CN102513105A - Hydrogen production catalyst - Google Patents
Hydrogen production catalyst Download PDFInfo
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- CN102513105A CN102513105A CN201110427204XA CN201110427204A CN102513105A CN 102513105 A CN102513105 A CN 102513105A CN 201110427204X A CN201110427204X A CN 201110427204XA CN 201110427204 A CN201110427204 A CN 201110427204A CN 102513105 A CN102513105 A CN 102513105A
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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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
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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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Abstract
The invention provides a cerium-based composite oxide loaded noble metal catalyst for catalyzing alcohols and hydrocarbons to carry out hydrogen production by reforming, comprising two parts including noble metal and a carrier. The noble metal is one or combination of more than two of rhodium, platinum, palladium, iridium, ruthenium and gold; and the carrier is a cerium-based composite oxide carrier which takes a cerium-lanthanum solid solution as a representative. The catalyst can be applied in the form of a grain state or a powder state and also can be coated on a porous integral ceramic to be used as a monolithic catalyst. The invention further provides a manufacturing method of the catalyst, which comprises the following steps of preparing a cerium-based composite oxide and loading the noble metal. Some preferable implementation schemes of the catalyst utilize biological ethanol as a raw material and the prepared hydrogen can be considered to a renewable energy source; and the catalyst can be applied to the condition of a high space velocity.
Description
Technical field
The present invention relates to a kind of catalyst; Be specifically related to a kind of noble metal that is used for catalysis low temperature reformation hydrogen production and load on the catalyst on the cerium-based composite oxides, particularly a kind of being used for ethanol is the lower alcohol hydrogen manufacturing of representative and is the rudimentary hydrocarbon hydrogen manufacturing of representative with the dodecane.
Background technology
The energy and environmental problem are two big subject matters of present face of mankind; This mainly is because the present energy great majority that rely on of people are fossil energies; And fossil fuel is not only non-renewable, and reserves are fewer and feweri, and in the process of using, also emits a large amount of pollutants.Therefore the alternative energy source of seeking a kind of reproducible cleaning is extremely urgent.
Hydrogen is a kind of desirable energy carrier, because hydrogen and oxygen are reflected at when emitting energy, unique product is a water, is clean energy resource truly.But the hydrogen that in the Nature, does not almost have the simple substance state to exist, so producing of hydrogen becomes a crucial step in the process that Hydrogen Energy uses.
The raw material of hydrogen manufacturing mainly contains hydrogeneous raw materials such as water, alcohols, alkane, oil, methane, and reforming through the conversion of CO steam also is an effective hydrogen manufacturing route.
By water decomposition hydrogen manufacturing is a kind of desirable mode, but at present because there is following problem to be difficult to solve, water hydrogen manufacturing also is in conceptual phase.At first, if through water electrolysis hydrogen production, consumed power, therefore the energy that the amount of consumed power will be emitted in the Hydrogen Energy use, is uneconomic on energy efficiency.If secondly through photolysis water hydrogen, present catalyst, for example titanium oxide; Utilization ratio to sunshine is very low, under a lot of situation, promptly uses ultraviolet light; The efficient of photocatalytic hydrogen production by water decomposition also is lower, is difficult to reach at short notice practical application energy needed density.
Therefore, the hydrogen production process that is expected to practical application in the short period of time still will rely on oxygen-bearing hydrocarbon or hydrocarbon.Because the application of Hydrogen Energy generally will depend on fuel cell, in order to be applicable to the application of mobile fuel cell, hydrogen feedstock mainly adopts liquid material.The liquid material that can be used for hydrogen manufacturing mainly contains alcohols, alkane, oil product.In numerous raw materials, the H/C of methyl alcohol and ethanol is the highest.Yet methyl alcohol has toxicity.Comparatively speaking, ethanol can obtain from the sweat of biological raw material, is reproducible, and does not have toxicity, therefore becomes the desirable feedstock of present hydrogen manufacturing.Can solve the energy and environment two large problems simultaneously by bio-ethanol hydrogen manufacturing.
