CN108622855A - A kind of method that natural gas catalysis oxidation prepares synthesis gas - Google Patents
A kind of method that natural gas catalysis oxidation prepares synthesis gas Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
Abstract
The present invention relates to a kind of methods that natural gas catalysis oxidation prepares synthesis gas, it is using oxidant gas and natural gas as unstripped gas, the catalyst bed of multilayer filling is catalyst system, it is 0.5 0.7 according to the volume ratio of oxidant gas and natural gas, it it is 200 500 DEG C in catalyst inlet temperature, reactor inlet pressure is 1 50bar, and unstripped gas charging rate is calculated as 5000 2000000hr with volume space velocity‑1Under the conditions of, hydrogen is prepared, the synthesis gas that carbon monoxide is key component.The present invention combines the catalyst of two kinds of Various Functions, form multi-layer catalyst reaction bed, the excellent selective oxidation ability of noble metal catalyst is played, the natural gas high-temperature vapor Reforming catalyst ability that non-precious metal catalyst can be provided is utilized again, reduces natural gas its conversion cost to the maximum extent.
Description
Technical field
The present invention relates to the sides that gas chemical industry's technical field more particularly to a kind of natural gas catalysis oxidation prepare synthesis gas
Method.
Background technology
Oil and coal are to support human society industrialization progress over more than 100 years so far as traditional fossil resource
Valuable source.But petroleum reserves gradually decays in recent years, a large amount of greenhouse gases generated after Coal Energy Source use, such as dioxy
Phenomena such as changing carbon and nitrogen oxide, sulfur oxide etc., having caused global warming and haze, promoting the energy to be sought for chemical field can
The renewable sources of energy substitute the utilization of oil, coal etc. such as solar energy, wind energy, biological energy source.And environmental pollution in fossil energy
The opening of minimum methane also increasingly attracts attention with utilization.
In the past 20 years, the utilization of shale gas have expanded rapidly methane and natural gas resource.2000 to 2013 it
Between, the yield of U.S.'s shale gas rapidly increases to 7.4 billion cubic meters by daily 0.3 billion cubic meter.Increase nearly 25 times.Shale gas
Yield also occupy 30% or more of natural gas total output.The price of natural gas is also by every million calorific values unit in 2010
(MMBTU) 13 dollars are reduced to nearly 2 dollars.
China is to verify the maximum countries and regions of shale gas reserves at present.37 tcm of proved reserves, can
11 tcm of mine reserves.Yield in 2010 is only 0.25 billion cubic meter.It is vertical that producing capacity in 2015 reaches 6,000,000,000
Square rice.As shale gas exploration, production technique are constantly progressive, shale gas will occupy in the energy resource structure in China or even the world
More importantly status.In order to the renewable energies such as fossil feedstocks and solar energy, biomass energy, wind energy such as coal, oil
Source distinguishes, and has the expert of energy field that the shale gas energy is known as emerging energy, and predict, rigid in renewable energy technologies
Ground zero, cost excessively high today will be following several using shale gas as efficient, the reasonable utilization of the natural gas resource of main source
The main means for reducing greenhouse effects in 10 years, reducing haze.
Shale gas resource in addition to substitution part using coal as power plant's raw material of raw material other than, more efficient utilization ways be by
It is converted to synthesis gas (the mainly gaseous mixture of carbon monoxide and hydrogen), then produces motor petrol, diesel oil using it as intermediate
Equal fuel and aviation kerosine, or utilize ripe synthesizing methanol technical transform for methanol it, and using methanol as catalytic material
Producing dimethyl ether by dehydrating produces the important industrial chemicals such as ethylene, propylene by MTO (methanol-to-olefins) technology.It wherein will be natural
Gas (shale gas) Efficient Conversion is the root of approach utilized above at the technology of synthesis gas, and the advance and efficiency of technology are direct
Determine the cost of downstream product.
The technology of present most ripe producing synthetic gas by natural gas conversion is that the catalytic water of natural gas (mainly methane) is steamed
Gas conversion (also referred to as catalyzed aqueous vapour is reformed), is abbreviated as SMR technology.The technology utilizes tubular type by way of indirectly heat
Reactor, the steam reforming that the combustion heat is passed to by combustion parts natural gas by tube wall strong endothermic in reaction tube are anti-
It answers (1-1).
