CN104128187A - Ni/La2O3 catalyst used for reforming LPG low water carbon ratio water vapor and preparation method thereof - Google Patents

Ni/La2O3 catalyst used for reforming LPG low water carbon ratio water vapor and preparation method thereof Download PDF

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CN104128187A
CN104128187A CN201410311175.4A CN201410311175A CN104128187A CN 104128187 A CN104128187 A CN 104128187A CN 201410311175 A CN201410311175 A CN 201410311175A CN 104128187 A CN104128187 A CN 104128187A
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catalyst
nickel
lanthanum
lpg
preparation
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尚兴付
汪学广
黄震
田宗磊
丁伟中
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University of Shanghai for Science and Technology
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University of Shanghai for Science and Technology
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
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    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention relates to a Ni/La2O3 catalyst used for reforming LPG low water carbon ratio water vapor and a preparation method thereof, which belongs to the technical field of catalyst preparation technology. The LPG water vapor reforming catalyst of lanthana load nickel can be obtained by reduction of perovskite composite oxide of nickel and lanthanum. The atom mol ratio of lanthanum to nickel is 1:1, and the preparation method is a deposition-combustion method. According to the invention, a 2mol/L ammonium carbonate solution enables slow titration in a mixing solution of lanthanum nitrate, nicdel nitrate and citric acid to form suspending liquid, the suspending liquid is dried and roasted to obtain the LaNiO3 perovskite composite oxide, and is reduced through hydrogen at 600 DEG C to obtain the Ni/La2O3 catalyst. The catalyst has the advantages of high catalytic activity, wide usage temperature, good catalysis stability, high mechanical strength and low production cost. The service life experiment result shows that that catalyst is a potential water vapor reforming catalyst with low temperature, low water carbon ratio and high carbon alkanes.

