CN1317078C - Cerium-titanium composite oxide-carried metal catalyst, and its preparing method and use - Google Patents

Cerium-titanium composite oxide-carried metal catalyst, and its preparing method and use Download PDF

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CN1317078C
CN1317078C CNB200510013099XA CN200510013099A CN1317078C CN 1317078 C CN1317078 C CN 1317078C CN B200510013099X A CNB200510013099X A CN B200510013099XA CN 200510013099 A CN200510013099 A CN 200510013099A CN 1317078 C CN1317078 C CN 1317078C
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cerium
catalyst
composite oxide
titanium
solution
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CN1676218A (en
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刘源
白雪
张媛
叶季蕾
闻学兵
王小燕
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Tianjin University
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Tianjin University
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Abstract

The present invention discloses a cerium titanium composite oxide supported metal catalyst and a preparation method and application thereof. The catalyst uses cerium titanium composite oxide as supporters to support the active constituents of nickel or platinum or cobalt, and the mass content of the active constituents is from 0.5% to 40%. The preparation method comprises: Ce(NO3)3 and TiCl4 are directly mixed, or Ce(NO3)3 and TiCl4 are added to H2O2 to be mixed to prepare a cerium titanium solution; or (NH4)2Ce(NO3)6 and TiCl4 are mixed to prepare the cerium titanium solution; ammonia water is added to the cerium titanium mixed solution, mixtures are mixed, stirred, aged and separated, and a filter cake is washed, separated, dried and calcined to obtain the cerium titanium composite oxide supporters; the supporters are impregnated in a solution of Ni(NO3)2, H2PtCl6 or Co(NO3)2, and the catalyst in which the nickel or the platinum or the cobalt is supported by the cerium titanium composite oxide is obtained by wash, separation, drying and calcination. The catalyst is used for the reformation and the partial oxidation reactions of hydrocarbon compounds. The present invention has the advantage of simple and feasible preparation and production processes, and the dispersivity of the nickel in the prepared catalyst is good, and the catalyst has the advantages of high activity, high selectivity and good stability when used for the reformation and the partial oxidation reactions of the hydrocarbon compounds.

