CN101327440A - Composite catalyst for producing hydrogen by methane steam reforming technology - Google Patents

Composite catalyst for producing hydrogen by methane steam reforming technology Download PDF

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Publication number
CN101327440A
CN101327440A CNA2008100222177A CN200810022217A CN101327440A CN 101327440 A CN101327440 A CN 101327440A CN A2008100222177 A CNA2008100222177 A CN A2008100222177A CN 200810022217 A CN200810022217 A CN 200810022217A CN 101327440 A CN101327440 A CN 101327440A
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catalyst
nickel
composite catalyst
methane
composite
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鲁伊恒
邵群
徐国财
李寒旭
陈晓玲
陈明强
张晓梅
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Anhui University of Science and Technology
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Anhui University of 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
    • 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 present invention relates to a composite catalyst used for reforming methane steam to produce hydrogen. The composite catalyst is characterized in that the composite catalyst consists of nickel-based metal atom catalyst and phosphor, molybdenum and tungsten heteropoly acid catalyst and considers aluminium sesquioxide as a support. The composite catalyst has a chemical formula as follows: H3PMo6W6O40/Al2O3/Ni-Ce-Sr, in the formula, the weight proportion of P-Mo-W heteropoly acid and nickel-based catalyst is 15 to 25 to 75 to 85; the mol ratio of every component in the nickel-based catalyst is that Ni to Ce to Sr to Al2O3 is equal to 0.8 to 1.2 to 0.8 to 1.2 to 0.8 to 1.2 to 2.0 to 2.5. The composite catalyst is used for reforming the methane steam to produce the hydrogen; when the reaction temperature is 440 DEG C, methane conversion rate is 100 percent, thereby showing that the catalyst has high catalyzing activity.

Description

A kind of composite catalyst that is used for producing hydrogen by methane steam reforming technology
One, technical field
The present invention relates to a kind of catalyst, specifically a kind of composite catalyst that is used for producing hydrogen by methane steam reforming technology.
Two, background technology
Highly purified hydrogen is the primary raw material of hydrogen-air-fuel battery (PEMFC), utilizes methane, biogas (containing methane 30-60%) or Device in Gas (containing methane 30-50%%) to purify after the steam catalytic reforming prepares hydrogen.The steam methane catalytic reforming comprises mainly and produces synthesis gas and aqueous vapor replaced for two steps that its reaction principle is: CH 4+ H 2O → CO+3H 2(Δ H o=+206kJ/mol) and CO+H 2O → CO 2+ H 2(Δ H o=-41kJ/mol).Present Ni/Al 2O 3Be catalyst the most frequently used in this technology,, add certain auxiliary agent usually, thereby suppress the formation of catalyst surface carbon for preventing the catalyst surface carbon distribution.As MgO 2-CaO 2-Ni/ α-Al 2O 3Catalyst, this method is with immersion process for preparing, with MgO 2And CaO 2Be auxiliary agent; Ni-CeO 2-ZrO 2/ θ-Al 2O 3Catalyst with immersion process for preparing, causes the factor of catalysqt deactivation that temperature, carbon distribution, atmosphere are arranged, wherein the high more easy more formation NiAl of temperature 2O 4Solid solution causes catalysqt deactivation, Al 2O 3Content is high more, also forms NiAl easily 2O 4Pd-CeO in addition 2/ γ-Al 2O 3There are the catalyst preparation process complexity in catalyst, this method with two immersion process for preparing, and use the shortcoming of precious metal palladium; Vapor phase method prepares molybdenum carbide catalyst, although this method catalyst stability is better, the conversion of methane temperature is too high, reaches 947 ℃, and CO 2And H 2O can be oxidized to molybdenum oxide with molybdenum carbide, and it is lost activity.
The methane carbon dioxide reformation reaction principle is [35]: CH 4+ CO 2→ 2CO+2H 2(Δ H o=+247kJ/mol), CO 2+ H 2→ CO+H 2O (Δ H o=+40.96kJ/mol).Catalyst has Ni-CeO 2-ZrO 2/ Al 2O 3Catalyst, this catalyst adopts hydrothermal synthesis method, Al 2O 3Content is very big to activity of such catalysts influence, average conversion only about 85%.CeO 2Modification Ni/Al 2O 3Catalyst adopts the sol-gel process preparation, although this method catalytic activity and stability are better, complicated process of preparation need be carried out under pressure furnace and super critical condition.Nickel Ca-Ti ore type La-Sr-Ni catalyst adopts the preparation of spontaneous combustion method, and this method needs the amion acetic acid of consume expensive, so cost is higher.