Description

Ni/La for LPG low steam carbon ratio steam reforming 2o 3catalysts and its preparation method
Technical field
The invention discloses a kind of Ni/La for LPG low steam carbon ratio steam reforming 2o 3catalysts and its preparation method, belongs to catalyst preparation process technical field.
Background technology
LPG has that combustion heat value is high, energy density is large, market steady sources, store convenient transportation, have the ripe advantages such as commercialization distribution network, for the automobile mounted hydrogen manufacturing of development of fuel cells, has huge potential commercial value.Hydro carbons water vapour catforming hydrogen production method is current most widely used hydrogen production process, and catalyst carbon deposit has harmful effect to its activity, life-span, mechanical strength, for preventing carbon deposit, need pass into excessive steam (S/C=3～5).Raising steam consumption means the increase of energy consumption, and equipment is huge, and floor space is large, and investment and operating cost are expensive.An effective solution is to adopt pre-converted technique.Before reburner, increase exactly an adiabatic reactor, make hydro carbons in raw material at low temperature, low steam carbon ratio, under the conditions such as high-speed, steam-reforming is CH 4and H 2deng micro-molecular gas.And then through more than 700 ℃ high temperature by CH 4reform and generate H 2, CO and CO 2.
The process of hydro carbons pre-inversion enriched Gas is generally carried out within the scope of 400～550 ℃, adopts highly active ni catalysts, guarantees high-carbon hydrocarbon cracking at a lower temperature, steam-reforming, hydrogenation and transformationreation, finally reaches methanation and CO shifting balance.The endothermic reaction such as cracking, conversion and methanation, conversion waits exothermic reaction to form coupling, and heating load, reduces and extraneous heat exchange mutually.Pre-inversion reaction and classical inverse should be different, and tradition transforms mainly take hydrocarbon and producing hydrogen from steam conversion as main, need under higher temperature, carry out; And pre-inversion requires cracking and hydrogenation reaction to carry out simultaneously, by technological parameter, adjust, make overall thermal effect less, realize and carrying out in adiabatic reactor.Pre-converting catalyst is different from reforming catalyst, under low steam carbon ratio condition, should have following characteristic: the low temperature active that (1) is high; (2) high carbon deposition resistance; (3) good heat endurance.Therefore, should guarantee that catalyst has higher activity, increase the service life again and repeatedly recycle rear catalyst activity and stability.
Ni/Al 2o 3catalyst is due to its high activity and be cheaply considered to a kind of up-and-coming hydro carbons steam reforming catalyst (Appl. Catal. A. 314 (2006): 9,81; Int. J. Hydrogen Energy. 33 (2008): 7427; Chin. J. Catal. 30 (2009): 690).Yet active metal Ni species are easily oxidized to nickel oxide under steam and oxygen atmosphere, make nickel-base catalyst complete deactivation.
LaNiO 3perovskite composite oxide has higher heat endurance, the Ni/La forming after reduction 2o 3catalyst can make active component nickel grain diameter little and be dispersed in La 2o 3in, thereby make catalyst there is good carbon accumulation resisting ability, be widely used in the catalytic reforming reaction of alkane.In Catalysis Today 107 – 108 (2005) 474 – 480 and Catalysis Today 212 (2013) 98 – 107, take glycine and nitrate is raw material, by combustion method, prepares LaNiO 3perovskite composite oxide is for carbon dioxide and methane reforming.In Energy Fuels 2009,23,4883 – 4886, take glycine and nitrate is raw material, by combustion method, prepares LaNiO 3perovskite composite oxide, and for the dry reforming reaction of methane.Catalysis Today 171 (2011) 24 – 35 be take citric acid and lanthanum nitrate and nickel nitrate as raw material, adopt sol-gal process to prepare LaNiO 3perovskite composite oxide, for the catalytic decomposition of methane.It is raw material that Applied Catalysis A:General 450 (2013) 73 – 79 be take glycine and nitrate, by combustion method, prepares LaNiO 3perovskite composite oxide is for catalysis ethanol hydrogen and CNT.The present invention prepares LaNiO by precipitation-combustion method 3perofskite type oxide, the lanthana nickel-loaded LPG steam reforming reaction catalyst of making after reduction, has quite high activity and long-time stability.Under low steam carbon ratio condition, successfully to have carried out repeatedly recycling, catalytic activity is in daily startup and close down not reduction of operation.
Summary of the invention
The object of the present invention is to provide the Ni/La that a kind of catalytic activity is high, serviceability temperature is wide, catalytic stability is good, mechanical strength is high, production cost is low 2o 3low steam carbon ratio LPG steam reforming catalyst.
