CN105478120B - A kind of preparation method of red mud base Fe-series catalyst and its application in methane cracking hydrogen production - Google Patents
A kind of preparation method of red mud base Fe-series catalyst and its application in methane cracking hydrogen production Download PDFInfo
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- CN105478120B CN105478120B CN201510802366.5A CN201510802366A CN105478120B CN 105478120 B CN105478120 B CN 105478120B CN 201510802366 A CN201510802366 A CN 201510802366A CN 105478120 B CN105478120 B CN 105478120B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
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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
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
- C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
- C01B3/26—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using catalysts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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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
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
Abstract
The present invention relates to a kind of preparation method of red mud base Fe-series catalyst and its application in methane cracking.The characteristics of this method is using aluminum oxide industry waste material i.e. red mud as raw material, and a certain amount of iron is introduced thereto by homogeneous co-precipitation process again after the molten processing of peracid, after by drying, calcining and hydrogen reducing, obtain a kind of red mud base Fe-series catalyst.Its pore structure is more flourishing compared with red mud, and the content of active metal iron also increases, and catalyst particle size is highly uniform and the decentralization of metallic iron is preferable.The advantage of the method has catalysis and the mineral composition of co-catalysis function in red mud is taken full advantage of, improve the pore structure of red mud in itself, the introducing of iron improves the content of its active component simultaneously, substantially increases the Activity and stabill of red mud catalytic methane cracking hydrogen production reaction.The present invention not only reduces the preparation cost of methane cracking hydrogen production catalyst, also opens road for red mud comprehensive utilization of resources.
Description
Technical field
The invention belongs to methane catalytic decomposition hydrogen producing technology field, and in particular to a kind of preparation of red mud base Fe-series catalyst
Method and its application in methane cracking hydrogen production.
Background technology
Red mud (RM) is the waste residue of aluminum smelting industry, due to wherein containing substantial amounts of iron oxide (Fe2O3) and crimson color is presented,
Oxide in other red mud also containing metals such as a large amount of aluminium, silicon, titaniums.Red mud is main at present or heap is carried out in a manner of building a dam
Deposit, this aspect causes the waste of valuable metal resource in red mud, on the other hand because red mud has strong basicity, land occupation
Also soil and underground water are polluted while resource.Therefore recycling utilization are carried out to red mud, useful metal is reclaimed, reduces ring
Border pollution is imperative.There is comprehensive utilization of the personnel to red mud to be studied at present.Such as Chinese patent CN
102502944A elaborates a kind of zone heterogeneous catalytic oxidation technology for removing pollutants by red-mud catalyst, is remarkably improved ozone and organic contamination
Thing realizes the coupling of absorption and oxidative degradation and finally realizes going for persistent organic pollutants in the absorption of catalyst surface
Remove；Patent CN 103706338A are template by the way that polystyrene microsphere is modified while introduced to red mud, improve red mud
Pore structure, effectively increase the effect of red mud adsorbing and removing organic dyestuff；After patent CN 103420359A are with dry crush
Red mud be raw material, catalysis low-carbon hydro carbons decomposes production CNT, realizes the high value added utilization of red mud.
Hydrogen Energy is very extensive as a kind of secondary energy sources efficiently, clean, its purposes.Hydrogen production process common at present includes
Photodissociation, the electrolysis of water, methane-steam reforming, methane portion oxidation and biomass vaporization etc..Due to CH4Direct Pyrolysis is only
Carbon and hydrogen are produced, in the absence of CO and CO2, the purge process of hydrogen is simplified, therefore the direct catalytic pyrolysis of methane is produced in recent years
The method of high-purity hydrogen receives extensive concern.But along with the generation of carbon deposit, meeting during methane catalytic decomposition hydrogen manufacturing
The active sites of catalyst are caused to be covered and inactivated.Conventional methane catalyst for cracking such as noble metal, transition-metals and their oxides
, all inevitably there is the deactivation phenomenom of catalyst in composite catalyst, carbon material and charcoal Base Metal composite catalyst etc..