Methane portion oxidation reforming reaction principle is: CH 4+ 1/2O 2→ CO+2H 2, Δ H o=-35.5kJ/mol.Catalyst has the Ni/ γ-Al of barium modification 2O 3Catalyst, this method prepares with coprecipitation, adds barium and can suppress oarse-grained NiAl 2O 4Form, active component is increased relatively, thereby improve catalytic activity; NiO-CeO 2-TiO 2Composite oxide catalysts, this method prepares with citric acid complex method, has catalytic activity preferably, and methane conversion can reach 95.%, and selectivity can reach 86%, but needs to consume citric acid, and cost increases.
Methane steam reforming has the advantage of technology maturation, but also exists reaction temperature higher, and the shortcoming that energy consumption is bigger needs the research new catalyst to reduce reaction temperature and carbon distribution.And CO 2During reformation and partial oxidation process are reformed, though can save the part energy, the industrialization of still being unrealized at present, especially partial oxidation process reformation danger is bigger, and reaction is complicated.
Heteropoly acid is widely used in the Industrial Catalysis reaction, because heteropoly acid is the special polynuclear complex that is connected, has the particular space structure through bridging oxygen by central atom and coordination atom, it both can be used as acid type, also can be used as redox bifunctional catalyst, and have higher activity at low temperatures.In heteropoly acid, mix different metal ions such as iron, nickel, cobalt, copper, manganese, vanadium, caesium etc. and can change catalyst, be expected to reduce reaction temperature in addition to the redox property of substrate with to product selectivity.
Heteropoly acid caesium oxometallate H 3+n-xCs xPMo 12-nV nO 40(n=0-4 x=0-3) can be used for the acrylic acid catalyst of oxidation of propane system, and reaction temperature is 400 ℃ [Li Xiukai etc., SCI, 2005,26 (9): 1716-1721].Fe 0.2The HPC heteropolyacid catalyst is Fe 0.2H xPAs 0.2Mo 10VO yThe catalyst that can be used for iso-butane catalytic oxidation system methacrylic acid uses catalyst in the time of 380 ℃, and the conversion ratio of iso-butane can reach about 75% [Cai Tiejun etc., Journal of Molecular Catalysis, 2006,20 (4): 326-329].
Three, summary of the invention
The present invention is intended to for producing hydrogen by methane steam reforming technology provides a kind of catalyst, and technical problem to be solved is compound to improve catalytic activity, to reduce the methane conversion temperature by nickel-base catalyst and heteropolyacid catalyst.
The composite catalyst that the present invention is alleged and the difference of existing catalyst are that nickel based metal catalyst atom (being called for short nickel-base catalyst down) and heteropoly phosphorus molybdenum tungstic acid catalyst (being called for short the P-Mo-W heteropoly acid down) are the composite catalyst of carrier with the alundum (Al, and following chemical formula is arranged:
H 3PMo 6W 6O 40/Al 2O 3/Ni-Ce-Sr
In the formula, the mass ratio 15～25: 75～85 of P-Mo-W heteropoly acid and nickel-base catalyst; Preferred 20: 80; Ni (nickel) and Ce (cerium), Sr (strontium) and Al 2O 3Mol ratio be Ni: Ce: Sr: Al 2O 3=0.8～1.2: 0.8～1.2: 0.8～1.2: 2.0～2.5 preferred 1: 1: 1: 2.3.
The preparation method of this composite catalyst is earlier preparation P-Mo-W heteropoly acid (I) and nickel-base catalyst (II), with (I) and (II) is mixed with composite catalyst then:
1, the preparation of P-Mo-W heteropoly acid (I)
(1) with the sodium tungstate (NaWO of 0.076mol 42H 2O) and the sodium molybdate (NaMoO of 0.076mol 42H 2O) and 0.013mol sodium dihydrogen phosphate (NaH 2PO 42H 2O) dissolve in respectively in the 50ml hot water, and then solution is mixed.
(2) the water-bath heating is stirred to 90 ℃, drips 30ml concentrated hydrochloric acid (about 30min) lentamente to solution then under the stirring of fierceness, and the dropping concentrated hydrochloric acid initial stage has yellow floccule to generate, and occurs white cotton-shaped suspension when reaching a certain amount of, stirring reaction 2 hours.