Novel nickel-based LPG water vapor reforming catalyst of the present invention, it is characterized in that being formed by the perovskite composite oxide reduction of lanthanum, nickel, wherein nickel is with the atomic molar of lanthanum than being 1:1, and the preparation technology of catalyst of the present invention adopts inorganic salts precipitation-combustion method, mainly comprises following steps:
A) by the lanthanum of catalyst, nickel element atomic ratio, be 1:1, prepare a certain amount of Ni (NO 3) 26H 2o, La (NO 3) 39H 2the mixed aqueous solution of O and citric acid, making metal ion molar concentration is 0.2 mol/L, the concentration of citric acid is 0.4 mol/L;
B) mixed solution preparing is moved to 40 ℃ of thermostat water baths, the speed with the sal volatile of 1 mol/L with 1 mL/min slowly splashes into, and ceaselessly stirs; Mixing speed is 200 revs/min, and being titrated to PH is 6-7, generates precipitation, and solution becomes suspension;
C) suspension obtaining is moved to dry 24 h in the baking oven of 100 ℃, the roasting in Muffle furnace of dried powder, is raised to 400 ℃ of roasting 5 h from room temperature, is more progressively warmed up to 600 ℃ of roasting 5 h, and programming rate is 1 ℃/min.By the extrusion modling in mould under the pressure of 25～35 kN of the powder after roasting; With by broken, sieve, obtaining particle diameter is 35～45 object particles, obtains LaNiO 3perovskite composite oxides;
D) by LaNiO 3perovskite composite oxides is at 600 ℃ and H 2under atmosphere, reduce completely after 3～4 h, obtain Ni/La 2o 3catalyst.
Accompanying drawing explanation
Fig. 1 is the LaNiO preparing after the embodiment of the present invention 1 roasting 3xRD figure after the XRD figure of perovskite composite oxide and reduction.
Fig. 2 is the catalytic evaluation result of Kaolinite Preparation of Catalyst in embodiment 1.
Fig. 3 is the comparison of embodiment 1 and comparative example's 1 catalytic performance test result.
Fig. 4 is full airspeed and the corresponding equilibrium valve (representing with dotted line) that embodiment transforms completely at differential responses temperature LPG
Fig. 5 is the experimental result of embodiment catalyst circulation operation.
The specific embodiment
By following examples, the present invention is further described.
embodiment 1
Take each 0.04 mol of nickel nitrate and lanthanum nitrate, citric acid 0.08 mol adds deionized water, is stirred to dissolving.The concentration of controlling nickel nitrate and lanthanum nitrate is 0.2 mol/L, and the concentration of citric acid is 0.4 mol/L.Solution moves to 40 ℃ of water-baths, constantly stirs, and with the sal volatile of 1 mol/L preparing, with peristaltic pump, take the mixed solution that 1 mL/min titration prepares is 6-7 to PH, formation suspension.Continue to stir 2 h, by 80 ℃ of evaporates to dryness of the suspension solution obtaining, transfer in baking oven, 120 ℃ of dry 12 h, then forward roasting in Muffle furnace to, are raised to 400 ℃ of roasting 5 h from room temperature with the heating rate of 1 ℃/min, are more progressively warmed up to 600 ℃ of roasting 5 h.By the extrusion modling in punching block under the pressure of 25～35 kN of the powder after roasting; With by broken, sieve, obtaining particle diameter is 35～45 object particles, obtains perovskite composite oxides LaNiO 3.Then from room temperature with 10 othe heating rate of C/min is warmed up to 600 ℃, with 15 vol% H 2/ N 2reduce after 3 h and obtain Ni/La 2o 3catalyst.
comparative example 1
Adopt traditional infusion process to prepare lanthana supported nickel catalyst, with the nickel nitrate dipping lanthanum sesquioxide of 0.2 mol/L; Nickel content in catalyst, oven dry, roasting, reducing condition keep the Ni/La preparing with precipitation-combustion method 2o 3unanimously.
assessment experiment
LPG is purchased from the new nine automobile-used Energy Co., Ltd. of ring difficult to understand in Shanghai, and its composition is: C 2h 63.1 vol%, C 3h 884.0 vol%; C 4h 1012.9 vol%, directly do not apply through purified treatment.
The activity of catalyst is evaluated in traditional atmospheric fixed bed reactor carries out, quartz tube reactor is long 900 mm, diameter is 10 mm, 0.1 g catalyst and the mixing of 0.9 g quartz sand are placed on to quartz ampoule middle part, be placed in the middle of two-layer silica wool, the actual temperature of catalyst detects with the thermocouple being placed in beds.Reacting gas is controlled by mass flowmenter, and water enters 300 ℃ of preheaters that quartz ball is housed of constant temperature by micro pump control and mixes.The air speed of controlling reaction is 11000 mL/g cath, steam/hydrocarbons ratio S/C=1.Before evaluation response, catalyst should be 15 vol.% H at hydrogen gas mixture 2/ N 2in (flow is 30 Ml min -1) and temperature be at 600 ℃, to reduce 4 h; For avoiding initial carbon deposition, reducing gas was converted to nitrogen and required water gaging steam after 5 minutes, close nitrogen and change LPG into and enter reaction system, through the gas of catalytic reaction discharge, at room temperature condenser is cooling, by dead plaster, removes all water.Finally, use online GC-FID gas-chromatography, adopt CP – SIL 5 CB posts to analyze dry gas hydrocarbon products, another GC-TCD gas chromatograph is to CH4, CO, CO 2and H 2analyze.By soap film flowmeter measurement gas exit velocity, the gas of outlet is except H 2, CO, CO 2and CH 4, there is no other gas.Then between 400 ~ 550 ℃, survey LPG conversion ratio.LPG conversion ratio calculates by several formula below.