CH4+H2O=3H2+CO (1-1)
Reaction (1-1) is a strong endothermic reaction, and reaction heat is 205.66KJ/mol CH4.In order to improve the balance of methane
Conversion ratio, reaction carry out usually between 700-1000 DEG C.The natural gas of burning offer reaction heat accounts for natural gas and always consumes outside boiler tube
The 1/3 of amount.The generated a large amount of carbon dioxide of flue gas emission.
The characteristics of technology is that industrialization is early, and technology maturation can produce H2:CO molar ratios are close to 3:1 synthesis gas,
It is suitable for hydrogen manufacturing or synthesis ammonia.But excessively high hydrogen:Carbon monoxide ratio is unsuitable for the application of methanol and FT synthetic oils.Due to
The limitation of heat transfer, reactor for treatment amount is small, and usual gas space velocity is in 5000-10000hr-1.Equipment tubing needs heat safe height
Nickel alloy steel, investment in fixed assets are big.Gradually by the preceding self-heatings developed of 20-30 in newly-built High-efficiency Gas is using device
(ATR) technology of reformation is replaced.
ATR technologies are on the basis of SMR technology, by the way that indirectly heat is changed to the improvement that direct-fired mode carries out
Technology.Natural gas and oxygen are carried out by part combustion reaction (1-2) by burner noz(zle) in the entrance of fixed bed reforming reactor.
CH4+O2=2H2O+CO2 (1-2)
It is passed through vapor, vapor in the reactor simultaneously:Between methane (mole)=1-1.5.Strongly exothermic burning is anti-
The catalyzed aqueous vapour that should be downstream reforms (1-1) and carbon dioxide dry gas reforming reaction (1-3) provides heat, and it is flat to reach self-heating
Weighing apparatus, therefore the technology is known as autothermal reforming reaction.
CH4+CO2=2H2+2CO (1-3)
The group of the synthesis gas produced becomes H2:CO (molar ratio)=2.4-2.8;As a result of the adiabatic reaction of self-heating
Device designs, and the volume ratio SMR of reactor is small.But the C in natural gas2Burning of the above hydrocarbon on reactor top
Section is easy coking, causes the obstruction of reactor.Therefore it needs to reduce C in raw material2The above constituent content.Gas can usually be passed through
Body purify or ATR reactors before pre-reforming realize.Improve equipment investment.In addition, the H of synthesis gas2:(2.5 is left for CO ratios
It is right) also above the H needed for synthesizing methanol and FT synthetic fuel oils2:The requirement of CO=2.Superfluous hydrogen needs are used.
Twentieth century eighties, Dutch Shell Co. Ltd develops on the basis of coal dry powder gasification technology and has industrialized one
Item natural gas non-catalytic partial oxidation technology.H is produced by reaction (1-4)2:CO is synthesized than the synthesis gas close to 2 for FT
In the industrial process of oil.
CH4+0.5O2=2H2+CO (1-4)
Reactor is the reacting furnace of sky.In order to avoid the coking in non-catalytic oxidation, the O2 of reactor feedstocks:CH4
Proportion requirement at 0.68-0.7 (mole) needs that steam is added.Since structure of reactor is simple, equipment investment ratio
SMR and ATR are low, but its carbon efficiencies is also below ATR technologies.It is difficult to be promoted.
Twentieth century nineties, Univ Minnesota-Twin Cities USA propose the concept of methyl hydride catalyzed selective oxidation.Its core
Technical principle is to make methane that selective oxidation reaction (1-4) occur with oxygen under high-selectivity catalyst effect.It is relatively small
Exothermic heat of reaction amount make reaction is adiabatic at 800-1100 DEG C to carry out.Concophillips Company on this basis, obtains relevant
Patented technology US7056488B2, US7871961B2 etc..It mainly describes using Noble Metal Rhodium as main active component, is aided with various
The catalyst preparation technology of auxiliary agent.It realizes under conditions of air speed 1000-1000000hr-1, the highly selective oxygen of natural gas
Metaplasia is at H2:Synthesis gas of the CO (molar ratio) close to 2.
However, the process of so-called natural gas selective catalysis conversion production synthesis gas, is similar to ATR to a certain extent
Process.When oxygen is in contact with the catalyst of inlet at a certain temperature with the mixture of natural gas, not as reaction
(1-4) carries out 100% selective oxidation reaction like that, and it is more likely that carrying out selective oxidation and part combustion reaction competition
Reaction.That is, other than reaction (1-4), reaction also below occurs.