Description

Cerium-titanium composite oxide-carried metal catalyst and preparation method and application
Technical field
The present invention relates to a kind of cerium-titanium composite oxide-carried metal catalyst and preparation method and application, belong to the metal supported catalyst technology that hydrocarbon is reformed and partial oxidation is used.
Background technology
Existing main the having of catalyst that is used for hydrocarbon reformation and partial oxidation:
(1) nickel (Ni) is the catalyst of active component
Such catalyst is active component with nickel, and the carrier of having reported at present has Al 2O 3, silicon and aluminium composite oxides, SiO 2, TiO 2, MgO, ZrO 2Deng metal oxide or CeO 2-ZrO 2, Al 2O 3On the composite metal oxides such as-MgO.As Ni/Al 2O 3 [1], Ni/TiO 2 [2], Ni/CeO 2, Ni/ZrO 2, Ni/SiO 2 [3], Cu, Co, Fe, Ni/ZrO 2 [4], Ni/MgO [5]Deng.These catalyst all have higher initial activity and selectivity, but because the generation of carbon deposit or focus can make catalyst stability not high, service life is short.Adopt composite oxides to make carrier or add other material and can effectively improve catalyst performance, report Ni/CeO arranged 2-ZrO 2 [6], Ni/Al 2O 3-CeO 2 [7], Ni/CaO-CeO 2-ZrO 2 [8]Deng.Ni and CeO 2-ZrO 2Strong interaction is arranged, CeO 2Easily reduction makes and can produce mobile oxygen in the reforming process, and it is very high to participate in reaction decoking activity by Lattice Oxygen.CaO and ZrO 2Join CeO 2In, improve CH effectively 4The partial oxidation activity has reduced carbon deposit, but stability and activity still need to improve.
(2) noble metal catalyst
Such catalyst comprises that noble metals such as Pt, Pd, Ru, Rh, Ir are supported on Al 2O 3, CeO 2, MgO, CeO 2-ZrO 2On oxide or composite metal oxide.This class catalyst can both show good active and selectivity in reformation and partial oxidation.Pt/Al 2O 3, Rh/SiO 2, Pd/CeO 2Deng in the reformation of methane and partial oxidation, very high activity all being arranged, Pd/CeO 2, Pt/CeO 2, Rh/Al 2O 3, Pd/ γ-Al 2O 3, Ir/CeO 2Deng also show very high activity and selectivity in the reformation of ethanol, totally active high than non-precious metal catalyst, anti-coking is strong, has good reaction stability.Bhattacharya etc. have prepared a series of loaded Pd catalyst, and carrier is IIIA family, IVA family and La series metal oxide and γ-Al 2O 3And SiO 2,, remove SiO under certain condition 2Outward, the CO selectivity all can reach more than 99% on other catalyst that support, CH 4Conversion ratio is 33.4%～66.9%; The catalyst that international monopoly provides is supported on La system, IIB family, IV family metal oxide and Al with Pt family metal 2O 3On, having higher CO selectivity equally, usefulness monolithic ceramic materials such as Schmidt support Rh, Pt, Ir, Pd, Pd/La 2O 3Make catalyst, carry out the POM reaction under certain condition, the result points out that the catalytic performance of Rh is best; Propositions such as Buyevskaya are used Rh (carrier-free) or are supported on γ-Al 2O 3On catalyst system and catalyzing study, be used for methane portion oxidation, be supported on γ-Al 2O 3On Rh, the Rh ion is can suppressed by vector stable, better performances.
But when making the catalyst activity component owing to noble metal, common shortcoming is a CO too high levels in the product, when being used for the PEMFC fuel cell, must its content be reduced to 10～30ppm through complicated step, and noble metal costs an arm and a leg very difficult realization the in generally promoting the use of.
List of references
[1]Leroi，Pascaline；Madani，Behrang；Pham-Huu，Cuong；Ledoux，Marc-Jacques；Savin-Poncet，Sabine?Catalysis?Today?53-58，91-92(2004)
[2]Yan，Q.G.；Weng，W.Z.；Wan，H.L.；Toghiani，H.；Toghiani，R.K.；Pittman?Jr，C.U.Applied?CatalysisA：General?43-58，239(2003)
[3]Matsumura，Yasuyuki；Nakamori，Toshie
Applied?Catalysis?A：General?258(1)，107-114(2004)
[4] catalysis journal, 20 (1): 73-75 (1999)
[5]Fujimoto，K.；Yamazaki，O.Tomishige，K.AppliedCatalysisA：General
The content invention
The object of the present invention is to provide a kind of cerium-titanium composite oxide-carried metallic catalyst and preparation method and application, reformation and partial oxidation that this catalyst is used for hydrocarbon have high activity, high selectivity and good stable, and its preparation method process is simple.
The present invention is realized by following technical proposals, a kind of cerium-titanium composite oxide-carried metallic catalyst, it is characterized in that: this catalyst is a carrier with cerium, titanium composite oxide, nickel-loaded or platinum or cobalt active component on it, the mass content of active component (by composition calculated by content of oxides) is 0.5%～40%.
Above-mentioned Preparation of catalysts method is characterized in that comprising following process:
The preparation of carrier:
With Ce (NO 3) 3And TiCl 4Be raw material, and be 0.1～0.9, directly mixed preparing cerium titanium solution by the atomic ratio (Ce/Ti) of cerium titanium; Or press H 2O 2With Ce (NO 3) 3Mol ratio be 0.5～2.0, add H 2O 2Mixed preparing cerium titanium solution; Or with (NH 4) 2Ce (NO 3) 6And TiCl 4Be raw material, and be 0.1～0.9, mixed preparing cerium titanium solution by the atomic ratio (Ce/Ti) of cerium titanium; Adding mass percent to cerium titanium mixed solution is 2%～28% ammoniacal liquor, control pH value is 7.5～11.5, mix and stirred 10 minutes to 4 hours, aging then (placement) 1 hour to 40 hours, carry out Separation of Solid and Liquid more after filtration, solid (sediment) material that filter cake obtains after deionized water and ethanol washing separation is then 50 ℃～180 ℃ dryings, dried solid was calcined 2～6 hours at 350 ℃ to 900 ℃, and obtaining cerium-titanium composite oxide is carrier.
