product, and selectivity can be up to 99.9%.
Catalyst of the present invention has the following advantages:
(1) catalyst of the present invention can directly obtain methyl alcohol in methane oxidization catalyzing reaction under the cryogenic conditions, and reaction temperature can be low to moderate 60 ℃, is different from required reaction temperature greater than 300 ℃ among other preparation methods, can cut down the consumption of energy greatly;
When (2) adopting this catalyst methane oxidation reaction, reaction system simple (comprising methane, air and catalyst) helps the reaction unit miniaturization; Do not need to use other that disagreeableness acid of environment or strong oxidizer etc. are added reactant, equipment is not had corrosion;
(3) the product kind is single, does not have other oxidation products such as formaldehyde, formic acid in the product, has only methyl alcohol to generate, and has avoided product to separate complicated technology such as post processing and is of value to the miniaturization design of reaction unit;
(4) yield of product methyl alcohol and selectivity are all very high, and yield was up to 63.2% o'clock, and the methyl alcohol selectivity still can keep 99.9%.
As seen, utilize catalyst of the present invention can reach simply, efficiently with the purpose of directly oxidizing methane system methyl alcohol.This catalyst can be a methyl alcohol with the natural gas converted in-situ, the exploitation of ocean gas hydrate is served in the injecting source that both can be used as chemical method, also can be used as simultaneously gas hydrates thermodynamics inhibitor and serve the pipeline conveying of natural gas, thereby reduce the buying and the cost of transportation of chemical reagent.
The specific embodiment
Below by embodiment catalyst provided by the invention and catalytic result thereof are further described, but protection domain not thereby limiting the invention.
Experimental technique described in the following embodiment if no special instructions, is conventional method; Described reagent and material if no special instructions, all can obtain from commercial channels.
Embodiment 1, be the catalyst and the catalytic effect of active component with the cupric oxide
1) Schweinfurt green is dissolved in to make concentration in the distilled water be 1.0 * 10
-2The solution of mol/L is got 1g and be impregnated in the above-mentioned solution of 35mL through the ZSM-5 (Catalyst Factory, Nankai Univ) of sodium ion exchange, and deionised water was filtered, spent to stirring at room after 24 hours.Again through the process of twice solution impregnation, stirring, filtration, washing, the carrier that obtains at last makes catalyst 1 air drying, 110 ℃ of roastings 24 hours with the carrier that obtains.The molecular sieve in the described catalyst 1 and the mass ratio of copper are 100: 2.1.Described metallic copper loads on the molecular sieve with the form of copper oxide particle, and the average grain diameter of described copper oxide particle is 3.6nm.
2) in autoclave (1L), be reactant with the air mixture that contains 4% methane, with 0.1g catalyst 1 methane oxidization catalyzing, reaction pressure is 1.5MPa, reacts 3 hours down in 150 ℃.Reaction result sees Table 1.
Embodiment 2, be the catalyst and the catalytic effect of active component with the cupric oxide
1) Schweinfurt green is dissolved in to make concentration in the distilled water be 2 * 10
-2The solution of mol/L is got 1g and be impregnated in the above-mentioned solution of 35mL through the ZSM-5 of sodium ion exchange, and deionised water was filtered, spent to stirring at room after 24 hours.Again through twice solution impregnation, stirring, filtration, washing process, the carrier that obtains at last makes catalyst 2 air drying, 110 ℃ of roastings 24 hours with the carrier that obtains.The molecular sieve in the described catalyst 2 and the mass ratio of copper are 100: 2.5.Described metallic copper loads on the molecular sieve with the form of copper oxide particle, and the average grain diameter of described copper oxide particle is 4.0nm.
2) in autoclave (1L), be reactant with the air mixture that contains 4% methane, with 0.1g catalyst 2 methane oxidization catalyzings, reaction pressure is 1.5MPa, reacts 3 hours down in 60 ℃.Reaction result sees Table 1.
Embodiment 3, be the catalyst and the catalytic effect of active component with cupric oxide and gold
1) Schweinfurt green and gold chloride (copper is 4: 1 with the mol ratio of gold) mixed dissolution being made copper ions concentration in distilled water is 1 * 10
-2Mol/L and gold ion concentration are 2.5 * 10
-3The mixed solution of mol/L is got 1g and be impregnated in the above-mentioned solution through the ZSM-5 of sodium ion exchange, and stirring at room was filtered, washed after 24 hours.Again through twice solution impregnation, stirring, filtration, washing process, the carrier that obtains at last makes catalyst 3 air drying, 110 ℃ of roastings 24 hours with the carrier that obtains.The mass ratio of the molecular sieve in the described catalyst 3, copper, gold was followed successively by 100: 1.9: 0.1, and described copper and gold load on the molecular sieve with the form of combined oxidation attitude nano particle, and the average grain diameter of described nano particle is 6.5nm.
2) in autoclave (1L), be reactant with the air mixture that contains 4% methane, with 0.1g catalyst 3 methane oxidization catalyzings, reaction pressure is 0.5MPa, reacts 3 hours down in 150 ℃.Reaction result sees Table 1.