Catalysis ethanol hydrogen manufacturing mainly can be divided into three kinds of modes, that is: hydrogen production by ethanol steam reforming, partial oxidation of ethanol to prepare hydrogen, ethanol self-heating reforming hydrogen manufacturing.Hydrogen production by ethanol steam reforming is the reforming reaction that ethanol and water take place, and its hydrogen selective is high, and the temperature that still requires is wanted more than 500 ℃ generally than higher, and the catalysis of selecting for use mainly is nickel-base catalyst.In order to reduce reaction temperature, still to rely on noble metal catalyst, because precious metal catalyst more helps the fracture of C-C key than Ni in lower temperature.Through the long-term research to hydrogen production by ethanol steam reforming, people find the problem that wherein exists gradually, and for example, catalyst is easy to inactivation in the process of using, and the reason of inactivation mainly is the generation of the sintering and the carbon distribution of noble metal.Through further discovering, partial oxidation reformation ethanol hydrogen production since the existence of oxygen not only can suppress the generation of carbon distribution but also not need the supply of energy.But the problem of its existence is that the selectivity of hydrogen is low, can cause a large amount of wastes of hydrogen feedstock like this, and the accessory substance that produces also is difficult to eliminate.The ethanol self-heating reforming hydrogen manufacturing is the combination of above dual mode, and the reaction temperature of its requirement is lower, also not lot of energy input, and the existence of oxygen can suppress the generation of carbon distribution.Based on above reason, the ethanol self-heating reforming hydrogen manufacturing more and more receives people's attention.
The catalyst of ethanol hydrogen production has certain versatility for above three kinds of ethanol hydrogen production modes, also rarely has the researcher to point out the difference of required catalyst under the different hydrogen manufacturing conditions at present.This possibly be because ethanol hydrogen production is a kind of optionally reaction, be not the reduction reaction that simple oxidation reaction neither be simple, and entire reaction is the coefficient results of a plurality of reactions, so whether the oxygen G&W exists the selection that is not determining catalysis.Generally, there is the catalyst of better activity under other two kinds of conditions, also to have performance preferably to the ethanol self-heating reforming hydrogen manufacturing.And the catalyst that helps ethanol hydrogen production is to other alcohols hydrogen manufacturing, and alkane hydrogen manufacturing even diesel oil hydrogen manufacturing all have certain activity, because the intermediate reaction of catalytic organism hydrogen production reaction is identical or close.Because water gas shift reation is a crucial intermediate reaction in the ethanol hydrogen production process, therefore helping the ethanol hydrogen production catalyst generally can extremely help water gas shift reation.
In known catalyst, rhodium has shown very good C-C bond fission ability, is active component commonly used at present.For the ethanol hydrogen production catalyst, the selection of carrier also is crucial.Originally people select for use specific area bigger mostly; Use wider silica and alumina support; Having the researcher to adopt basic supports such as zinc oxide, magnesia afterwards, mainly is to have cerium oxide or the cerium zirconium sosoloid carrier that stores the oxygen function and study many at present.But there is certain problem in cerium oxide carrier, as, specific area is less, and poor stability uses easy inactivation for a long time.Cerium zirconium sosoloid is the main component of three-way catalyst, is used for the carrier of hydrogen production reaction catalyst, though certain activity is arranged, the mechanism difference of two kinds of reactions is very big after all, so its specific activity is more limited.And cerium and zirconium usually all exist with the form of 4 valencys in cerium zirconium sosoloid, and the amount of the oxygen vacancies of introducing is limited.And if the adding lanthanum because it shows 3 valencys, can be introduced more oxygen vacancies.The most important thing is that China is the very abundant country of rare earth resources, lanthanum, cerium are the abundantest compositions of rare earth mineral.Cerium, lanthanum are the effective and reasonable utilization that the extensive use of the catalyst of principal component helps China's rare earth resources, improve the added value of rare earth industry.The adding of transition metal such as iron, cobalt, nickel also can improve the active and stable of catalyst for preparing hydrogen to a certain extent in addition.
Therefore, developing a kind of is active component with the noble metal, is the catalyst of carrier with the cerium-based composite oxides, has higher activity and selectivity in the hope of it, and better endurance is very necessary at present work.Use reproducible raw material, producing hydrogen efficiently is a crucial approach that solves energy problem at present, has very important Significance for Environment.