For red mud as a kind of discarded object, its cost is extremely low, and is wherein rich in the gold for largely possessing catalysis and co-catalysis function
Category and its oxide.Though being applied to catalytic methane solves the problems, such as that catalyst cost is expensive, due to red mud in itself
Active metal iron content it is not high, and pore structure is undeveloped, and which results in its catalytic activity and stability be not high.Therefore
By other means are needed to improve the catalytic activity of red mud and service life.
The content of the invention
In summary, in view of the shortcomings of the prior art, the invention provides a kind of preparation side of red mud base Fe-series catalyst
Method and its application in methane cracking hydrogen production.The present invention is that red mud first is carried out into acidleach processing, then one is added into suspension
After quantitative iron salt solutions co-precipitation processing is carried out with ammoniacal liquor, the pore structure of red mud in itself is improved with this, while improve activity
The content of metallic iron, substantially increase the activity and service life of red mud base catalyst methane cracking.This aspect is realized
The high value added utilization of red mud, on the other hand reduce the cost of methane cracking catalyst.In order to achieve the above object, this hair
Bright technical scheme is as follows：
A kind of preparation method of red mud base Fe-series catalyst, comprises the steps：
A, red mud is dried into 1-4h at 100-120 DEG C, it is standby less than 75 μm of red mud powder that crushing grinding is sized to granularity；
B, take 5-20 mass parts red mud powders obtained by step a to be positioned in beaker, add the deionized water of 50-100 parts by volume
1-5min is ultrasonically treated, then the inorganic acid solution of 400-800 parts by volume, water bath with thermostatic control and magnetic agitation 2h are added into beaker,
Bath temperature is 40-80 DEG C, stir speed (S.S.) 120-300r/min；
C, the molysite of 5-30 mass parts is dissolved in the absolute ethyl alcohol of 50-100 parts by volume, poured into the beaker in step b
After stirring, dropwise addition ammonia precipitation process is 7-10 up to suspension PH, stands aging 0.5-2h；
D, step c products therefroms are placed at 105-130 DEG C after precipitation filtering, washing to neutrality and dry 2-6h, afterwards
Particle of the crushing grinding into granularity less than 1mm is calcined；Calcining heat is 400-700 DEG C, calcination time 1-6h, then in pipe
It is reduced with pure hydrogen in formula stove, recovery time 1-4h, reduction temperature is 400-700 DEG C；Catalyst after reduction
Grinding screening is less than 75 μm, as red mud base Fe-series catalyst for granularity.
Further, the inorganic acid in described inorganic acid solution is hydrochloric acid or nitric acid, concentration 1-6mol/L.
Further, described molysite is Fe (NO3)3Or FeCl3；Ammoniacal liquor mass fraction used is 20-30% during precipitation.
A kind of application of red mud base Fe-series catalyst in methane cracking hydrogen production：
A, 0.5 part of catalyst prepared by the first step is taken to be seated in gas-solid catalysis device；
B, first it is passed through nitrogen to be heated up, stops being passed through nitrogen when temperature rises to 650 ± 5 DEG C of reaction temperature, immediately
It is passed through methane gas and starts methane cracking hydrogen production.
Beneficial effect：
1st, red mud base Fe-series catalyst prepared by the present invention, its pore structure is more flourishing compared with red mud, active metal
The content of iron also increases, and catalyst particle size is highly uniform and the decentralization of metallic iron is preferable.
2nd, the present invention realizes the catalytic methane cracking hydrogen production under conditions of more gently, and catalytic activity and life-span are all big
It is big to improve.
3rd, the present invention takes full advantage of original to being catalyzed favourable metal oxide such as Fe in red mud2O3、SiO2、 Al2O3
Deng so that this moieties is retained, and is eliminated in red mud to being catalyzed the metals such as unfavorable Ca and Na.
4th, present invention reduces the preparation cost of methane cracking catalyst, the high value added utilization of red mud is realized.