Load active component:
With the cerium-titanium composite oxide carrier that makes, be immersed in the Ni (NO of mass content 0.5%～40% (by composition calculated by content of oxides) 3) 2, H 2PtCl 6Or Co (NO 3) 2Solution in soaked 12 hours～36 hours, isolate solid then, 50 ℃～180 ℃ dryings after 10～30 hours, in 600 ℃～900 ℃ calcinings 1 hour～6 hours, obtain cerium-titanium composite oxide carrier loaded nickel, or load platinum, or load the catalyst of cobalt.
Above-mentioned catalyst is used for the reformation and the partial oxidation reaction of hydrocarbon.
The invention has the advantages that preparation and production procedure are simple, the high dispersive of the catalyst nickel that makes can reduce carbon deposit, is used for hydrocarbon reformation and partial oxidation reaction and has high activity, high selectivity and good stable.
Description of drawings:
Fig. 1 is one of catalytic performance test result of catalyst in the example 1: CH 4Conversion ratio varies with temperature curve;
Fig. 2 be catalyst in the example 1 the catalytic performance test result two: the CO selectivity is with temperature curve;
Fig. 3 be catalyst in the example 1 the catalytic performance test result three: H 2Selectivity varies with temperature curve;
Fig. 4 is NiO10wt%/Ce in the example 1 0.5Ti 0.5O 2100 hours stability change curves of-700 catalyst;
Fig. 5 be in the example 1 respectively 300 ℃ of temperature and 700 ℃, 300 ℃ and 800 ℃, the NiO10wt%/Ce of 300 ℃ and 900 ℃ each roasting 2h gained 0.5Ti 0.5O 2The X-ray diffractogram of catalyst, the sintering temperature of A spectrogram are 300 ℃ and 700 ℃, and the sintering temperature of B spectrogram is 300 ℃ and 800 ℃, and the sintering temperature of C spectrogram is 300 ℃ and 900 ℃;
Fig. 6 is the energy test result of catalyst in the example 2: methane conversion, carbon monoxide selective, hydrogen selective change curve;
Fig. 7 is the X-ray diffractogram of catalyst in the example 2;
The specific embodiment
Embodiment 1: the 10wt%NiO/Ce of co-precipitation-immersion process for preparing series of temperature roasting 0.5Ti 0.5O 2Catalyst preparation process:
Preparing carriers: (1) 0.5mol/LCe (NO 3) 3The preparation of solution: the accurate weighing 75.55gCe of balance 2(CO 3) 38H 2O is measured the nitric acid of 50ml 15mol/L with graduated cylinder.Nitric acid is added drop-wise to Ce slowly 2(CO 3) 38H 2Among the O, and constantly stir until dissolving.To dissolve good Ce (NO then 3) 3Solution moves in the volumetric flask of 500ml, adds distilled water, is mixed with 0.5mol/LCe (NO 3) 3Solution.(2) TiCl 4The preparation of solution: measure 23.4mlTiCl with graduated cylinder 4Hydrochloric acid solution is placed in the fume hood, slowly drips distilled water, TiCl in this solution 4Solution decomposes under the effect of water, discharges a large amount of white cigarettes and produces yellow solid simultaneously.Continuation drips distilled water and dissolves until it on yellow solid, generate yellow solution.(3) get the Ce (NO of 428.6ml0.5mol/L 3) 3The TiCl of solution and (2) preparation 4The solution homogeneous mixture solotion.Get an amount of NH 3H 2O and the Ce for preparing, Ti mixed solution and stream are titrated to puts into the water of a certain amount of pH value between 7-13, constantly stirs simultaneously, and stir speed (S.S.) is about 100N/min.After titration finishes, continue to stir 4 hours.Placed at room temperature aging 24 hours.Then aging good precipitation is washed suction filtration.With distilled water washing three times, use distilled water 400ml, during washing with stirring at every turn; The ethanol washed twice is used in the washing back, uses ethanol 100ml, with stirring at every turn.Filter cake behind washing and the suction filtration is placed in 80 ℃ the constant temperature oven carried out drying 24 hours.It is standby to weigh up quantity of sample 80 ℃ of good filter cakes placement coolings at room temperature of drying.
Load active component: weigh the support samples (pressing hydroxide calculates) of the above-mentioned preparation of 20g, be converted into oxide mass then.Take by weighing 5.779gNi (NO by the oxide mass that converts 3) 26H 2O is dissolved in an amount of distilled water.Then above-mentioned load weighted sample is flooded wherein, and stir 20-30min.The sample that dipping is good is placed standing over night at room temperature, in 80 ℃ constant temperature oven dry 12 hours then.Sample is divided into three parts then, respectively at 300 ℃ and 700 ℃, 300 ℃ and 800 ℃, 300 ℃ and 900 ℃ of each roastings 2 hours.Promptly obtain the mass content 10%NiO/Ce of different sintering temperature roastings 0.5Ti 0.5O 2
The catalyst performance test: carry out on the fixed bed quartz tube reactor of the performance test of catalyst under normal pressure, the quartz tube reactor specification is Φ 10 * 2.The laboratory sample consumption is 200mg, and granularity is the 40-60 order, and the unstripped gas air speed is 55,200ml/hg CatRaw material consists of: 20vol.%CH 4, 10vol.%O 2, 70vol.%N 2Sample is warming up to 650 ℃ from room temperature, uses N 2Purge, use 5vol%H at 650 ℃ 2-Ar reduces 30min, makes reaction gas after the reduction into.Under the reaction gas condition, temperature change is to reaction temperature.Reaction is since 650 ℃, establishes a temperature spot to 850 ℃ for per 50 ℃.Each temperature spot reaction 1 hour.The on-line analysis of SP-2100 type gas-chromatography, 5A molecular sieve column and GDX-502 post, TCD detects.
