CN101462058A - Catalyst for producing synthesis gas by reforming natural gas-carbon dioxide for industry - Google Patents
Catalyst for producing synthesis gas by reforming natural gas-carbon dioxide for industry Download PDFInfo
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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 provides an industrial catalyst for producing synthesis gas by natural gas-carbon dioxide reforming. The catalyst comprises the following components in percentage by weight: 5 to 19 percent of Ni, 20 to 70 percent of La, and 0 to 2 percent of precious metal; and the catalyst is prepared by powder molding or the impregnation of a carrier by an active constituent, and the carrier is a molecular sieve and a molding additive. The catalyst has high catalytic activity through a micro-reactor and pilot magnification activity evaluation; and compared with other catalysts, the catalyst has strong carbon deposition resistance and steady performance. The catalyst is suitable to produce the synthesis gas by reforming natural gas and carbon dioxide, and also is suitable to produce the synthesis gas by reforming combined raw materials such as flue gas, coke-oven gas and coal bed gas of fuel electric plants, dry gas of oil refineries and the like.
Description
Technical field:
The invention belongs to chemical field, be specifically related to a kind of industrial catalyst of reforming natural gas and carbon dioxide preparing synthetic gas.
Background technology:
Along with increase gradually to energy demand, the comprehensive utilization of natural gas and minimizing " greenhouse effects " gas discharging having caused people's extensive concern.China's natural gas resource is abundant, but still has the associated gas of oil exploitation and coal seam mine gas not to make full use of.And find that there is a large amount of natural gas resource (methane hydrate) in the seabed.In addition, a large amount of CO
2Gas has constituted global warming, constitutes serious threat for the following ecological balance.The main component of natural gas is methane (accounting for 75～95%), and industrialization has been for many years for methane vapor reforming preparing synthetic gas or hydrogen manufacturing.Methane portion oxidation synthesis gas (CH
4+ 1/2O
2=CO+2H
2△ H=-35.6KJ/mol) method though energy consumption is relatively low, exists catalyst hot issue and potential danger.In addition, as if being oxidant, need to increase synthesis gas and N with the air
2The separation investment of gas.If is oxidant with the pure oxygen, need to increase the investment of oxygen from air separation, therefore fail industrialization always.
Chinese patent 200410065196.9 discloses a kind of with CO
2CH for oxygen source
4The method of portion oxidation synthesis gas.Be CO
2Decompose down at 800～1000 ℃, and make and decompose the oxygen permeation membrane that the oxygen that produces constantly sees through Ca-Ti ore type, see through side and methyl hydride catalyzed reaction preparing synthetic gas at film then.The method is similar to the method for directly passing through oxygen permeation membrane separation of air oxygen, and has brought CO
2The energy consumption problem that decomposes, and the stability of perovskite oxygen permeation membrane and elevated-temperature seal problem are industrial is difficult to solution.
Natural gas or methane-CO 2 reformation (CH
4+ CO
2=CO+2H
2, △ H=247kJ/mol) and the preparing synthetic gas reaction is feasible from thermodynamics.And can produce the purity height, CO/H
2Ratio is about 1 synthesis gas.More suitable synthetic by F-T, prepare the diesel raw material of high-quality jet raw material and high cetane number.But owing to, not only reduced catalyst activity at the catalyst surface carbon distribution, and the structure of destructible catalyst, even stop up reactor, and energy consumption is higher relatively.Therefore, the industrial catalyst of development high activity, high stability is one of key factor that realizes the reforming natural gas and carbon dioxide preparing synthetic gas.
European patent EP 0692451 (1996) discloses at Ni/La
2O
3The method of reforming natural gas and carbon dioxide preparing synthetic gas on the catalyst.At 10mg Ni/La
2O
3With 20mg Al
2O
3On, obtain metastable CH at 750 ℃
4And CO
2Conversion ratio.Think La
2O
3Introducing help improving the stability of catalyst.But because the Ni direct impregnation is at La
2O
3On the carrier, very low (the about 4m of specific surface area of catalyst
2/ g), experimental result is found, still has a large amount of carbon distributions to produce.
Chinese patent 99110100.6 discloses a kind of preparation method of reforming natural gas and carbon dioxide catalyst for preparing synthetic gas.It is characterized in that cobalt and noble metal (as Pt, Pd) dual-active component loads on γ-Al by infusion process
2O
3On the carrier, this catalyst moves under the low-speed condition, and unstripped gas consists of CH
4/ CO
2=0.69.