2CH4+ 3O2=2CO+4H2O (1-5)
CH4+ O2=CO2+2H2 (1-6)
React (1-5), (1-6) may occur on catalyst surface, it is also possible to gap between catalyst granules or
In catalyst duct, occurred with non-catalytic reaction mechanism.The larger space in gap in the catalyst simultaneously, it is also possible to occur
Full combustion reaction (1-2).Since Selective Oxidation is all compared in part combustion reaction (1-5) (1-6) and completely burned reaction (1-4)
Thermal discharge is big, therefore, in the part that catalyst bed contacts at first with reaction raw materials, will generate hot localised points.Its temperature can
It can reach 1000-1150 ゜ C.Such high temperature easily causes catalyst carrier sintering and causes under catalyst activity surface
Drop.The decline of catalyst surface can reduce catalyst choice again, improve catalyst temperature, accelerator activator surface further drops
It is low.This vicious circle leads to catalyst inactivation quickly.
Invention content
To solve the above problems, the present invention is intended to provide a kind of method that natural gas catalysis oxidation prepares synthesis gas, uses
Catalyst system of the catalyst bed as the natural gas catalytic oxidation of multilayer filling, by urging for two kinds of Various Functions
Agent combines, and forms multiple catalyst reaction bed, that is, has played the excellent selective oxidation ability of noble metal catalyst, and utilize
The natural gas high-temperature vapor Reforming catalyst ability that non-precious metal catalyst can be provided, reduce to the maximum extent it is natural its
Conversion cost.
Specifically, the present invention provides a kind of method that natural gas catalysis oxidation prepares synthesis gas, with oxidant gas and
Natural gas is unstripped gas, and the catalyst bed of multilayer filling is catalyst system, according to the volume of oxidant gas and natural gas
Than being 200-500 DEG C, reactor inlet pressure 1-50bar in catalyst inlet temperature for 0.5-0.7, unstripped gas charging speed
Degree is calculated as 5000-2000000hr with volume space velocity-1Under the conditions of, hydrogen is prepared, the synthesis that carbon monoxide is key component
Gas..
Preferably, the catalyst bed is two layers of bed structure, wherein first layer is noble metal catalyst, the second layer
For the steam reforming catalyst agent that transition metal is main active component.
Preferably, the loadings of the noble metal catalyst are calculated as 5000-2000000hr with the air speed of unstrpped gas-1。
Preferably, the volume ratio of noble metal catalyst and transition-metal catalyst is preferably 1:10-1:1, more preferably 1:10-
1:5.
Preferably, the noble metal catalyst is the metal oxide modified aluminium oxide catalyst (Rh-Pt/ of rhodium platinum load
MOx-Al2O3), wherein metal M is selected from magnesium, calcium or lanthanide series.
Preferably, the steam reforming catalyst agent be using nickel as main active component, be carried on refractory material carrier, and
It is aided with the catalyst system of auxiliary agent.
Preferably, the refractory material is selected from aluminium oxide, spinelle, perovskite and/or violet spar etc..
Preferably, the auxiliary agent is selected from magnesium, potassium, cobalt, chromium and/or cerium etc..
Preferably, the oxidant gas is purity oxygen, oxygen-enriched air or air etc..
Compared with prior art, the technical advantages of the present invention are that:The present invention provides a kind of catalysis of novel natural gas
The method that oxidation prepares synthesis gas, catalyst bed the urging as the natural gas catalytic oxidation for using multilayer to fill
Agent system, the caltalyst tie up to superhigh temperature (>1100 ゜ C) reaction condition under, still be able to keep high-specific surface area.When anti-
After answering the oxygen in raw material to be completely consumed in the top layer certain thickness of catalyst bed, catalyst bed lower part is loaded non-expensive
Metallic catalyst is the vapor and CO 2 reformation catalyst of extraordinary methane, the final high synthesis for realizing oxidation reaction
Gas selectivity.