The catalytic performance test result of the catalyst that The performance test results example 1 is prepared is shown in down Fig. 1,2,3,4:
From the result, can obtain in the catalyst activity and the selectivity of 300 ℃ and 700 ℃ roastings best;
The stability experiment test: carry out on the fixed bed quartz tube reactor of the performance test of catalyst under normal pressure, the quartz tube reactor specification is Φ 10 * 2.The laboratory sample consumption is 200mg, and granularity is the 40-60 order, and the unstripped gas air speed is 55,200ml/hg CatRaw material consists of: 20vol%CH 4, 10vol%O 2, 70vol%N 2Sample is warming up to 650 ℃ from room temperature, uses N 2Purge, use 5vol.%H at 650 ℃ 2-Ar reduces 30min, makes reaction gas after the reduction into.Under the reaction gas condition, temperature change to 750 ℃.Constant temperature beginning in 1 hour collected specimens.The on-line analysis of SP-2100 type gas-chromatography, 5A molecular sieve column and GDX-502 post, TCD detects.
The stability test of the catalyst of example 1 preparation the results are shown in down Fig. 5:
Embodiment 2: the mass content 10%NiO/Ce of 700 ℃ of roastings of co-precipitation-immersion process for preparing 0.15Ti 0.85O 2Catalyst
Preparation process:
Preparing carriers: (1) TiCl 4The preparation of solution: measure 8.9mlTiCl with graduated cylinder 4Hydrochloric acid solution is placed in the fume hood, slowly drips distilled water, TiCl in this solution 4Solution decomposes under the effect of water, discharges a large amount of white cigarettes and produces yellow solid simultaneously.Continuation drips distilled water and dissolves until it on yellow solid, generate yellow solution.(2) get the Ce (NO of 28.8ml0.5mol/L 3) 3The TiCl of solution and (1) preparation 4The solution homogeneous mixture solotion.All the other steps are the same.
Load active component: weigh the support samples (pressing hydroxide calculates) of the above-mentioned preparation of 10g, be converted into oxide mass then.Take by weighing 3.608gNi (NO by the oxide mass that converts 3) 26H 2O is dissolved in an amount of distilled water.Then above-mentioned load weighted sample is flooded wherein, and stir 20-30min.The sample that dipping is good is placed standing over night at room temperature, in 80 ℃ constant temperature oven dry 12 hours then.Sample is in 300 ℃ and 700 ℃ roasting 2 hours respectively.Promptly obtain NiO10wt%/Ce 0.15Ti 0.85O 2Be designated as I-N10CT4-700 respectively.The sample that roasting is good grinds to form 40-60 purpose particle and is used for the catalytic performance test.
The catalyst performance test is with example 1; The performance test results: as Fig. 6,7.
Embodiment 3: the 1wt%Pt/Ce of 700 ℃ of roastings of co-precipitation-immersion process for preparing 0.15Ti 0.85O 2Catalyst
The preparation method:
Preparing carriers: (1) TiCl 4The preparation of solution: measure 8.9mlTiCl with graduated cylinder 4Hydrochloric acid solution is placed in the fume hood, slowly drips distilled water, TiCl in this solution 4Solution decomposes under the effect of water, discharges a large amount of white cigarettes and produces yellow solid simultaneously.Continuation drips distilled water and dissolves until it on yellow solid, generate yellow solution.(2) get the Ce (NO of 28.8ml0.5mol/L 3) 3The TiCl of solution and (1) preparation 4The solution homogeneous mixture solotion.All the other steps are the same.
Load active component: weigh the support samples (pressing hydroxide calculates) of the above-mentioned preparation of 10g, be converted into oxide mass then.Measure 0.005mol/L H by the oxide mass that converts 2PtCl 6Solution 8.2ml.Support samples is flooded wherein, and stir 20-30min.The sample that dipping is good is placed standing over night at room temperature, in 80 ℃ constant temperature oven dry 12 hours then.Then in 300 ℃ and 700 ℃ roasting 2 hours respectively.Promptly obtain the Pt10wt%/Ce of different sintering temperature roastings 0.15Ti 0.85O 2
The catalyst performance test is with example 1.
Embodiment 4: the 10wt%CoO/Ce of 700 ℃ of roastings of co-precipitation-immersion process for preparing 0.15Ti 0.85O 2Catalyst
The preparation method:
Preparing carriers: (1) TiCl 4The preparation of solution: measure 8.9mlTiCl with graduated cylinder 4Hydrochloric acid solution is placed in the fume hood, slowly drips distilled water, TiCl in this solution 4Solution decomposes under the effect of water, discharges a large amount of white cigarettes and produces yellow solid simultaneously.Continuation drips distilled water and dissolves until it on yellow solid, generate yellow solution.(2) get the Ce (NO of 28.8ml0.5mol/L 3) 3The TiCl of solution and (1) preparation 4The solution homogeneous mixture solotion.All the other steps are the same.
Load active component: weigh the support samples (pressing hydroxide calculates) of the above-mentioned preparation of 10g, be converted into oxide mass then.Measure 0.5mol/LCo (NO by the oxide mass that converts 3) 2Solution 21.4ml.Above-mentioned load weighted support samples is flooded wherein, and stir 20-30min.The sample that dipping is good is placed standing over night at room temperature, in 80 ℃ constant temperature oven dry 12 hours then.Then in 300 ℃ and 700 ℃ roasting 2 hours respectively.Promptly obtain the CoO10wt%/Ce of different sintering temperature roastings 0.15Ti 0.85O 2
The catalyst performance test is with example 1.