Chinese patent 01135912.9 discloses a kind of reforming natural gas and carbon dioxide catalyst for preparing synthetic gas method, and (wherein a kind of is 6～13%Ni, and another kind is 1.5～3.5%MoO to utilize bimetallic
3Or WO
3) active component loads on SiO by infusion process
2And γ-Al
2O
3On the carrier.Although the activity rating result (reaction condition: air speed 8400mL/g.h, 780 ℃ of temperature, normal pressure) in these catalyst 20 hours shows CH
4And CO
2Conversion ratio all more than 90%.But this catalyst is 30～60 purpose beaded catalysts, can not use on industrial large-sized device.Up to the present, do not see the preparation of natural gas/CO 2 reformation industrial catalyst and the relevant report that evaluation is amplified in pilot scale yet.
Summary of the invention
Technical problem to be solved
Technical problem to be solved by this invention provides industrial catalyst of a kind of reforming natural gas and carbon dioxide preparing synthetic gas and preparation method thereof and the application in industry is amplified, and is serious to overcome existing catalyst carbon deposit, can't industrialized shortcoming.
Technical scheme
One of technical scheme provided by the invention is a kind of industrial catalyst of reforming natural gas and carbon dioxide preparing synthetic gas, the presoma of described activity of such catalysts component is 2 rock-steady structure compound for the La:Ni mol ratio, wherein each composition weight percentage composition is: Ni5～19%, La20～70%, noble metal 0～2%, and described catalyst is to form by the powder moulding or by the activity component impregnation carrier.
One of preferred version of above-mentioned catalyst is, described noble metal is one or more among Ru, Rh, the Pd, and the weight percentage in described catalyst is 0.01～2%.
Two of the preferred version of above-mentioned catalyst is that described carrier is ZSM-5, MCM-41, SBA-15 or γ-Al
2O
3In one or more.
As described herein, ZSM-5, MCM-41, SBA-15, γ-Al
2O
3Be meant that respectively (as: ZSM-5 is that specific area is about 250-280m to business-like and synthetic catalyst carrier
2/ g and aperture are the 0.5nm micro porous molecular sieve, γ-Al
2O
3Be that specific area is about 180-300m
2/ g and aperture are the 3-4nm oxide carrier, and MCM-41 is that specific area is about 600-1100m
2/ g and aperture are 3-4nm mesopore molecular sieve carrier, and SBA-15 is that specific area is about 600-920m
2/ g and aperture are 4-9nm mesopore molecular sieve carrier).
Three of the preferred version of above-mentioned catalyst is that described catalyst is support type or non-loading type.
Four of the preferred version of above-mentioned catalyst is that described catalyst shape is the cylinder of diameter 3mm.
Two of technical scheme provided by the invention is above-mentioned Preparation of catalysts method, in turn includes the following steps:
A) with nickel salt, lanthanum salt, precious metal salt dissolving, add organic complexing agent, stir and form the sol-gel body;
B) the gained gel worn out successively, foam, drying, make each composition weight percentage composition and be: Ni5～19%, La20～70%, the precursor compound of noble metal 0～2%, roasting obtains the powder catalyst;
C) in the powder catalyst, add adhesive, make mechanical-moulded catalyst.
One of preferred version of above-mentioned Preparation of catalysts method is that described noble metal is one or more among Ru, Rh, the Pd.
Two of the preferred version of above-mentioned Preparation of catalysts method is, described nickel salt is nickel nitrate or nickelous carbonate, and described lanthanum salt is lanthanum nitrate or lanthana, and described precious metal salt is one or more in chloride, oxide or the nitrate.
Three of the preferred version of above-mentioned Preparation of catalysts method is that described organic complexing agent is citric acid or ethylene glycol or its combination; Adhesive is aluminium glue or silica gel or its combination.
Four of the preferred version of above-mentioned method for preparing catalyst is, the ageing time of described step b) is 2～5 days, and the baking temperature scope is 70～120 ℃, and in constant pressure and dry 10～20 hours, the sintering temperature scope was 500～800 ℃, roasting 6～10 hours.