Brief description of the drawings
Fig. 1 is transmission electron microscope (TEM) picture of red mud after drying.
Fig. 2 is transmission electron microscope (TEM) picture of the 20Fe/MRM catalyst precursors of 600 DEG C of calcinings.
Fig. 3 is power spectrum (EDX) figure of 20Fe/MRM catalyst Fe elements.
Fig. 4 is the N of red mud and 20Fe/MRM catalyst after drying2- adsorption/desorption isotherms figure.
Fig. 5 is the graph of pore diameter distribution of red mud and 20Fe/MRM catalyst after drying.
Fig. 6 be reduction-state red mud Fe contents different from four kinds catalyst at 650 DEG C catalytic methane crack obtained first
Alkane conversion rate curve figure.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated：
Embodiment 1
A kind of preparation method of red mud base Fe-series catalyst, comprises the steps in parts by weight：
Red mud is first dried into 1-4h at 100-120 DEG C, crushing grinding is sized to granularity less than 75 μm, after taking 10g to dry
Red mud sample be put into 1000ml large beakers, 100ml deionized waters are poured into beaker, ultrasonic cleaning is put into after stirring
Ultrasonic 3min in machine；The watery hydrochloric acid for the 1mol/L that 500ml is prepared in advance is poured into beaker again, band is put into after being sufficiently stirred
Have in 60 DEG C of water bath with thermostatic control 2h in the water-bath of magnetic agitation, electromagnetic agitation speed is 300r/min；By Fe mass percent
10% (i.e. Fe (NO3)3·9H2Simple substance Fe quality accounts for the percentage of 10g raw material red mud quality after drying in O) accurately weigh
7.21g Fe (NO3)3·9H2O is dissolved in 50ml absolute ethyl alcohols, is poured into beaker and is stirred, then with ammoniacal liquor to beaker
Interior suspension carries out precipitation process, while is stirred vigorously with glass bar；Stop being added dropwise when suspension PH is close to 8.0 or so
Ammoniacal liquor, will precipitation stand aging 1h after be filtered by vacuum, while with deionized water and absolute ethyl alcohol by washing of precipitate to neutrality, after general
Precipitation is put into 120 DEG C of air dry oven and takes out the particle being ground into less than 1mm after dry 2h, places into Muffle furnace Program
600 DEG C of calcining 2h are warming up to, heating rate is 5 DEG C/min；The catalyst precursor after calcining is put into tube furnace again and uses H2
Reduce 4h, hydrogen flowing quantity H2Air speed is 40ml/ming；Catalyst is taken out and is ground into particle of the granularity less than 75 μm i.e.
Can, now catalyst is named as 10Fe/MRM.
A kind of application of red mud base Fe-series catalyst in methane cracking hydrogen production：
Take 0.5g 10Fe/MRM catalyst samples to be seated in the middle section of normal pressure gas and solid phase catalyzing reaction unit, connect
Good device is first hunted leak, and is passed through N afterwards2Heating, N2Flow is 40ml/min, and heating rate is 30 DEG C/min, is split when being warming up to
Stop being passed through N during 650 ± 5 DEG C of temperature of solution2, switch to methane gas and carry out methane catalytic decomposition hydrogen manufacturing；Adjust mass flowmenter
It is 40ml/min to make its flow perseverance, i.e., air speed is 80 ml/ming.The methane conversion of methane catalytic decomposition hydrogen manufacturing is with the time
Change curve as shown in Fig. 6.
Methane conversion calculation formula
Wherein,For the H in the cracking tail gas of gas analyzer measure2Percentage composition,For mutually gas in the same time
CH in the cracking gas of analysis-e/or determining4Percentage composition.