The method that novel natural gas catalysis oxidation provided by the invention prepares synthesis gas, by the catalyst of two kinds of Various Functions
In conjunction with forming multiple catalyst reaction bed, that is, played the excellent selective oxidation ability of noble metal catalyst, and be utilized non-
The natural gas high-temperature vapor Reforming catalyst ability that noble metal catalyst can be provided reduces its natural conversion to the maximum extent
Cost.
Description of the drawings
Fig. 1 is the structure chart for meeting the reactor selected by the natural gas catalysis oxidation of a preferred embodiment of the present invention.
Reference numeral:1-1 indicates the main body of reactor;1-A indicates oxidant (oxygen, oxygen-enriched air or normal air);
1-B indicates natural gas;1-C indicates synthesis gas
1-2 is unstripped gas air inlet pipe and mixer;
1-3 is reactor reducer and catalyst bed top inert filler;
1-4A is first layer catalyst bed;1-4B is second layer catalyst bed;
1-5 supports for catalyst bed.
Specific implementation mode
With reference to specific embodiment, the superiority of the present invention is elaborated.
Wherein, the present embodiment specific implementation step is, with material mixed gas (O2:NG=0.3-0.5 (molar ratio)) big
When passing through reactor under minimum linear velocity (about 1 meter per second), gradually passes through preheating material gas or directly heat the side of catalyst
Method slowly improves the temperature of catalyst, when catalyst bed outlet, which is stablized, is increased to inlet temperature or more rapidly, shows to be catalyzed
Oxidation reaction starts, and catalyst inlet temperature at this time is the initiation temperature of the catalyst.At this point, adjustment catalyst bed entrance
Temperature adjusts the O2 of material mixed gas to predetermined temperature (being usually 200-500 DEG C):NG molar ratios are between 0.55-0.65.Control
Raw material composition, air speed and reactor inlet temperature processed are stablized, into the steady state operation of reactor.Using chromatography, mass spectrum or other
Analysis method measures the composition of reactor outlet and reactor inlet, and turning for natural gas is calculated by material balance and product composition
The selectivity of rate and synthesis gas.
Wherein, index of correlation can be according to calculating defined below:
Methane conversion XCH4:
Hydrogen selective SH2:
Carbon monoxide selective SCO:
In synthesis gas
Wherein, FCH4, entrance, FCH4, outlet, FH2, outlet, FCO, outletRespectively methane entrance molar flow exports molar flow, hydrogen
With the outlet molar flow of carbon monoxide.These parameters can be according to product composition analysis as a result, the data such as feed rate calculate.
Refering to fig. 1, it is the reactor met selected by the natural gas catalysis oxidation of a preferred embodiment of the present invention
Structure chart is that 100 purposes are more with aperture it can be seen from the figure that in the embodiment of the present invention in the reaction tube of 10 millimeters of diameter
Hole zirconia ceramics is support, and the loading catalyst on zirconia ceramics, specific embodiment and its implementation result are as follows:
One, the rhodium platinum catalyst and non-precious metal catalyst of samarium modified aluminas load load in mixture
Comparative example 1:Single layer noble metal low-speed
The rhodium platinum catalyst (Rh-Pt/Sm2O3-Al2O3) of 0.8ml samarium modified aluminas load, low-speed is selected to load;
Comparative example 2:Single layer noble metal high-speed
The rhodium platinum catalyst (Rh-Pt/Sm2O3-Al2O3) of 0.2ml samarium modified aluminas load, high-speed is selected to load;
Embodiment 1:Load in mixture catalyst, the low loading amount of noble metal
Two layers of catalyst with different function is loaded in reactor, bottom is the conversion of 1.4ml industry secondary reformer natural gases
Catalyst recharges the rhodium platinum catalyst (Rh-Pt/Sm2O3-Al2O3) of 0.2ml samarium modified aluminas load on it.
Embodiment 2:Load in mixture catalyst, the high loading amount of noble metal
Two layers of catalyst with different function is loaded in reactor, bottom is the conversion of 1.1ml industry secondary reformer natural gases
Catalyst recharges the rhodium platinum catalyst (Rh-Pt/Sm2O3-Al2O3) of 0.5ml samarium modified aluminas load on it.
Wherein, embodiment 1 and the accordingly rhodium platinum catalyst of the samarium modified aluminas load used in comparative example
(Rh-Pt/Sm2O3-Al2O3) it is same batch of sample.