Three of technical scheme provided by the invention is above-mentioned Preparation of catalysts method, in turn includes the following steps:
A) with nickel salt, lanthanum salt, precious metal salt dissolving, add organic complexing agent, stir and form the sol-gel body;
B) drainage of gained gelinite is gone in the carrier to flood, dry then, roasting obtains catalyst; Wherein, carrier is ZSM-5, MCM-41, SBA-15, γ-Al
2O
3In one or more.
One of preferred version of above-mentioned method for preparing catalyst is for the baking temperature scope of described step b) is 70～120 ℃, constant pressure and dry 10～20 hours, and the sintering temperature scope is 500～800 ℃, roasting 6～10 hours.
Four of technical scheme provided by the invention is a kind of above-mentioned application of catalyst in the industry of reforming natural gas and carbon dioxide preparing synthetic gas is amplified, reaction raw materials is that percent by volume is 0.6～1.0 natural gas and carbon dioxide, range of reaction temperature is 600～950 ℃, reaction pressure scope 0.1～0.8MPa.
Beneficial effect
Catalyst of the present invention amplifies activity rating through microreactor and industry test, the catalytic activity height, and compare with other catalyst, anti-carbon can be strong.The life-span is investigated catalyst performance stabilised more than 100 hours.
Industrial catalyst of the present invention is applicable to the industry test amplifying device, not only be adapted to pure natural gas and CO 2 reformation preparing synthetic gas, and be adapted to the combination raw materials preparing synthetic gas by reforming such as flue gas, coke-stove gas, coal bed gas and refinery dry gas in thermal power plant.
The specific embodiment:
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
The experimental technique of unreceipted actual conditions in the following example, usually according to normal condition, as the catalyst handbook, or the condition of advising according to manufacturer.
Embodiment 1
Raw material: nickel nitrate: Ni (NO
3)
26H
2O
Lanthanum nitrate: La (NO
3)
36H
2O
Citric acid: HO
2CCH
2(OH) (CO
2H) CH
2CO
2H
Ethylene glycol: HOCH
2CH
2OH
Aluminium glue: AlOOH
According to the ratio that La and Ni mol ratio equal 2, prepare certain density Ni (NO
3)
2And La (NO
3)
3Mixed aqueous solution, add the citric acid and the ethylene glycol solution of 1.5 times of concentration of metal ions then.Under 50～60 degrees centigrade condition, stirred 20 hours, promptly get the gel of green transparent.This gel wore out 2～3 days under constant temperature, and normal pressure foamed dry 20 hours in 70～80 ℃ of baking ovens then.Promptly obtain the catalyst based presoma of Ni of porous.The roasting 6 hours in 500 ℃ of air of this presoma can make the Ni-La powder catalyst of nano particle.This catalyst adds 10% aluminium glue and is in harmonious proportion evenly through grinding, and is processed into then
Industrial catalyst, the Ni weight percentage is 9～13% in the component, the La weight percentage is 34～54%.
In catalyst activity is estimated, industrial catalyst is broken into the beaded catalyst of the about 1～2mm of diameter, in 850 ℃ of hydrogen streams (20mL/min), reduced 1 hour unstripped gas (CH before the reaction
4/ CO
2) ratio of components be 1.0, the raw material air speed is 1.01 * 10
4h
-1, 850 ℃ of reaction temperatures, reaction pressure 0.1MPa, 11 hours evaluation result of catalyst sees Table 1.
Activity of such catalysts evaluation among table 1 embodiment 1
| Reaction time (hour) | CO 2Conversion ratio (%/mol) | CH 4Conversion ratio (%/mol) | CO selectivity (%/mol) | H 2Selectivity (%/mol) | Carbon productive rate (%/mol) |
| 1.6 | 87.7 | 66.3 | 95.6 | 71.7 | 3.4 |
| 2.1 | 88.4 | 67.8 | 91.3 | 69.5 | 6.8 |
| 3.9 | 85.7 | 67.9 | 90.6 | 70.1 | 7.2 |
| 4.4 | 87.8 | 65.2 | 92.7 | 72.0 | 5.6 |
| 5.5 | 86.2 | 64.3 | 92.4 | 73.3 | 5.8 |
| 7.5 | 85.6 | 58.8 | 92.2 | 74.3 | 5.6 |
| 8.8 | 86.2 | 60.9 | 99.6 | 65.5 | 0.3 |
| 9.8 | 87.6 | 63.9 | 88.1 | 74.1 | 9.0 |
| 10.5 | 86.6 | 59.7 | 99.3 | 63.9 | 0.5 |
Embodiment 2
According to the identical method of embodiment 1, mix La (NO
3)
3And Ni (NO
3)
2Solution adds a spot of RuCl
3Or RhCl
3In mixed liquor, dissolve, add the organic reagents such as citric acid of 1.5 times of concentration of metal ions then.