Embodiment 2：
A kind of preparation method of red mud base Fe-series catalyst, comprises the steps in parts by weight：
Red mud is first dried into 1-4h at 100-120 DEG C, crushing grinding is sized to granularity less than 75 μm, after taking 10g to dry
Red mud sample be put into 1000ml large beakers, 100ml deionized waters are poured into beaker, ultrasonic cleaning is put into after stirring
Ultrasonic 3min in machine；The watery hydrochloric acid for the 1mol/L that 500ml is prepared in advance is poured into beaker again, band is put into after being sufficiently stirred
Have in 60 DEG C of water bath with thermostatic control 2h in the water-bath of magnetic agitation, electromagnetic agitation speed is 300r/min；By Fe mass percent
20% (i.e. Fe (NO3)3·9H2Simple substance Fe quality accounts for the percentage of 10g raw material red mud quality after drying in O) accurately weigh
14.42g Fe (NO3)3·9H2O is dissolved in 50ml absolute ethyl alcohols, is poured into beaker and is stirred, then with ammoniacal liquor to burning
Suspension in cup carries out precipitation process, while is stirred vigorously with glass bar；Stop drop when suspension PH is close to 8.0 or so
Ammonification water, will precipitation stand aging 1h after be filtered by vacuum, while with deionized water and absolute ethyl alcohol by washing of precipitate to neutrality, after
The particle for being put into and taking out and being ground into less than 1mm after dry 2h in 120 DEG C of air dry oven will be precipitated, place into Muffle furnace intermediate range
Sequence is warming up to 600 DEG C of calcining 2h, and heating rate is 5 DEG C/min；The catalyst precursor after calcining is put into tube furnace again and used
H2Reduce 4h, hydrogen flowing quantity H2Air speed is 40ml/ming；Catalyst is taken out and is ground into particle of the granularity less than 75 μm i.e.
Can, now catalyst is named as 20Fe/MRM.
A kind of application of red mud base Fe-series catalyst in methane cracking hydrogen production：
Take 0.5g 10Fe/MRM catalyst samples to be seated in the middle section of normal pressure gas and solid phase catalyzing reaction unit, connect
Good device is first hunted leak, after be passed through N2Heating, N2Flow is 40ml/min, and heating rate is 30 DEG C/min, is split when being warming up to
Stop being passed through N during 650 ± 5 DEG C of temperature of solution2, switch to methane gas and carry out methane catalytic decomposition hydrogen manufacturing；Adjust mass flowmenter
It is 40ml/min to make its flow perseverance, i.e., air speed is 80 ml/ming.The methane conversion of methane catalytic decomposition hydrogen manufacturing is with the time
Change curve as shown in Fig. 6.
Methane conversion calculation formula
Wherein,For the H in the cracking tail gas of gas analyzer measure2Percentage composition,For mutually gas in the same time
CH in the cracking gas of analysis-e/or determining4Percentage composition.
Embodiment 3：
A kind of preparation method of red mud base Fe-series catalyst, comprises the steps in parts by weight：
Red mud is first dried into 1-4h at 100-120 DEG C, crushing grinding is sized to granularity less than 75 μm, after taking 10g to dry
Red mud sample be put into 1000ml large beakers, 100ml deionized waters are poured into beaker, ultrasonic cleaning is put into after stirring
Ultrasonic 3min in machine；The watery hydrochloric acid for the 1mol/L that 500ml is prepared in advance is poured into beaker again, band is put into after being sufficiently stirred
Have in 60 DEG C of water bath with thermostatic control 2h in the water-bath of magnetic agitation, electromagnetic agitation speed is 300r/min；By Fe mass percent
30% (i.e. Fe (NO3)3·9H2Simple substance Fe quality accounts for the percentage of 10g raw material red mud quality after drying in O) accurately weigh
21.63g Fe (NO3)3·9H2O is dissolved in 50ml absolute ethyl alcohols, is poured into beaker and is stirred, then with ammoniacal liquor to burning
Suspension in cup carries out precipitation process, while is stirred vigorously with glass bar；Stop drop when suspension PH is close to 8.0 or so
Ammonification water, will precipitation stand aging 1h after be filtered by vacuum, while with deionized water and absolute ethyl alcohol by washing of precipitate to neutrality, after
The particle for being put into and taking out and being ground into less than 1mm after dry 2h in 120 DEG C of air dry oven will be precipitated, place into Muffle furnace intermediate range
Sequence is warming up to 600 DEG C of calcining 2h, and heating rate is 5 DEG C/min；The catalyst precursor after calcining is put into tube furnace again and used
H2Reduce 4h, hydrogen flowing quantity H2Air speed is 40ml/ming；Catalyst is taken out and is ground into particle of the granularity less than 75 μm i.e.