3) in autoclave (1L), be reactant with the air mixture that contains 4% methane, with 0.1g catalyst 3 methane oxidization catalyzings, reaction pressure is 1.5MPa, reacts 3 hours down in 200 ℃.Reaction result sees Table 1.
4) in autoclave (1L), be reactant with the air mixture that contains 4% methane, with 0.1g catalyst 3 methane oxidization catalyzings, reaction pressure is 2.0MPa, reacts 3 hours down in 150 ℃.Reaction result sees Table 1.
5) in autoclave (1L), be reactant with the air mixture that contains 4% methane, with 0.1g catalyst 3 methane oxidization catalyzings, reaction pressure is 10MPa, reacts 3 hours down in 150 ℃.Reaction result sees Table 1.
6) in autoclave (1L), be reactant with the air mixture that contains 60% methane, with 0.1g catalyst 3 methane oxidization catalyzings, reaction pressure is 2.0MPa, reacts 3 hours down in 150 ℃.Reaction result sees Table 1.
Embodiment 4, be the catalyst and the catalytic effect of active component with cupric oxide and ruthenium
1) Schweinfurt green and ruthenic chloride (mol ratio of copper and ruthenium is 4: 1) mixed dissolution being made copper ions concentration in distilled water is 1 * 10
-2Mol/L and ruthenium ion concentration are 2.5 * 10
-3The mixed solution of mol/L is got 1g and be impregnated in the above-mentioned solution through the ZSM-5 of sodium ion exchange, and stirring at room was filtered, washed after 24 hours.Again through twice solution impregnation, stirring, filtration, washing process, the carrier that obtains at last makes catalyst 4 air drying, 110 ℃ of roastings 24 hours with the carrier that obtains.The mass ratio of the molecular sieve in the described catalyst 4, copper, palladium was followed successively by 100: 2.0: 0.08, and described copper and palladium load on the molecular sieve with the form of combined oxidation attitude nano particle, and the average grain diameter of described nano particle is 5.3nm.
2) in autoclave (1L), be reactant with the air mixture that contains 60% natural gas, with 0.1g catalyst 4 methane oxidization catalyzings, reaction pressure is 1.5MPa, reacts 3 hours down in 100 ℃.Reaction result sees Table 1.
Embodiment 5, be the catalyst and the catalytic effect of active component with the cupric oxide
1) Schweinfurt green is dissolved in to make concentration in the distilled water be 1.0 * 10
-2The solution of mol/L, get 1g through amido modified SBA-15 (preparation method of molecular sieve is referring to document Appl.Surf.Sci.2009,255,7672-7678) impregnated in the above-mentioned solution of 35mL, stirring at room is after 24 hours, filters, the deionized water washing.Again through twice solution impregnation, stirring, filtration, washing process, the carrier that obtains at last makes catalyst 5 air drying, 110 ℃ of roastings 24 hours with the carrier that obtains.The molecular sieve in the described catalyst 5 and the mass ratio of copper are 100: 2.5.Described metallic copper loads on the molecular sieve with the form of copper oxide particle, and the average grain diameter of described copper oxide particle is 3.4nm.
2) in autoclave (1L), be reactant with the air mixture that contains 4% methane, with 0.1g catalyst 5 methane oxidization catalyzings, reaction pressure is 1.0MPa, reacts 3 hours down in 150 ℃.Reaction result sees Table 1.
Embodiment 6, be the catalyst and the catalytic effect of active component with cupric oxide and platinum
1) Schweinfurt green and chloroplatinic acid (copper and platinum mol ratio are 4: 1) mixed dissolution being made copper ions concentration in distilled water is 1 * 10
-2Mol/L and platinum ion concentration are 2.5 * 10
-3The mixed solution of mol/L, get 1g through amido modified SBA-15 (preparation method of molecular sieve is referring to document Appl.Surf.Sci.2009,255,7672-7678) impregnated in the above-mentioned solution, stirring at room is after 24 hours, filters, washing.Again through twice solution impregnation, stirring, filtration, washing process, the carrier that obtains at last makes catalyst 6 air drying, 110 ℃ of roastings 24 hours with the carrier that obtains.The mass ratio of the molecular sieve in the described catalyst 6, copper, platinum was followed successively by 100: 2.4: 0.5, and described copper and platinum load on the molecular sieve with the form of combined oxidation attitude nano particle, and the average grain diameter of described nano particle is 3.8nm.
2) in autoclave (1L), be reactant with the air mixture that contains 4% methane, with 1g catalyst 6 methane oxidization catalyzings, reaction pressure is 1.0MPa, reacts 3 hours down in 100 ℃.Reaction result sees Table 1.