(3) filter, after the cooling of acquisition filtrate, add the concentrated hydrochloric acid of 20ml again, be transferred in the separatory funnel, and add the ether (, can add a spot of concentrated hydrochloric acid again) of 20ml if can not form three liquid phases.
(4) the vibration separatory funnel makes the liquid layering in the separatory funnel, leaves standstill, and the grease of separatory funnel bottom is refunded in the clean separatory funnel again.
(5) add 10ml concentrated hydrochloric acid, 20ml ionized water and 5ml ether again in separatory funnel, this mixed solution that vibrates behind the standing demix, is put into evaporating dish to the liquid of separatory funnel bottom.
(6) add a spot of ionized water in evaporating dish, evaporation and concentration to solution has crystal to separate out in 60 ℃ of water-baths, filters, and crystal is placed dry 2 hours (70 ℃) of vacuum drying chamber, promptly obtains H 3PMo 6W 6O 40Heteropoly acid.
2, the preparation of nickel-base catalyst (II)
Be that metallic atom Ni auxiliary agent Ce and Sr are adsorbed on carrier A l 2O 3In, elder generation is with nitrate aqueous solution and the carrier A l of Ni, Ce and Sr 2O 3Mix, flood, dehydrate the back roasting and obtain Al 2O 3/ NiO-CeO-SrO, last hydrogenating reduction obtains Al 2O 3/ Ni-Ce-Sr.
Concrete preparation process is as follows:
Compound concentration is respectively 1.70,1.70 and Ni (the NO of 1.70mol/L 3) 2, Ce (NO 3) 2And Sr (NO 3) 2The aqueous solution standby
Adopt the synthetic Al of coprecipitation 2O 3/ NiO-CeO-SrO nickel based metal oxide: preparation Ni (NO 3) 26H 2O and Ce (NO 3) 2The aqueous solution standby, the charge ratio of catalyst and carrier is Ni: Ce: Sr: Al 2O 3=1.0: 1.0: 1.0: 2.33 (mol).The actual nickel nitrate 0.017mol that feeds intake.By proportioning preparation 10g presoma (II), then Ni (NO 3) 26H 2O, Ce (NO 3) 2, Sr (NO 3) 2, Al2O3 drops into 4.94g, 4.49g, 3.60g, 4.04g respectively.With 4.94gNi (NO 3) 26H 2O, 4.49g Ce (NO 3) 23.60gSr (NO 3) 2Join respectively in the 10ml deionized water and dissolve, treat its dissolving fully after, the solution of three components is all poured among the 4.04gAl2O3, stirring mixes fully it, dipping 24h stirs, and macerate is heated with stirring to pasty state.Evaporate to dryness in 120 ℃ of vacuum drying 2 hours, in 400 ℃ and 780 ℃ roasting 2 hours respectively, naturally cools to room temperature with pastel, obtains nickel based metal oxide Al 2O 3/ NiO-CeO-SrO.
In fixed bed reactors under 700 ℃, logical pure hydrogen reductase 12 hour, nickel-base catalyst (II).
3, the preparation of composite catalyst
Accurately take by weighing (I) (H by 20% and 80% mass ratio 3PMo 6W 6O 40) 0.4000g and (II) 1.6000g, with in the deionized water the former fully being dissolved, and pour into to stir among the latter it is fully mixed, 80～90 ℃ stirred in water bath, dipping 24h, with moisture heating evaporation in the macerate, the stirring evaporate to dryness, vacuum drying promptly gets H 3PMo 6W 6O 40/ Al 2O 3/ Ni-Ce-Sr solid-carrying type composite catalyst.
XRD detects:
Measure the X-ray powder diffraction by changeing the target X-ray diffractometer.Instrument model: the Japanese D/max-Ra of company of science, XRD test condition: CuK αRadiation, 40KV, 100mA.
The X-ray diffractometer---Beijing general desorption device XRD of Co., Ltd test condition:
10 ° of θ initial angles, 70 ° of end angles, go on foot wide 0.02 °, wavelength 1.5406nm, 36kV, 40mA
Four. description of drawings
The XRD figure spectrum of Fig. 1 .P-Mo-W heteropoly acid (I).
The IR collection of illustrative plates of Fig. 2 .P-Mo-W heteropoly acid (I).