In formula, X lPGfor the conversion ratio of LPG, S i, S h2be respectively the selective of product, N represents molar flow, and i is CO, CO 2, CH 4.
In daily startup and shutoff operation, first by nickel acid lanthanum perovskite composite oxides 600 ℃ of reduction, first 450 ℃ of reactions, air speed is 11000 mL/g cath carries out liquefied petroleum gas steam reforming reaction, and water/carbon mol ratio is 1, and operation 13 h, make reaction system and catalyst complete stability.After first round reaction, liquefied petroleum gas switches to isopyknic N 2and water vapor purging.In used catalyst 2 h, original position is cooled to 200 ℃ from 450 ℃.N 2after water vapor purging 4 h, catalyst temperature is elevated to 450 ℃ with 8 ℃/min heating rate again, through 5.5 h, N 2with steam convert to completely first round reacting phase with condition start second and take turns circular response.By water vapor purging, and then the reaction in the 3rd and the 4th cycle is to carry out under same operator scheme subsequently.
In Fig. 1, (a) is 600 oCthe XRD figure of the preparation after roasting, corresponding LaNiO 3perovskite PDF card number is (JCPDS 33-0710).(b) be 600 oxRD figure after C hydrogen reducing, corresponds to nickel and lanthana, shows LaNiO 3after hydrogen reducing, there is the LaNiO of perovskite structure 3change lanthana supported nickel catalyst into.
Fig. 2 is LPG steam reforming reaction result.Reaction condition is: air speed is 11000 mL/g cath, steam/hydrocarbons ratio is 1, reaction temperature is 450 ℃.As seen from the figure, the Ni/La preparing by precipitation-combustion method 2o 3catalyst has higher activity, can make LPG be converted into CH completely 4, CO, CO 2and H 2, in the long-time operation of 380 h, the conversion ratio of LPG does not significantly decrease, and shows good stability, and reacted catalyst does not find that there is carbon distribution phenomenon.
Fig. 3 is embodiment 1 and comparative example's 1 catalytic activity contrast, as shown in the figure, in the reaction of 13 h, Ni/La prepared by precipitation-combustion method 2o 3after 5 h reactions, the conversion ratio of LPG is stabilized in 95 % always, and the Ni/La preparing by infusion process in comparative example 2o 3catalyst, after catalytic reaction is carried out 4 h, after the conversion of LPG reaches the maximum conversion rate of 87 %, LPG conversion ratio progressively declines, and is reacted to after 12 h, and the conversion ratio of LPG drops to 21 %.From comparative test result, can find out that the catalyst that catalyst that the present invention is prepared by precipitation-combustion method is prepared than traditional infusion process has higher catalytic activity and stability.
Fig. 4 represents that temperature is 425 when water/carbon ratio=1 oc to 550 oc is interval, and under different temperatures, LPG is converted into CH completely 4, CO, CO 2and H 2full airspeed used.As shown in the figure, different temperatures full airspeed is with almost linear increase of temperature rising.425 oduring C, the full airspeed that LPG transforms is completely 4100 mL/g cath, 550 oduring C, full airspeed is 16500 mL/g cath.Do not have the thermal cracking of carbon deposit and hydrocarbon to occur, the equilibrium valve that selectively approaches calculation of thermodynamics of product, shows the methanation of oxycarbide and hydrogen, and the water-gas shift reaction of reforming system has reached chemical balance.Ni/La prepared by this explanation precipitation auto-combustion method 2o 3catalyst has the features such as high activity, high stability.
Fig. 5 is Ni/La 2o 3catalyst is closed down the catalytic activity figure in operating process at LPG pre-reforming.Reaction condition: 450 oc reaction, steam/hydrocarbons ratio=1, air speed=11000 mL/g cath, uses nitrogen and steam treatment when reaction is interrupted.First round circular response carries out 13 h, makes reaction system complete stability.Second takes turns reaction has carried out 5.5 h, and later circular response adopts identical pattern.When passing into LPG, enter reaction system, initial conversion ratio surpasses 90 %.In 1.5 h, be raised to very soon about 95 %, reach same catalytic activity.After taking turns cycling through 3 as seen from Figure 5, the catalytic activity of catalyst remains unchanged, and has higher stability.It is a kind of very potential low temperature low steam carbon ratio High-carbon alkane steam reforming catalyst.