Embodiment 7, be the catalyst and the catalytic effect of active component with cupric oxide and gold
1) Schweinfurt green and gold chloride (copper is 4: 1 with the mol ratio of gold) mixed dissolution being made copper ions concentration in distilled water is 1 * 10
-2Mol/L and gold ion concentration are 2.5 * 10
-3The mixed solution of mol/L, get 1g through amido modified MCM-41 (preparation method of molecular sieve is referring to document Appl.Surf.Sci.2009,255,7672-7678) impregnated in the above-mentioned solution, stirring at room is after 24 hours, filters, washing.Again through twice solution impregnation, stirring, filtration, washing process, the carrier that obtains at last makes catalyst 3 air drying, 110 ℃ of roastings 24 hours with the carrier that obtains.The mass ratio of the molecular sieve in the described catalyst 3, copper, gold was followed successively by 100: 2.1: 0.6, and described copper and gold load on the molecular sieve with the form of combined oxidation attitude nano particle, and the average grain diameter of described nano particle is 3.5nm.
2) in autoclave (1L), be reactant with the air mixture that contains 4% methane, with 0.1g catalyst 7 methane oxidization catalyzings, reaction pressure is 1.5MPa, reacts 3 hours down in 150 ℃.Reaction result sees Table 1.
The part of test results of the methyl hydride catalyzed oxidation reaction for preparing methanol of table 1
As can be seen from Table 1, the catalyst that provides of the present invention has catalytic performance in the preparing methane by low-temperature oxidization of methane reaction, shown methyl alcohol yield and selectivity preferably.This catalyst can make methane under 60 ℃ of reaction temperatures oxidation reaction take place.The reaction yield of methyl alcohol obviously improves with the increase of reaction pressure.Therefore, the invention provides the reaction method that the methane oxidation with characteristic such as efficient, that product is single, selectivity is high, reaction temperature is low, reaction system is simple prepares methyl alcohol.Described catalyst has the application prospect that is applicable to ocean natural gas converted in-situ system methyl alcohol.
Claims (10)
1. one kind is used for the catalyst that methane oxidation prepares methyl alcohol, form by molecular sieve carrier and the active component that loads on the described carrier, it is characterized in that: described active component comprises cupric oxide, and wherein, the copper mass ratio is 100 in described molecular sieve and the described cupric oxide: 1-5.
2. catalyst according to claim 1 is characterized in that: described active component is a cupric oxide.
3. catalyst according to claim 1 is characterized in that: described active component is by at least a composition the in cupric oxide and the following noble metal: Au, Pt, Pd, Rh, Ru and Ir; Wherein, the copper in described molecular sieve, the described cupric oxide and the mass ratio of described noble metal are followed successively by 100: 1-5: 0-1, but do not comprise 100: 1-5: 0.
4. according to arbitrary described catalyst among the claim 1-3, it is characterized in that: described molecular sieve is micro porous molecular sieve or mesopore molecular sieve.
5. catalyst according to claim 4, it is characterized in that: described micro porous molecular sieve is a ZSM type molecular sieve, preferred ZSM-5 molecular sieve, described mesopore molecular sieve is SBA molecular sieve or MCM molecular sieve, the preferred SBA-15 molecular sieve of described SBA molecular sieve, the preferred MCM-41 molecular sieve of described MCM molecular sieve.
6. according to arbitrary described catalyst among the claim 1-5, it is characterized in that: described active component loads on the described molecular sieve with particle form, and the average grain diameter of described particle is 1-20nm, is preferably 1-8nm.
7. arbitrary described Preparation of catalysts method among the claim 1-6 comprises the steps:
1) preparation contains mantoquita or contains mantoquita and the aqueous solution of precious metal salt, and the concentration of copper ion is 0.5 * 10 in the described aqueous solution
-2Mol/L-2.5 * 10
-2Mol/L, the concentration of precious metal ion is 0-2.7 * 10
-2Mol/L; Described mantoquita is selected from least a in the soluble copper salt, as Schweinfurt green, copper nitrate or copper chloride; Described precious metal salt is selected from following at least a: gold chloride, chloroaurate, chloroplatinic acid, chloroplatinate, the acid of chlorine palladium, palladium, radium chloride, ruthenic chloride, chloro-iridic acid, chloroiridate, nitrotrimethylolmethane Phenylphosphine alloy, nitroso amino close platinum, oxalic acid closes platinum potassium and dicarbapentaborane closes ruthenium;
2) described molecular sieve carrier be impregnated in the aqueous metal salt of step 1) preparation, after stirring at room 24-36 hour, filter washing; Repeating step 2) operation at least twice loads on the molecular sieve metal in the described mixed aqueous solution, obtains the precursor of described catalyst;
3) with precursor drying, the 100-500 ℃ roasting of described catalyst 24 hours, obtain described catalyst.
8. arbitrary described catalyst prepares application in the methyl alcohol at methane oxidation among the claim 1-6.
9. application according to claim 8, it is characterized in that: the method that described methane oxidation prepares methyl alcohol is: will react after reactant and the described catalyst mix, described reactant is methane and Air mixing gas, the reaction temperature of described reaction is 60-200 ℃, and reaction pressure is 0.5-10.0MPa.
10. application according to claim 9 is characterized in that: in the described reactant volume ratio of methane and air for≤4% or 〉=50%.
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2009
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