Fig. 3. the XRD figure spectrum before nickel-base catalyst (II) hydrogenating reduction.
Fig. 4. the XRD figure spectrum behind nickel-base catalyst (II) hydrogenating reduction.
Fig. 5. the XRD figure spectrum before the composite catalyst reaction.
Fig. 6. the reacted XRD figure spectrum of composite catalyst.
Fig. 7. the gas chromatogram before the methane reforming hydrogen manufacturing.
Fig. 8. the gas chromatogram after the methane reforming hydrogen manufacturing.
Fig. 9. self-heating methane reforming hydrogen manufacturing schematic flow sheet, 1. gas steel cylinders, 2. steam generators, 3. air steel cylinders, 4. mass flowmenters, 5. condensers, 6. reactor 7.XMT101 digital display adjusting apparatus, 8. six-way valves, 9. gas chromatographs, 10. chromatographic work stations, 11. data processors among the figure.
Five, the specific embodiment
1.P-Mo-W the preparation of heteropoly acid (I)
Sodium tungstate (the NaWO of accurate weighing 0.076mol 42H 2O) and the sodium molybdate (NaMoO of 0.076mol 42H 2O) and 0.013mol sodium dihydrogen phosphate (NaH 2PO 42H 2O) dissolve in respectively in the 50ml hot water, and then solution is mixed.The water-bath heating is stirred to 90 ℃, slowly drips 30ml concentrated hydrochloric acid (about 30min) to solution then under the stirring of fierceness, stirring reaction 2h, and the initial stage has yellow floccule to generate, and occurs white cotton-shaped suspension subsequently.Filter, the filtrate cooling continues to add the dense HCl of 20ml, and the 20ml ether makes the liquid layering, leave standstill, add the dense HCl of 10ml again, 20ml deionized water, 5ml ether, standing demix, the portion liquid of taking off is inserted in the evaporating dish, adds a small amount of ionized water, and evaporation and concentration to crystal is separated out, and filters, the dry H that gets 3PMo 6W 6O 40Crystallization.
2. the preparation of nickel-base catalyst (II)
Adopt coprecipitation, earlier preparation Ni (NO 3) 2And Ce (NO 3) 2The aqueous solution standby, the preparation Ni mass fraction be 10%.The charge ratio of catalyst and carrier is Ni: Ce: Sr: Al 2O 3=1.0: 1.0: 1.0: 2.33 (mol).Preparation presoma (II) gross mass 10.00g, the actual inventory of nickel nitrate is 0.017mol.With 4.94gNi (NO 3) 26H 2O, 4.49g Ce (NO 3) 23.60gSr (NO 3) 2Join respectively in the 10ml deionized water and dissolve, treat its dissolving fully after, the solution of three components is all poured among the 4.04gAl2O3, stirring mixes fully it, dipping 24h stirs, and macerate is heated with stirring to pasty state.Evaporate to dryness in 120 ℃ of vacuum drying 2 hours, in 400 ℃ and 780 ℃ roasting 2 hours respectively, naturally cools to room temperature with pastel, compd A l 2O 3/ NiO-CeO-SrO.With this compound in fixed bed reactors under 700 ℃ of conditions, logical pure hydrogen reductase 12 h, nickel-base catalyst (II) Al 2O 3/ Ni-Ce-Sr.
3. composite catalyst (P-Mo-W heteropoly acid and Ni-Ce-Sr/Al 2O 3The metallic atom compound) preparation
P-Mo-W heteropoly acid (I) and nickel-base catalyst (II) mix in 20% and 80% ratio of gross mass respectively.Accurately take by weighing (I) H 3PMo 6W 6O 40Be 0.4000g, (II) Ni-Ce-Sr/Al 2O 3Be the 1.6000g catalyst, in deionized water (I) fully dissolved, and pour in (II), stir, it is fully mixed, dipping 24h will flood the adsorbate heating, dehydration by evaporation, and vacuum drying promptly makes composite catalyst.
Be used for the catalyst after the methane conversion load test, from Fig. 5 and Fig. 6 as can be seen, the XRD figure spectrum does not almost change before and after the load test, and this catalyst performance stabilised is described.