Summary of the invention
Deficiency to prior art; Low in order to solve existing catalyst for preparing hydrogen ethanol conversion, the hydrogen selectivity is low, shortcomings such as poor stability; The present invention provides a kind of novel noble metal to load on the Catalysts and its preparation method on the cerium-based composite oxides first; Can be used for ethanol is the lower alcohols hydrogen manufacturing of representative, is the long chain alkane hydrogen manufacturing of representative with the dodecane, and the reaction of CO vapor reforming hydrogen production.The present invention is preferred for bio-ethanol hydrogen manufacturing.
Therefore, one of the object of the invention is to provide a kind of catalyst that is used for the cerium-based composite oxides supported precious metal of catalyzing alcohols and hydro carbons low temperature reformation hydrogen production.Low temperature refers to below 500 ℃.
Said composite oxide catalysts comprises a kind of or two kinds and above noble metal, also comprises cerium oxide and at least a other rare-earth oxides or transition metal oxide.
A kind of or or its combination in said noble metal selected from rhodium (Rh), platinum (Pt), palladium (Pd), iridium (Ir), ruthenium (Ru), the gold (Au).
Preferably, a kind of or or its combination in said noble metal selected from rhodium (Rh), platinum (Pt), palladium (Pd), iridium (Ir), the ruthenium (Ru).
Said noble metal is preferably, Rh, Ir, Rh-Pt, Rh-Pd, Rh-Ru
Said rare earth metal comprises: lanthanum (La), yttrium (Y), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), scandium (Sc), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu); Said transition metal comprises: titanium (Ti), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), zirconium (Zr), niobium (Nb), molybdenum (Mo), tungsten (W);
Said cerium-based composite oxides carrier is preferably CeOx-LaOx, CeOx-ZrOx, CeOx-PrOx, CeOx-CuOx, CeOx-FeOx;
Said cerium-based composite oxides carrier forms type solid solution of cerium oxide type, and wherein the molar content of cerium oxide is 20～96%, is preferably 40～80%.
The mass content of said noble metal is 0.2～5wt.%, is preferably 0.5～1.5%.
Said cerium-based composite oxides Preparation of catalysts method is sluggish precipitation, sol-gel process, citric acid complex method, roasting direct method or hydrothermal synthesis method.
Said sluggish precipitation comprises the steps:
(1) the precursor salt with cerium oxide and rare earth metal or transition metal is made into mixed solution, and wherein the molar content of cerium salt is 20～96%.
(2) with excessive urea as precipitating reagent, under 80～95 ℃ of temperature conditions, stir 0.5～48h;
(3) after filtration and the washing, obtain filter cake, perhaps through the sediment that arrives centrifugal and washing;
(4) with filter cake or sediment oven dry,, obtain said cerium-based composite oxides in 300～900 ℃ of roastings in air;
Preferably, in the said step (1), at least a or two and above mixture in the preferred cerous chlorate of said cerium salt, cerous nitrate, ammonium ceric nitrate, the cerous sulfate;
Preferably, in the said step (1), said rare earth metal and transition metal salt comprise lanthanum salt, ytterbium salt, zirconates, molysite, mantoquita.Further be preferably lanthanum salt.Lanthanum salt is preferably at least a or two and above mixture that comprises in lanthanum nitrate, lanthanum sulfate, lanthanum chloride, lanthana, the lanthanum carbonate.
Preferably, in the said step (2), the preferred 1～24h of said mixing time, further preferred 4～15h, for example 5h, 6h, 8h or 12h;
Preferably, in the said step (2), said temperature is preferably 60～100 ℃, and more preferably 70～98 ℃, further preferred 80～95 ℃;
Preferably, in the said step (3), the deionized water washing is preferably adopted in said washing, and preferred 1～5 time of washing times for example 2～4 times, comprises 3 times;
Preferably, in the said step (4), said oven dry is preferable over 80～140 ℃ of oven dry down; Further preferably put into baking oven in 80～120 ℃ of oven dry; Drying time is preferably 1～36h, more preferably 2～24h, further preferred 4～12h;
Preferably, in the said step (4), said roasting is preferably through Muffle furnace roasting in 300～900 ℃ of air; Preferred 1～the 24h of said roasting time, preferred 2～12h, further preferred 4～6h; Sintering temperature is preferably 300～600 ℃, further preferred 450～550 ℃.
Said sol-gel process comprises the steps:
(1) the precursor salt with cerium oxide and rare earth metal or transition metal is made into mixed solution, and wherein the molar content of cerium salt is 20～96%.