Claims (3)

1. the Ni/La for LPG low steam carbon ratio steam reforming 2o 3catalyst, is characterized in that, in this lanthana supported nickel catalyst, the atomic molar of nickel, lanthanum is than being 1:1.
2. the Ni/La for LPG low steam carbon ratio steam reforming 2o 3the preparation method of catalyst, is characterized in that having following process and step:
A) prepare a certain amount of Ni (NO 3) 26H 2o, La (NO 3) 39H 2the mixed aqueous solution of O and citric acid, making metal ion molar concentration is 0.2 mol/L, and the atomic molar of nickel, lanthanum is than being 1:1, and the concentration of citric acid is 0.4mol/L;
B) mixed solution preparing is moved to 40 ℃ of thermostat water baths, with the sal volatile of 2 mol/L, with 1 mL/min speed, slowly splash into, and ceaselessly stir, mixing speed is 200 revs/min, and being titrated to PH is 6-7, forms suspension;
C) suspension obtaining is moved to dry 24 h in the convection oven of 100 ℃, the roasting in Muffle furnace of dried powder; From room temperature, be raised to 400 ℃ of roasting 5 h, be more progressively warmed up to 600 ℃ of roasting 5 h, programming rate is 2 ℃/min; By the extrusion modling in punching block under the pressure of 25 ~ 35 kN of the powder after roasting; With by broken, sieve, obtaining particle diameter is 35～45 object particles, obtains LaNiO 3perovskite composite oxide, then in nitrogen atmosphere, temperature is at 600 ℃, to reduce 3～4 h, finally obtains lanthana supported nickel catalyst.
3. the Ni/La for LPG low steam carbon ratio steam reforming as claimed in claim 2 2o 3the preparation method of catalyst, the nickel nitrate described in it is characterized in that and lanthanum nitrate can use nickel acetate, lanthanum acetate to substitute; Described ammonium carbonate can substitute with ammonium oxalate.
CN201410311175.4A 2014-07-02 2014-07-02 Ni/La2O3 catalyst used for reforming LPG low water carbon ratio water vapor and preparation method thereof Pending CN104128187A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101725293B1 (en) * 2015-11-04 2017-04-10 한국과학기술연구원 Nickel supported catalyst for combined steam and carbon dioxide reforming with natural gas
CN107983338A (en) * 2016-10-27 2018-05-04 中国科学院大连化学物理研究所 A kind of method for improving Ca-Ti ore type composite metal oxide catalyst performance
CN113019383A (en) * 2021-03-10 2021-06-25 中国科学院兰州化学物理研究所 Nickel/lanthanum oxide catalyst and preparation method and application thereof
CN114976066A (en) * 2022-06-02 2022-08-30 佛山科学技术学院 La with layered structure n+1 Ni n O 3n+1 Solid oxide fuel cell anode catalyst

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102133533A (en) * 2011-02-23 2011-07-27 上海大学 LPG water vapor pre-reforming catalyst and application method thereof
CN102133529A (en) * 2011-02-23 2011-07-27 上海大学 Novel nickel-based LPG water vapor reforming catalyst and preparation method thereof
CN102616820A (en) * 2012-04-24 2012-08-01 上海大学 Method for preparing mesoporous gamma-Al2O3 nano material with high specific surface area at low temperature
CN102649590A (en) * 2012-05-04 2012-08-29 上海大学 Method for preparing mesoporous material NiAl2O4 without specific surface active agent

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102133533A (en) * 2011-02-23 2011-07-27 上海大学 LPG water vapor pre-reforming catalyst and application method thereof
CN102133529A (en) * 2011-02-23 2011-07-27 上海大学 Novel nickel-based LPG water vapor reforming catalyst and preparation method thereof
CN102616820A (en) * 2012-04-24 2012-08-01 上海大学 Method for preparing mesoporous gamma-Al2O3 nano material with high specific surface area at low temperature
CN102649590A (en) * 2012-05-04 2012-08-29 上海大学 Method for preparing mesoporous material NiAl2O4 without specific surface active agent

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ZHEN HUANG ET AL.: "High catalytic performance and sustainability of the Ni/La2O3 catalyst for daily pre-reforming of liquefied petroleum gas under a low steam/carbon molar ratio", 《RSC ADVANCES》 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101725293B1 (en) * 2015-11-04 2017-04-10 한국과학기술연구원 Nickel supported catalyst for combined steam and carbon dioxide reforming with natural gas
US9782755B2 (en) 2015-11-04 2017-10-10 Korea Institute Of Science And Technology Nickel supported catalyst for combined steam and carbon dioxide reforming with natural gas
CN107983338A (en) * 2016-10-27 2018-05-04 中国科学院大连化学物理研究所 A kind of method for improving Ca-Ti ore type composite metal oxide catalyst performance
CN107983338B (en) * 2016-10-27 2021-05-07 中国科学院大连化学物理研究所 Method for improving catalytic performance of perovskite type composite metal oxide
CN113019383A (en) * 2021-03-10 2021-06-25 中国科学院兰州化学物理研究所 Nickel/lanthanum oxide catalyst and preparation method and application thereof
CN114976066A (en) * 2022-06-02 2022-08-30 佛山科学技术学院 La with layered structure n+1 Ni n O 3n+1 Solid oxide fuel cell anode catalyst
CN114976066B (en) * 2022-06-02 2024-02-02 佛山科学技术学院 La of lamellar structure n+1 Ni n O 3n+1 Solid oxide fuel cell anode catalyst

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Application publication date: 20141105