Can, now catalyst is named as 30Fe/MRM.
A kind of application of red mud base Fe-series catalyst in methane cracking hydrogen production：
Take 0.5g 10Fe/MRM catalyst samples to be seated in the middle section of normal pressure gas and solid phase catalyzing reaction unit, connect
Good device is first hunted leak, after be passed through N2Heating, N2Flow is 40ml/min, and heating rate is 30 DEG C/min, is split when being warming up to
Stop being passed through N during 650 ± 5 DEG C of temperature of solution2, switch to methane gas and carry out methane catalytic decomposition hydrogen manufacturing；Adjust mass flowmenter
It is 40ml/min to make its flow perseverance, i.e., air speed is 80 ml/ming.The methane conversion of methane catalytic decomposition hydrogen manufacturing is with the time
Change curve as shown in Fig. 6.
Methane conversion calculation formula
Wherein,For the H in the cracking tail gas of gas analyzer measure2Percentage composition,For mutually gas in the same time
CH in the cracking gas of analysis-e/or determining4Percentage composition.
Comparative example
The first step：The preparation of catalyst
Red mud is first dried into 1-4h at 100-120 DEG C, crushing grinding is sized to granularity less than 75 μm, after taking 10g to dry
Red mud sample be put into 1000ml large beakers, 100ml deionized waters are poured into beaker, ultrasonic cleaning is put into after stirring
Ultrasonic 3min in machine.The watery hydrochloric acid for the 1mol/L that 500ml is prepared in advance is poured into beaker again, band is put into after being sufficiently stirred
Have in 60 DEG C of water bath with thermostatic control 2h in the water-bath of magnetic agitation, electromagnetic agitation speed is 300r/min.Because the embodiment is pair
Ratio, therefore Fe (NO are added not into suspension3)3Solution, precipitation process directly is carried out to the suspension in beaker with ammoniacal liquor, together
When be stirred vigorously with glass bar.Stop that ammoniacal liquor is added dropwise when suspension PH is close to 8.0 or so, by vacuum after precipitation standing aging 1h
Filter, while with deionized water and absolute ethyl alcohol by washing of precipitate to neutrality, after will precipitate and be put into 120 DEG C of air dry oven
The particle being ground into less than 1mm is taken out after drying 2h, Muffle furnace Program is placed into and is warming up to 600 DEG C of calcining 2h, heating rate
For 5 DEG C/min.The catalyst precursor after calcining is put into tube furnace again and uses H2Reduce 4h, hydrogen flowing quantity H2Air speed is
40ml/min·g.Catalyst is taken out to the particle for being ground into granularity and being less than 75 μm, now catalyst is named as MRM.
Second step：Methane catalytic decomposition hydrogen manufacturing
Take 0.5g 10Fe/MRM catalyst samples to be seated in the middle section of normal pressure gas and solid phase catalyzing reaction unit, connect
Good device is first hunted leak, after be passed through N2Heating, N2Flow is 40ml/min, and heating rate is 30 DEG C/min, is split when being warming up to
Stop being passed through N during 650 ± 5 DEG C of temperature of solution2, switch to methane gas and carry out methane catalytic decomposition hydrogen manufacturing；Adjust mass flowmenter
It is 40ml/min to make its flow perseverance, i.e., air speed is 80 ml/ming.The methane conversion of methane catalytic decomposition hydrogen manufacturing is with the time
Change curve as shown in Fig. 6.