(2) stir 0.5～72h at ambient temperature, obtain colloidal sol;
(3) gained colloidal sol normal temperature, normal pressure are left standstill 0.5～12d, obtain gel;
(4) with the gel oven dry,, obtain said cerium-based composite oxides catalyst in 300～900 ℃ of roastings in air;
Preferably, in the said step (1), at least a or two and above mixture in the preferred cerous chlorate of said cerium salt, cerous nitrate, ammonium ceric nitrate, the cerous sulfate;
Preferably, in the said step (1), said rare earth metal and transition metal salt comprise lanthanum salt, ytterbium salt, zirconates, molysite, mantoquita.Further be preferably lanthanum salt.Lanthanum salt is preferably at least a or two and above mixture that comprises in lanthanum nitrate, lanthanum sulfate, lanthanum chloride, lanthana, the lanthanum carbonate.
Preferably, in the said step (2), the preferred 1～60h of said mixing time, further preferred 4～48h, for example 6h, 10h, 12h or 24h;
Preferably, in the said step (3), the preferred 1～10d of said time of repose, further preferred 2～7d, for example 3d, 4d, 5d or 6d;
Preferably, in the said step (4), said oven dry is preferable over 80～120 ℃ of oven dry down; Further preferably put into baking oven in 80～120 ℃ of oven dry; More drying time is preferably 1～36h, more preferably 2～24h, further preferred 4～12h;
Preferably, in the said step (4), said roasting is preferably through Muffle furnace roasting in 300～900 ℃ of air; Preferred 1～the 24h of said roasting time, preferred 2～12h, further preferred 4～6h; Sintering temperature is preferably 300～600 ℃, further preferred 450～550 ℃.
Said citric acid complex method comprises the steps:
(1) the precursor salt with cerium oxide and rare earth metal or transition metal is made into mixed solution, and wherein the molar content of cerium salt is 20～96%.
(2) in mixed solution, add a certain amount of citric acid, the mol ratio of metal ion total amount and citric acid is 0.5～5.0;
(3) under 20～95 ℃ of temperature conditions, stir 0.5～48h;
(4) normal temperature and pressure leaves standstill 0.5～5d;
(5) with the products therefrom oven dry,, obtain said cerium-based composite oxides catalyst in 300～900 ℃ of roastings in air;
Preferably, in the said step (1), at least a or two and above mixture in the preferred cerous chlorate of said cerium salt, cerous nitrate, ammonium ceric nitrate, the cerous sulfate;
Preferably, in the said step (1), said rare earth metal and transition metal salt comprise lanthanum salt, ytterbium salt, zirconates, molysite, mantoquita.Further be preferably lanthanum salt.Lanthanum salt is preferably at least a or two and above mixture that comprises in lanthanum nitrate, lanthanum sulfate, lanthanum chloride, lanthana, the lanthanum carbonate.
Preferably, in the said step (3), the preferred 1～40h of said mixing time, further preferred 2～24h, for example 3h, 5h, 10h or 20h;
Preferably, in the said step (4), the preferred 1～4d of said time of repose, for example 2d or 3d;
Preferably, in the said step (5), said oven dry is preferable over 80～120 ℃ of oven dry down; Further preferably put into baking oven in 80～120 ℃ of oven dry; More drying time is preferably 1～36h, more preferably 2～24h, further preferred 4～12h;
Preferably, in the said step (5), said roasting is preferably through Muffle furnace roasting in 300～900 ℃ of air; Preferred 1～the 24h of said roasting time, preferred 2～12h, further preferred 4～6h; Sintering temperature is preferably 300～600 ℃, further preferred 450～550 ℃.
Said hydrothermal synthesis method comprises the steps:
(1) salt with Ce and La is made into mixed solution, and in the said mixed solution, with the molar ratio computing of metallic element, the ratio of cerium and lanthanum is 0.4～30;
(2) stir 0.5～2h at ambient temperature after, solution is moved in the stainless steel cauldron of inner liner polytetrafluoroethylene;
(3) with agitated reactor at 80～200 ℃ of condition held 1～12d;
(4),, obtain said cerium-based composite oxides catalyst in 300～900 ℃ of roastings in air with products therefrom centrifuge washing, oven dry;
Preferably, in the said step (1), at least a or two and above mixture in the preferred cerous chlorate of said cerium salt, cerous nitrate, ammonium ceric nitrate, the cerous sulfate;
Preferably, in the said step (1), said rare earth metal and transition metal salt comprise lanthanum salt, ytterbium salt, zirconates, molysite, mantoquita.Further be preferably lanthanum salt.Lanthanum salt is preferably at least a or two and above mixture that comprises in lanthanum nitrate, lanthanum sulfate, lanthanum chloride, lanthana, the lanthanum carbonate.