Stirring under 60 ℃ the condition more than 10 hours, to form homogeneous transparent Ni-M-La colloidal sol (M=Ru and/or Rh).At room temperature aging 4～5 days, the normal pressure dry 10h that foams in 110～120 ℃ baking oven.Roasting 6 hours in 800 ℃ Muffle furnace then promptly makes and contains noble metal Ru or Rh (0.01～2%) nickel base nanometer catalyst.Prepare according to embodiment 1 same procedure then
Cylindrical industrial catalyst, each composition weight percentage composition is: Ni9～15%, La17～35%, Ru0.4%.
In catalyst activity is estimated, the beaded catalyst that catalyst breakage becomes the about 1～2mm of diameter is amplified in industry.At 850 ℃, reduction is 1 hour among the hydrogen flow rate 20mL/min, unstripped gas (CH before the reaction
4/ CO
2) ratio of components be 1:1.The raw material air speed is 3.35 * 10
3h
-1, 850 ℃ of reaction temperatures, reaction pressure 0.11MPa, 103 hours activity ratings of catalyst the results are shown in Table 2.
Activity of such catalysts evaluation among table 2 embodiment 2
| Reaction time (hour) | CO 2Conversion ratio (%/mol) | CH 4Conversion ratio (%/mol) | CO selectivity (%/mol) | H 2Selectivity (%/mol) | Carbon productive rate (%/mol) |
| 4.7 | 92.5 | 94.4 | 94.3 | 78.5 | 5.3 |
| 5.4 | 92.9 | 94.7 | 90.4 | 83.3 | 9.0 |
| 7.3 | 93.5 | 94.3 | 91.2 | 81.2 | 8.3 |
| 8.0 | 91.4 | 94.8 | 97.2 | 75.5 | 2.6 |
| 9.0 | 91.2 | 95.5 | 96.1 | 73.0 | 3.7 |
| 25.5 | 92.3 | 94.8 | 94.3 | 77.0 | 5.3 |
| 28.8 | 91.8 | 93.8 | 97.3 | 75.1 | 2.5 |
| 29.5 | 91.6 | 94.0 | 96.0 | 75.3 | 3.7 |
| 30.3 | 92.1 | 94.2 | 97.5 | 73.2 | 2.4 |
| 31.7 | 91.7 | 93.9 | 93.4 | 76.6 | 6.1 |
| 32.5 | 92.0 | 94.2 | 96.8 | 73.2 | 3.0 |
| 33.6 | 91.1 | 94.1 | 99.8 | 70.3 | 0.2 |
| 49.4 | 90.9 | 93.7 | 97.5 | 74.6 | 2.3 |
| 52.9 | 91.3 | 93.6 | 98.1 | 74.0 | 1.8 |
| 53.9 | 91.1 | 93.3 | 99.9 | 71.4 | 0.1 |
| 55.4 | 91.8 | 92.5 | 99.3 | 75.7 | 0.7 |
| 81.1 | 90.4 | 92.8 | 99.1 | 73.8 | 0.8 |
| 98.0 | 91.3 | 92.1 | 93.6 | 79.8 | 5.9 |
| 102.6 | 91.0 | 90.9 | 99.9 | 74.5 | 0.1 |
| 103.3 | 91.6 | 91.1 | 97.3 | 77.0. | 2.5 |
Embodiment 3
According to the identical method of embodiment 1, with La (NO
3)
3And Ni (NO
3)
2Mixed liquor inject the commercially available ZSM-5 molecular sieve of 200g (available from Catalyst Factory, Nankai Univ), constantly flooding 5 hours under the stirring condition, add 1.5 times of concentration of metal ions citric acids and ethylene glycol then, stir 60 ℃ conditions and make the gelinite that contains the ZSM-5 carrier.The method of pressing embodiment 1 then is aging, foaming and dry in baking oven, and 550 ℃ of roastings 6 hours in Muffle furnace at last promptly obtain the supported catalyst of nickeliferous 9% (weight ratio).Prepare the 9%Ni-La/ZSM-5 industrial catalyst according to the method for executing example 1 then
Each composition weight percentage composition is: Ni9%, and La40～46%, all the other are carrier, adhesive and auxiliary agent.