4. concrete application example
As shown in Figure 9, methane reforming reaction carries out in differential reactor, reactor is the stainless steel tube of 300mm * Φ 20mm, catalyst is filled in wherein, and product is after super-dry, behind six-way valve, with the online detection of 102G gas-chromatography, TCD detects, and the stainless steel column of TDX-01 of the chromatographic column adopting Lanzhou Chemistry and Physics Institute adopts the intelligent information Graduate School of Engineering N2000 of Zhejiang University type chromatographic work station.Methane flow is controlled to be 10ml/min in the reacting gas, and pressure is 0.01-0.03Mpa, and steam flow is 40ml/min, when reaction temperature reaches 440 ℃, the online testing result of reacting gas effluent, methane conversion reaches 100%, shows that catalyst has advantages of high catalytic activity.(before the reaction, the methane gas-chromatography goes out the peak retention time and is about 1.7min; After the reaction, the hydrogen gas-chromatography goes out the peak retention time and is about 0.7min.

Claims (2)

1, a kind of composite catalyst that is used for producing hydrogen by methane steam reforming technology is characterized in that: this composite catalyst is that nickel based metal catalyst atom and heteropoly phosphorus molybdenum tungstic acid catalyst are the composite catalyst of carrier with the alundum (Al, and following chemical formula is arranged:
H 3PMo 6W 6O 40/Al 2O 3/Ni-Ce-Sr，
In the formula, mass ratio 15～～25 of P-Mo-W heteropoly acid and nickel-base catalyst: 75～～85; Each component mol ratio is Ni: Ce: Sr: Al in the nickel-base catalyst 2O 3=0.8～1.2: 0.8～1.2: 0.8～1.2: 2.0～～2.5.
2, composite catalyst according to claim 1 is characterized in that: the mass ratio of P-Mo-W heteropoly acid and nickel-base catalyst 20: 80, each component mol ratio is Ni: Ce: Sr: Al in the nickel-base catalyst 2O 3=1: 1: 1: 2.3.
CNA2008100222177A 2008-06-27 2008-06-27 Composite catalyst for producing hydrogen by methane steam reforming technology Pending CN101327440A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
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CN102274704A (en) * 2010-06-11 2011-12-14 中国石油化工股份有限公司 Stripping method of deactivated catalyst in preparation of alkene from methanol
CN105107515A (en) * 2015-09-24 2015-12-02 成都理工大学 Nickel-molybdenum carbide composite catalyst for preparing synthesis gas through dry reforming of methane
CN106680407A (en) * 2017-01-06 2017-05-17 中国工程物理研究院核物理与化学研究所 Capillary chromatographic column for analyzing hydrogen isotope mixed gas
CN106770856A (en) * 2017-01-22 2017-05-31 中国工程物理研究院核物理与化学研究所 A kind of chromatography column for analyzing hydrogen isotope mixed gas
CN111547678A (en) * 2020-04-08 2020-08-18 华南农业大学 Method and system for preparing methanol by full-component thermal catalysis of marsh gas

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102274704A (en) * 2010-06-11 2011-12-14 中国石油化工股份有限公司 Stripping method of deactivated catalyst in preparation of alkene from methanol
CN102274704B (en) * 2010-06-11 2013-07-17 中国石油化工股份有限公司 Stripping method of deactivated catalyst in preparation of alkene from methanol
CN105107515A (en) * 2015-09-24 2015-12-02 成都理工大学 Nickel-molybdenum carbide composite catalyst for preparing synthesis gas through dry reforming of methane
CN105107515B (en) * 2015-09-24 2017-04-19 成都理工大学 Nickel-molybdenum carbide composite catalyst for preparing synthesis gas through dry reforming of methane
CN106680407A (en) * 2017-01-06 2017-05-17 中国工程物理研究院核物理与化学研究所 Capillary chromatographic column for analyzing hydrogen isotope mixed gas
CN106770856A (en) * 2017-01-22 2017-05-31 中国工程物理研究院核物理与化学研究所 A kind of chromatography column for analyzing hydrogen isotope mixed gas
CN106770856B (en) * 2017-01-22 2018-05-22 中国工程物理研究院核物理与化学研究所 A kind of chromatography column for being used to analyze hydrogen isotope mixed gas
CN111547678A (en) * 2020-04-08 2020-08-18 华南农业大学 Method and system for preparing methanol by full-component thermal catalysis of marsh gas
CN111547678B (en) * 2020-04-08 2022-03-25 华南农业大学 Method and system for preparing methanol by full-component thermal catalysis of marsh gas

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