Preferably, in the said step (3), said standing time preferred 1～12d, further preferred 2～8d, for example 3d, 4d, 5d or 6d;
Preferably, in the said step (4), said oven dry is preferable over 80～120 ℃ of oven dry down; Further preferably put into baking oven in 80～120 ℃ of oven dry; More drying time is preferably 1～36h, more preferably 2～24h, further preferred 4～12h;
Preferably, in the said step (4), said roasting is preferably through Muffle furnace roasting in 300～900 ℃ of air; Preferred 1～the 24h of said roasting time, preferred 2～12h, further preferred 4～6h; Sintering temperature is preferably 300～600 ℃, further preferred 450～550 ℃.
The carrying method of described catalyst noble metal is infusion process, the precipitation method, ion-exchange.
Said infusion process need comprise following steps
(1) with an amount of noble metal salt wiring solution-forming;
(2) an amount of cerium-based composite oxides impregnated in an amount of precious metal salt solution;
(3) oven dry after dipping is accomplished, roasting;
Preferably, in the said step (1), said precious metal salt is preferably rhodium salt, palladium salt, platinum salt, ruthenium salt, iridium salt.Rhodium salt is preferably radium chloride.Palladium salt is preferably palladium bichloride, palladium nitrate.Platinum salt is preferably platinum chloride, platinum nitrate.Ruthenium salt is preferably ruthenic chloride.Iridium salt is preferably iridium chloride, chloro-iridic acid.
Preferably, in the said step (3), said roasting is preferably through Muffle furnace roasting in 300～900 ℃ of air; Preferred 1～the 24h of said roasting time, preferred 2～12h, further preferred 4～6h; Sintering temperature is preferably 300～600 ℃, further preferred 450～550 ℃.
Described catalyst is applicable to that lower alcohols and rudimentary hydro carbons low temperature produces hydrogen, and said lower alcohol is preferably methyl alcohol, ethanol, propyl alcohol, butanols, glycerine, further is preferably ethanol; Said hydro carbons is methane, ethane, decane, dodecane, further is preferably dodecane.Low temperature is preferably 100～480 ℃, further is preferably 200～450 ℃.
One of the object of the invention also is to provide a kind of low-temperature catalyzed pure and mild hydrocarbon to produce the method for hydrogen, and said method is used the catalyst of cerium-based composite oxides supported precious metal of the present invention.This catalyst can carry out slurrying according to actual needs, loads to then on the various honeycomb ceramic carriers, and the catalyst that is prepared into moulding uses, also can be through using after the extrusion modling.Catalyst is placed reactor; Spray into mixed raw materials gas at the upper reaches of catalyst; After in reactor, reacting; Produce hydrogen, the hydrogen of generation separates through film or other separate modes are purified back or directly feed fuel cell or hydrogen storage material without purifying and be used or store;
Said hydrogen production process can be the lower alcohols reformation hydrogen production, also can be the hydrocarbon reformation hydrogen production; Said hydrogen production process is preferably the ethanol reformation hydrogen production.
The present invention has following advantage:
Said cerium-based composite oxides supported precious metal catalyst stability is high, can not have tangible inactivation in long-term work under the reaction condition, can guarantee the service life of catalyst;
In wider temperature range, can not produce liquid accessory substance basically, help follow-up use, not need the purification of tail gas basically;
The generation of CO is fewer, is difficult for making fuel cell to poison, and has improved the actual scope of application of catalyst.
Insensitive to reaction velocity, be applicable to the original position hydrogen manufacturing of moving fuel cell, cost is practiced thrift in the space that helps practicing thrift mobile device;
Has very excellent H
2Generate selectivity;
Has extraordinary stability;
Adopt nontoxic component, effectively reduced harm health and ecological environment.
The specific embodiment
For ease of understanding the present invention, it is following that the present invention enumerates embodiment.Those skilled in the art should understand, and said embodiment only is used for helping to understand the present invention, should not be regarded as concrete restriction of the present invention.