The filling industrial catalyst is 0.3 kilogram in the reactor that industry is amplified.With this catalyst at 850 ℃, 20%H
2/ N
2Reduction is 8 hours in the gaseous mixture, and feeding gas is that (mol ratio is CH for natural gas and carbon dioxide
4/ CO
2=1.0～0.6).Under the differential responses condition, the composition of exit gas sees Table 3.
Activity of such catalysts evaluation among table 3 embodiment 3
Embodiment 4
According to the catalyst activity appreciation condition of embodiment 3, changing charging CH
4/ CO
2Ratio after, it the results are shown in Table 4.
The activity rating of catalyst under different feeds ratio of components condition among table 4 embodiment 4
Embodiment 5
In catalyst activity is estimated, the industrial catalyst among the embodiment 3 is broken into the beaded catalyst of the about 1～2mm of diameter.Be reduction 1 hour under the condition of 20mL/min at 850 ℃, hydrogen flow rate before the reaction, CH in the unstripped gas
4/ CO
2Ratio of components be 0.98.The raw material air speed is 6.3 * 10
3h
-1, reaction temperature is that 850 ℃, reaction pressure are 0.1MPa, 80 hours evaluation results of catalyst see Table 5.
Activity of such catalysts evaluation among table 5 embodiment 5
| Reaction time (hour) | CO2 conversion ratio (%/mol) | CH4 conversion ratio (%/mol) | CO selectivity (%/mol) | H2 selectivity (%/mol) | Carbon productive rate (%/mol) |
| 0.8 | 92.4 | 89.7 | 87.6 | 69.0 | 11.3 |
| 1.7 | 90.9 | 89.1 | 93.7 | 66.7 | 5.7 |
| 3.4 | 90.5 | 89.8 | 93.4 | 61.1 | 6.0 |
| 4.3 | 90.5 | 87.2 | 94.4 | 65.1 | 5.0 |
| 4.8 | 89.9 | 88.2 | 98.2 | 62.7 | 1.6 |
| 5.5 | 90.0 | 90.0 | 97.0 | 62.5 | 2.7 |
| 7.6 | 89.7 | 90.2 | 96.1 | 62.0 | 3.5 |
| 9.1 | 89.9 | 90.4 | 94.5 | 61.4 | 5.0 |
| 10.0 | 89.6 | 91.7 | 91.6 | 59.7 | 7.6 |
| 23.0 | 89.3 | 90.4 | 92.3 | 63.4 | 7.0 |
| 25.2 | 88.6 | 88.4 | 99.9 | 54.7 | 0.2 |
| 26.1 | 89.1 | 87.0 | 95.4 | 66.2 | 4.1 |
| 27.6 | 88.3 | 88.2 | 98.5 | 55.3 | 1.4 |
| 28.8 | 89.0 | 89.0 | 95.0 | 63.9 | 4.5 |
| 30.3 | 88.3 | 88.0 | 98.4 | 56.5 | 1.4 |
| 31.7 | 88.7 | 88.7 | 96.0 | 58.8 | 3.6 |
| 32.5 | 88.1 | 89.5 | 94.6 | 57.6 | 4.8 |
| 33.0 | 88.2 | 89.4 | 95.1 | 59.1 | 4.3 |
| 33.7 | 87.5 | 90.0 | 97.9 | 56.2 | 1.9 |
| 49.2 | 88.7 | 85.6 | 97.6 | 59.6 | 2.1 |
| 51.5 | 87.7 | 86.6 | 98.0 | 57.0 | 1.7 |
| 53.2 | 88.8 | 86.7 | 95.3 | 58.5 | 4.1 |
| 54.2 | 88.1 | 86.1 | 95.9 | 58.7 | 3.6 |
| 55.1 | 88.2 | 86.3 | 94.1 | 59.1 | 5.1 |
| 56.0 | 88.4 | 85.6 | 94.3 | 59.2 | 5.0 |
| 56.5 | 87.9 | 85.4 | 96.6 | 57.8 | 3.0 |
| 57.0 | 88.1 | 85.3 | 96.7 | 59.8 | 2.8 |
| 71.8 | 87.6 | 85.3 | 96.7 | 58.1 | 2.9 |
| 72.2 | 87.0 | 85.4 | 99.1 | 58.1 | 0.8 |
| 72.9 | 86.9 | 85.5 | 97.2 | 57.9 | 2.4 |
| 75.3 | 86.3 | 85.6 | 99.4 | 53.2 | 0.5 |
| 75.4 | 85.9 | 85.0 | 99.7 | 53.3 | 0.3 |
| 76.3 | 87.0 | 85.6 | 97..0 | 56.2 | 2.6 |
| 77.3 | 85.3 | 84.9 | 99.4 | 53.8 | 0.5 |
| 78.4 | 86.8 | 85.7 | 97.3 | 55.6 | 2.3 |
| 79.4 | 85.8 | 85.4 | 99.8 | 53.3 | 0.2 |
| 80.7 | 87.5 | 85.2 | 97.5 | 54.8 | 2.2 |
Embodiment 6
Preparing the Ni weight percentage according to embodiment 3 identical methods is 10% Ni/La
2O
3/ MCM-41 catalyst, surplus composition are that mass ratio is the carrier La of 45:55
2O
3And MCM-41 (department of chemistry of University Of Tianjin catalyst chamber is synthetic according to open source literature J.Catal.249 (2007) 102).