By the reactor filled in the mixed containing methane/oxygen/nitrogen=60.5/34.5/5 (volume) of 6.7L/min
Close the Selective Oxidation that methane is carried out in gas.Reaction result is as shown in Table 1:
The rhodium platinum catalyst and multi-layer catalyst performance comparison of 1 single layer samarium modified aluminas of table load
Two:The rhodium platinum catalyst of magnesium-modified alumina load is loaded in mixture with non-precious metal catalyst
Comparative example 3:Noble metal low-speed
Catalyst is the rhodium platinum catalyst (Rh-Pt/MgO-Al2O3) of the magnesium-modified alumina loads of 0.8ml;
Comparative example 4:Noble metal high-speed
Catalyst is the rhodium platinum catalyst (Rh-Pt/MgO-Al2O3) of the magnesium-modified alumina loads of 0.2ml;Embodiment 3:It is mixed
Fill catalyst, the low loading amount of noble metal
Two layers of catalyst with different function is loaded in reactor, bottom is the conversion of 1.4ml industry secondary reformer natural gases
Catalyst recharges the rhodium platinum catalyst (Rh-Pt/MgO-Al2O3) of the magnesium-modified alumina loads of 0.2ml on it.
Embodiment 4:Load in mixture catalyst, the high loading amount of noble metal
Two layers of catalyst with different function is loaded in reactor, bottom is the conversion of 1.1ml industry secondary reformer natural gases
Catalyst recharges the rhodium platinum catalyst (Rh-Pt/MgO-Al2O3) of the magnesium-modified alumina loads of 0.5ml on it.
Rhodium platinum catalyst (the Rh- of magnesium-modified alumina load used in embodiment 4 and corresponding comparative example
Pt/MgO-Al2O3) it is same batch of sample.
Mixing containing methane/oxygen/nitrogen=60.5/34.5/5 (volume) of the reactor filled in 6.7L/min
The Selective Oxidation of methane is carried out in gas.Reaction result is as shown in Table 2.
The rhodium platinum catalyst of the magnesium-modified alumina load of 2 single layer of table and multi-layer catalyst performance comparison
Three, the rhodium platinum catalyst and non-precious metal catalyst of lanthanum modified aluminas load load in mixture
Comparative example 5:
Catalyst is the rhodium platinum catalyst (Rh-Pt/La2O3-Al2O3) of 0.8ml lanthanum modified aluminas load;
Comparative example 6:
Catalyst is the rhodium platinum catalyst (Rh-Pt/La2O3-Al2O3) of 0.2ml lanthanum modified aluminas load;
Embodiment 5:Load in mixture catalyst, the low loading amount of noble metal
Two layers of catalyst with different function is loaded in reactor, bottom is the conversion of 1.4ml industry secondary reformer natural gases
Catalyst recharges the rhodium platinum catalyst (Rh-Pt/La2O3-Al2O3) of 0.2ml lanthanum modified aluminas load on it.
Embodiment 6:Load in mixture catalyst, the high loading amount of noble metal
Two layers of catalyst with different function is loaded in reactor, bottom is the conversion of 1.1ml industry secondary reformer natural gases
Catalyst recharges the rhodium platinum catalyst (Rh-Pt/La2O3-Al2O3) of 0.5ml lanthanum modified aluminas load on it.
Rhodium platinum catalyst (the Rh- of lanthanum modified aluminas load used in embodiment 5 and corresponding comparative example
Pt/La2O3-Al2O3) it is same batch of sample.
Mixing containing methane/oxygen/nitrogen=60.5/34.5/5 (volume) of the reactor filled in 6.7L/min
The Selective Oxidation of methane is carried out in gas.Reaction result is as shown in Table 3.
The rhodium platinum catalyst and multi-layer catalyst performance comparison of 3 single layer lanthanum modified aluminas of table load
As can be seen that the present invention urging using multilayer filling from the comparison of above-described embodiment 1-6 and comparative example 1-6
Catalyst system of the agent bed as the natural gas catalytic oxidation, the methane initial conversion obtained, and
The initial selectivity of hydrogen and carbon monoxide with the methane initial conversion and hydrogen for using single noble metal catalyst and
The initial selectivity of carbon monoxide is suitable, and, catalyst system provided by the present invention has more stable property.