Embodiment 1
With cerous nitrate and lanthanum nitrate with 9: 1 wiring solution-formings; In this solution, add excessive urea, and continuous stirring 12h, suction filtration and washing then under 90 ℃ of temperature conditions; Filter cake is put into baking oven spend the night, after Muffle furnace roasting 5h in 500 ℃ of air makes powder in 110 ℃ of oven dry.Add an amount of rhodium chloride solution, adopting infusion process to process load capacity is 1% load type rhodium catalyst.Product after the load is put into baking oven spend the night, after Muffle furnace roasting 3h in 500 ℃ of air makes powder catalyst in 110 ℃ of oven dry.
With the catalyst compressing tablet that makes, grind, sieve, it is subsequent use to get 40～60 orders, is called catalyst A.
Embodiment 2
Other condition such as embodiment 1 are constant, and changing the Ce/La mol ratio is 8: 2, makes catalyst B.
Embodiment 3
Other condition such as embodiment 1 are constant, and changing the Ce/La mol ratio is 7: 3, makes catalyst C.
Embodiment 4
Other condition such as embodiment 1 are constant, and changing the Ce/La mol ratio is 6: 4, makes catalyst D.
Embodiment 5
Other condition such as embodiment 1 are constant, and changing the Ce/La mol ratio is 1: 1, makes catalyst E.
Embodiment 6
Make the cerium-based composite oxides supported precious metal catalyst with embodiment 1-5 and on fixed bed, carry out ethanol hydrogen production reactive activity and optionally investigation.
The use amount of catalyst is 100mg, and the flow of ethanol water is 0.06mL/min, O
2=6mL/min, N
2=300mL/min, the time of contact～the 18ms reaction temperature is 350 ℃, mass space velocity is 207,000mLh
-1Min
-1Product that produces in the course of reaction and balanced gas are all used gas Chromatographic Determination.Reaction result is as shown in table 1.
Table 1 various ce/La mol ratio cerium lanthanum solid solution load rhodium catalyst activity rating result
Can know by table 1; Catalyst B, C, D, E have reached ethanol 100% and have transformed in the time of 350 ℃; And acetaldehyde and acetone almost do not produce, and wherein the hydrogen selectivity of C is the highest, and its CO selectivity is minimum; That is to say that this catalyst makes reactant generate hydrogen to greatest extent, and suppress to have the generation of toxic byproduct CO, acetaldehyde and acetone.More than all catalyst all do not have to produce can be detected ethene, do not have the generation of acetaldehyde, acetone, ethene, suppressed the generation of carbon distribution to a certain extent.
Applicant's statement; The present invention explains detailed process equipment of the present invention and technological process through the foregoing description; But the present invention is not limited to above-mentioned detailed process equipment and technological process, does not mean that promptly the present invention must rely on above-mentioned detailed process equipment and technological process could be implemented.The person of ordinary skill in the field should understand, and to any improvement of the present invention, to the interpolation of the equivalence replacement of each raw material of product of the present invention and auxiliary element, the selection of concrete mode etc., all drops within protection scope of the present invention and the open scope.
Claims (10)
1. the catalyst of the cerium-based composite oxides supported precious metal of catalyzing alcohols and hydro carbons low temperature reformation hydrogen production; It is characterized in that comprising a kind of, two kinds or above noble metal; Said cerium-based composite oxides comprises cerium oxide and at least a other rare-earth oxides or transition metal oxide, and low temperature refers to below 500 ℃.
2. catalyst according to claim 1 is characterized in that, a kind of or combination more than 2 kinds in said noble metal selected from rhodium (Rh), platinum (Pt), palladium (Pd), iridium (Ir), ruthenium (Ru), the gold (Au);
Preferably, a kind of in said noble metal selected from rhodium (Rh), platinum (Pt), palladium (Pd), iridium (Ir), the ruthenium (Ru) or or its combination;
Said noble metal is preferably, Rh, Ir, Rh-Pt, Rh-Pd, Rh-Ru;
More elect Rh as.