In catalyst and activity rating, at 700 ℃, hydrogen flow rate is to reduce 1 hour unstripped gas (CH under the 20mL/min condition before the reaction
4/ CO
2) ratio of components be 1:1.The raw material air speed is 1.17 * 10
4h
-1, reaction temperature is that 850 ℃, reaction pressure are 0.1MPa, 10 hours evaluation results of catalyst see Table 6.
Activity of such catalysts evaluation among table 6 embodiment 6
| Reaction time (hour) | CO 2Conversion ratio (%/mol) | CH 4Conversion ratio (%/mol) | CO selectivity (%/mol) | H 2Selectivity (%/mol) | Carbon productive rate (%/mol) |
| 0.1 | 90.1 | 90.3 | 93.0 | 76.3 | 6.3 |
| 1.8 | 90.4 | 91.0 | 87.9 | 69.9 | 11.0 |
| 2.8 | 89.7 | 91.5 | 89.8 | 64.4 | 9.2 |
| 3.3 | 89.1 | 90.7 | 95.1 | 66.0 | 4.4 |
| 3.8 | 89.1 | 89.2 | 98.8 | 66.1 | 1.0 |
| 4.3 | 90.4 | 88.1 | 96.3 | 70.6 | 3.3 |
| 4.8 | 89.8 | 88.6 | 99.0 | 69.0 | 0.9 |
| 6.0 | 88.7 | 91.8 | 97.9 | 62.5 | 1.9 |
| 6.5 | 89.5 | 91.7 | 94.1 | 66.3 | 5.3 |
| 7.4 | 90.0 | 91.9 | 90.7 | 66.5 | 8.5 |
| 8.9 | 89.5 | 91.7 | 91.5 | 63.9 | 7.7 |
| 10.0 | 88.8 | 91.9 | 91.8 | 61.9 | 7.4 |
Embodiment 7
With reference to embodiment 1 same procedure, preparation La:Ni mol ratio is 2 presoma, then by dipping method with commercially available ZSM-5 carrier
Available from Catalyst Factory, Nankai Univ) mix with rare colloidal sol of nickel active component.Under continuous stirring condition with the rare sol impregnation ZSM-5 of this presoma molecular sieve 36 hours.Under 120 ℃ of conditions after the drying, 550 ℃ of calcined catalyst samples are 6 hours in Muffle furnace.What promptly obtain support type contains the industrial catalyst that the Ni weight percentage is 6～9% Ni/La/ZSM-5, wherein La
2O
3Weight percentage is lower than 20%.
With reference to embodiment 2 the same terms, directly applicable industry is carried out activity rating with cylinder shape catalyst, and at 850 ℃, hydrogen flow rate is 20mL/min reduction 1 hour, unstripped gas (CH before the reaction
4/ CO
2) ratio of components be 1:1.The raw material air speed is 1.2 * 10
3h
-1, 850 ℃ of reaction temperatures, reaction pressure 0.1MPa, 100 hours activity ratings of catalyst the results are shown in Table 7.