Methane conversion calculation formula
Wherein,For the H in the cracking tail gas of gas analyzer measure2Percentage composition,For mutually gas in the same time
CH in the cracking gas of analysis-e/or determining4Percentage composition.
The XRF of the catalyst precursor (after 600 DEG C of calcinings) prepared after drying in red mud and three embodiments is given below
Analysis result：
Above-described embodiment is all preferred embodiment, and this method can be realized by affiliated step in specification, but be not limited only to
Special parameter described in embodiment.
Although above the present invention is described in detail with a general description of the specific embodiments,
On the basis of the present invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Cause
This, these modifications or improvements, belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (1)
1. a kind of preparation method of red mud base Fe-series catalyst, it is characterised in that comprise the following steps：
Red mud is first dried into 1-4h at 100-120 DEG C, crushing grinding is sized to granularity less than 75 μm, takes 10g dried red
Mud sample product are put into 1000ml large beakers, and 100ml deionized waters are poured into beaker, are put into after stirring in supersonic cleaning machine
Ultrasonic 3min；The watery hydrochloric acid for the 1mol/L that 500ml is prepared in advance is poured into beaker again, is put into after being sufficiently stirred with magnetic force
In 60 DEG C of water bath with thermostatic control 2h in the water-bath of stirring, electromagnetic agitation speed is 300r/min；By Fe mass percent 10% (i.e.
Fe(NO3)3•9H2Simple substance Fe quality accounts in O dry after 10g raw material red mud quality percentage) the accurate Fe for weighing 7.21g
(NO3)3•9H2O is dissolved in 50ml absolute ethyl alcohols, is poured into beaker and is stirred, then with ammoniacal liquor to the suspension in beaker
Precipitation process is carried out, while is stirred vigorously with glass bar；Stop that ammoniacal liquor is added dropwise when suspension pH is close to 8.0 or so, will precipitate
Be filtered by vacuum after standing aging 1h, while with deionized water and absolute ethyl alcohol by washing of precipitate to neutrality, after precipitation is put into 120
DEG C air dry oven in dry to take out after 2h and be ground into particle less than 1mm, place into Muffle furnace Program and be warming up to 600 DEG C
2h is calcined, heating rate is 5 DEG C/min；The catalyst precursor after calcining is put into tube furnace again and uses H2Reduce 4h, hydrogen
Flow is H2Air speed is 40ml/ming；Catalyst is taken out to the particle for being ground into granularity and being less than 75 μm, now catalyst
It is named as 10Fe/MRM.
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| US11396006B2 (en) | 2020-01-28 | 2022-07-26 | Saudi Arabian Oil Company | Nickel-containing catalyst composition having enhanced acidity for bi-reforming processes |
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| US11242245B2 (en) * | 2020-01-28 | 2022-02-08 | Saudi Arabian Oil Company | Catalyst carrier for steam reforming processes |
| US11242246B2 (en) | 2020-01-28 | 2022-02-08 | Saudi Arabian Oil Company | Catalyst carrier for autothermal reforming processes |
| US11365120B2 (en) | 2020-01-28 | 2022-06-21 | Saudi Arabian Oil Company | Nickel-containing catalyst composition having enhanced acidity for steam reforming processes |
| US11338270B2 (en) | 2020-01-28 | 2022-05-24 | Saudi Arabian Oil Company | Catalyst compositions having enhanced acidity for autothermal reforming processes |
| CN113198445B (en) * | 2021-03-16 | 2022-08-12 | 山东大学 | Red mud SCR catalyst and preparation method and application thereof |
| CN114534744B (en) * | 2022-01-26 | 2022-12-09 | 常州大学 | Preparation method of solid acid catalyst based on aluminous ash-green carbon-based double-carrier |
| CN117358245B (en) * | 2023-12-07 | 2024-02-27 | 盐城师范学院 | Red mud-based thermal catalyst with shell-core structure, and preparation method and application thereof |
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