Four, using the methyl hydride catalyzed air oxidation reaction of the double-deck bifunctional catalyst
Hydrogen and the high synthesis gas of carbon monoxide content can be prepared by carrying out methane oxidation as oxidant using oxygen, still,
Oxygen cost is more much higher than air.In the application for not needing high-purity synthesis gas, oxygen can be replaced to carry out methane with air
Or the selective oxidation of natural gas.By taking the rhodium platinum catalyst (Rh-Pt/La2O3-Al2O3) of lanthanum modified aluminas load as an example;According to
With method as embodiment three classes, bifunctional catalyst point is loaded into the reaction tube of 10mm for two layers, is filled shown in table four
Reacting for methane and air is carried out under the amount of filling out and reaction condition, as a result as shown in Table 4.According to unstripped gas composition and product form
The conversion ratio that methane can be calculated is 91.3%, and the selectivity of hydrogen is 92.8%, and the selectivity of carbon monoxide is
94.1%.
4 noble metal catalyst of table loads in mixture catalyzing natural gas air oxidation performance with industrial reforming catalyst
To sum up, the method that natural gas catalysis oxidation provided by the invention prepares synthesis gas uses multilayer to fill
Catalyst system of the catalyst bed as the natural gas catalytic oxidation, the caltalyst tie up to superhigh temperature (>1100
DEG C) reaction condition under, still be able to keep high-specific surface area.When the oxygen in reaction raw materials is certain in the top layer of catalyst bed
After being completely consumed in thickness, the non-precious metal catalyst of catalyst bed lower part filling is the vapor and two of extraordinary methane
Carbonoxide reforming catalyst, the final high synthesis gas selectivity for realizing oxidation reaction.To play noble metal catalyst
Excellent selective oxidation ability, and the natural gas high-temperature vapor Reforming catalyst energy that non-precious metal catalyst can be provided is utilized
Power reduces natural gas conversion cost to the maximum extent.
It should be noted that the embodiment of the present invention has preferable implementation, and not the present invention is made any type of
Limitation, any one skilled in the art change or are modified to possibly also with the technology contents of the disclosure above equivalent effective
Embodiment, as long as without departing from the content of technical solution of the present invention, according to the technical essence of the invention to made by above example
Any modification or equivalent variations and modification, in the range of still falling within technical solution of the present invention.
Claims (10)
1. a kind of method that natural gas catalysis oxidation prepares synthesis gas, which is characterized in that
Using oxidant gas and natural gas as unstripped gas, the catalyst bed of multilayer filling is catalyst system, according to oxidant
The volume ratio of gas and natural gas is 0.5-0.7, is 200-500 DEG C in catalyst inlet temperature, reactor inlet pressure 1-
50bar, unstripped gas charging rate are calculated as 5000-2000000hr with volume space velocity-1Under the conditions of, hydrogen, an oxidation is prepared
Carbon is the synthesis gas of key component.
2. the method as described in claim 1, which is characterized in that the catalyst bed is two layers of bed structure, wherein first
Layer is noble metal catalyst, and the second layer is the steam reforming catalyst agent that transition metal is main active component.
3. method as claimed in claim 2, which is characterized in that noble metal catalyst loadings are calculated with the air speed of unstrpped gas
For 5000-2000000hr-1。
4. method as claimed in claim 2, which is characterized in that the volume ratio of noble metal catalyst and transition-metal catalyst is
1:10-1:1.
5. method as claimed in claim 4, which is characterized in that the volume ratio of noble metal catalyst and transition-metal catalyst is
1:10-1:5.
6. method as claimed in claim 2, which is characterized in that the noble metal catalyst is the metal oxide of rhodium platinum load
Modified alumina catalyst (Rh-Pt/MOx-Al2O3), wherein metal M is selected from magnesium, calcium or lanthanide series.
7. method as claimed in claim 2, which is characterized in that it is main activearm that the steam reforming catalyst agent, which is with nickel,
Point, it is carried on refractory material carrier, and be aided with the catalyst system of auxiliary agent.
8. the method for claim 7, which is characterized in that the refractory material is selected from aluminium oxide, spinelle, perovskite
And/or violet spar.
9. the method for claim 7, which is characterized in that the auxiliary agent is selected from magnesium, potassium, cobalt, chromium and/or cerium.
10. the method as described in claim 1, which is characterized in that the oxidant gas is purity oxygen, oxygen-enriched air or sky
Gas.
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