Activity of such catalysts evaluation among table 7 embodiment 7
| Reaction time (hour) | CO 2Conversion ratio (%/mol) | CH 4Conversion ratio (%/mol) | CO selectivity (%/mol) | H 2Selectivity (%/mol) | Carbon productive rate (%/mol) |
| 0.1 | 94.9 | 97.5 | 98.9 | 84.4 | 1.1 |
| 5.0 | 94.3 | 97.8 | 96.8 | 79.9 | 3.1 |
| 6.7 | 94.6 | 97.7 | 99.0 | 81.2 | 1.0 |
| 7.4 | 94.7 | 97.5 | 95.7 | 85.4 | 4.1 |
| 8.5 | 94.0 | 97.2 | 96.1 | 86.3 | 3.8 |
| 21.6 | 94.5 | 97.8 | 92.8 | 88.8 | 6.9 |
| 23.0 | 93.9 | 97.9 | 93.4 | 84.2 | 6.3 |
| 27.1 | 95.8 | 96.9 | 96.6 | 83.6 | 3.3 |
| 27.9 | 95.4 | 97.6 | 96.1 | 84.6 | 3.8 |
| 29.2 | 95.5 | 97.3 | 93.2 | 87.7 | 6.6 |
| 47.3 | 94.7 | 97.5 | 99.5 | 80.7 | 0.5 |
| 51.3 | 95.3 | 97.3 | 95.9 | 84.5 | 4.0 |
| 53.0 | 95.3 | 97.4 | 93.4 | 87.1 | 6.3 |
| 69.8 | 94.2 | 97.5 | 97.1 | 83.0 | 2.8 |
| 71.5 | 94.6 | 97.5 | 97.5 | 80.7 | 2.4 |
| 73.5 | 94.5 | 97.9 | 96.6 | 82.9 | 3.3 |
| 75.8 | 95.8 | 97.5 | 93.8 | 87.3 | 6.7 |
| 76.8 | 94.5 | 97.7 | 95.2 | 84.0 | 4.6 |
| 80.0 | 94.8 | 97.3 | 98.9 | 82.2 | 1.1 |
| 100.2 | 94.8 | 97.3 | 94.7 | 86.4 | 5.1 |
Claims (10)
1. the industrial catalyst of a reforming natural gas and carbon dioxide preparing synthetic gas, each composition weight percentage composition of described catalyst is: Ni5～19%, La20～70%, noble metal 0～2%, and described catalyst is to form by the powder moulding or by the activity component impregnation carrier.
2. catalyst according to claim 1 is characterized in that, described noble metal is one or more among Ru, Rh, the Pd, and the weight percentage in described catalyst is 0.01～2%.
3. catalyst according to claim 1 is characterized in that, described carrier is ZSM-5, MCM-41, SBA-15 or γ-Al
2O
3In one or more.
4. catalyst according to claim 1 is characterized in that, described catalyst is support type or non-loading type.
5. catalyst according to claim 1 is characterized in that, described catalyst shape is the cylinder of diameter 3mm.
6. described Preparation of catalysts method of claim 1 in turn includes the following steps:
A) with nickel salt, lanthanum salt, precious metal salt dissolving, add organic complexing agent, stir and form the sol-gel body;
B) the gained gel worn out successively, foam, drying, make each composition weight percentage composition and be: Ni5～19%, La20～70%, the precursor compound of noble metal 0～2%, roasting obtains the powder catalyst;
C) in the powder catalyst, add adhesive, make mechanical-moulded catalyst.
7. Preparation of catalysts method according to claim 6 is characterized in that, described noble metal is one or more among Ru, Rh, the Pd.
8. Preparation of catalysts method according to claim 6 is characterized in that, described nickel salt is nickel nitrate or nickelous carbonate, and described lanthanum salt is lanthanum nitrate or lanthana, and described precious metal salt is one or more in chloride, oxide or the nitrate.
9. Preparation of catalysts method according to claim 6 is characterized in that, described organic complexing agent is citric acid or ethylene glycol or its combination; Adhesive is aluminium glue or silica gel or its combination.
10. the application of the described catalyst of claim 1 in the industry of reforming natural gas and carbon dioxide preparing synthetic gas is amplified, reaction raw materials is that percent by volume is 0.6～1.0 natural gas and carbon dioxide, range of reaction temperature is 600～950 ℃, reaction pressure scope 0.1～0.8MPa.
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