Claims (3)

1. the catalyst of a cerium-titanium composite oxide-carried metal, it is characterized in that: this catalyst is that 0.1～0.9 cerium-titanium composite oxide is a carrier with the atomic ratio of cerium and titanium in the cerium titanium oxide, nickel-loaded or platinum or cobalt active component on the carrier, the mass content of active component is 0.5%～40%.
2. catalyst method for preparing the described cerium-titanium composite oxide-carried metal of claim 1 is characterized in that comprising following process:
1) preparation of carrier:
With Ce (NO 3) 3And TiCl 4Be raw material, and be 0.1～0.9, directly mixed preparing cerium titanium solution by the atomic ratio of cerium titanium; Or press H 2O 2With Ce (NO 3) 3Mol ratio be 0.5～2.0, add H 2O 2Mixed preparing cerium titanium solution; Or with (NH 4) 2Ce (NO 3) 6And TiCl 4Be raw material, and be 0.1～0.9, mixed preparing cerium titanium solution by the atomic ratio of cerium titanium; Adding mass percent to cerium titanium mixed solution is 2%～28% ammoniacal liquor, control pH value is 7.5～11.5, mix and stirred 10 minutes to 4 hours, aging 1 hour to 40 hours then, carry out Separation of Solid and Liquid again, filter cake obtains solid matter after deionized water and ethanol washing separation, then 50 ℃～180 ℃ dryings, dried solid was calcined 2～6 hours at 350 ℃ to 900 ℃, and obtaining cerium-titanium composite oxide is carrier; Or dried solid is directly as carrier;
2) load active component:
With the cerium-titanium composite oxide carrier that step 1) makes, dipping is 0.5%～40% Ni (NO by oxide calculated mass content 3) 2, H 2PtCl 6Or Co (NO 3) 2Soaked in the solution 12 hours～36 hours, and isolated solid then, 50 ℃～180 ℃ dryings after 10～30 hours, in 600 ℃～900 ℃ calcinings 1 hour～6 hours, obtain cerium-titanium composite oxide carrier loaded nickel, or load platinum, or load the catalyst of cobalt.
3. the Application of Catalyst of the described cerium-titanium composite oxide-carried metal of claim 1 is characterised in that the reformation and the partial oxidation reaction that are used for hydrocarbon.
CNB200510013099XA 2005-01-17 2005-01-17 Cerium-titanium composite oxide-carried metal catalyst, and its preparing method and use Expired - Fee Related CN1317078C (en)

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CN102513105A (en) * 2011-12-16 2012-06-27 中国科学院生态环境研究中心 Hydrogen production catalyst
CN105670710B (en) * 2016-02-02 2018-05-08 河南省科学院能源研究所有限公司 A kind of method using hydrogen peroxide as raw material reforming biomass crude synthesis gas
CN107398281A (en) * 2017-06-28 2017-11-28 顾秋军 A kind of FCC regenerated flue gas denitration catalyst, preparation method and its usage
CN107433197A (en) * 2017-06-29 2017-12-05 顾渊 A kind of denitration catalyst, preparation method and its usage
CN114618490B (en) * 2022-03-30 2023-07-14 刘盛楹 Catalyst for hydrogen production by reforming natural gas, and preparation method and application thereof
CN116139910B (en) * 2023-02-15 2024-03-22 昆明理工大学 New use of nickel-based re-hydroxylation silicon-based catalyst

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