3. according to claim 1,2 described catalyst; It is characterized in that said rare earth metal comprises: lanthanum (La), yttrium (Y), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), scandium (Sc), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu); Said transition metal comprises: titanium (Ti), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), zirconium (Zr), niobium (Nb), molybdenum (Mo), tungsten (W);
Said cerium-based composite oxides carrier is preferably CeOx-LaOx, CeOx-ZrOx, CeOx-PrOx, CeOx-CuOx, CeOx-FeOx;
CeOx-LaOx more preferably.
4. according to the described catalyst of claim 1-3, it is characterized in that said cerium-based composite oxides carrier forms type solid solution of cerium oxide type.
5. according to the described catalyst of claim 1-4, it is characterized in that the mass content of said noble metal is 0.2～5wt.%, is preferably 0.5～1.5%.
6. according to the described catalyst of claim 1-5, it is characterized in that the molar content of cerium oxide is 20～96% in the said cerium-based composite oxides carrier, is preferably 40～80%.
7. according to the described catalyst of claim 1-6, it is characterized in that said cerium-based composite oxides Preparation of catalysts method is sluggish precipitation, sol-gel process, citric acid complex method, roasting direct method or hydrothermal synthesis method;
Said sluggish precipitation comprises the steps:
(1) the precursor salt with cerium oxide and rare earth metal or transition metal is made into mixed solution, and wherein the molar content of cerium salt is 20～96%;
(2) with excessive urea as precipitating reagent, under 80～95 ℃ of temperature conditions, stir 0.5～48h;
(3) after filtration and the washing, obtain filter cake; Perhaps through the sediment that arrives centrifugal and washing;
(4) with filter cake or sediment oven dry,, obtain said cerium-based composite oxides in 300～900 ℃ of roastings in air;
Preferably, in the said step (1), at least a or two and above mixture in the preferred cerous chlorate of said cerium salt, cerous nitrate, ammonium ceric nitrate, the cerous sulfate;
Preferably, in the said step (1), said rare earth metal and transition metal salt comprise lanthanum salt, ytterbium salt, zirconates, molysite, mantoquita, further are preferably lanthanum salt; Lanthanum salt is preferably at least a or two and above mixture that comprises in lanthanum nitrate, lanthanum sulfate, lanthanum chloride, lanthana, the lanthanum carbonate;
Preferably, in the said step (2), the preferred 1～24h of said mixing time, further preferred 4～15h, for example 5h, 6h, 8h or 12h;
Preferably, in the said step (2), said temperature is preferably 60～100 ℃, and more preferably 70～98 ℃, further preferred 80～95 ℃;
Preferably, in the said step (3), the deionized water washing is preferably adopted in said washing, and preferred 1～5 time of washing times for example 2～4 times, comprises 3 times;
Preferably, in the said step (4), said oven dry is preferable over 80～140 ℃ of oven dry down; Further preferably put into baking oven in 80～120 ℃ of oven dry; Drying time is preferably 1～36h, more preferably 2～24h, further preferred 4～12h;
Preferably, in the said step (4), said roasting is preferably through Muffle furnace roasting in 300～900 ℃ of air; Preferred 1～the 24h of said roasting time, preferred 2～12h, further preferred 4～6h; Sintering temperature is preferably 300～600 ℃, further preferred 450～550 ℃;
Said sol-gel process comprises the steps:
(1) the precursor salt with cerium oxide and rare earth metal or transition metal is made into mixed solution, and wherein the molar content of cerium salt is 20～96%;
(2) stir 0.5～72h at ambient temperature, obtain colloidal sol;
(3) gained colloidal sol normal temperature, normal pressure are left standstill 0.5～12d, obtain gel;
(4) with the gel oven dry,, obtain said cerium-based composite oxides catalyst in 300～900 ℃ of roastings in air;
Preferably, in the said step (1), at least a or two and above mixture in the preferred cerous chlorate of said cerium salt, cerous nitrate, ammonium ceric nitrate, the cerous sulfate;
Preferably, in the said step (1), said rare earth metal and transition metal salt comprise lanthanum salt, ytterbium salt, zirconates, molysite, mantoquita, further are preferably lanthanum salt; Lanthanum salt is preferably at least a or two and above mixture that comprises in lanthanum nitrate, lanthanum sulfate, lanthanum chloride, lanthana, the lanthanum carbonate;
Preferably, in the said step (2), the preferred 1～60h of said mixing time, further preferred 4～48h, for example 6h, 10h, 12h or 24h;
Preferably, in the said step (3), the preferred 1～10d of said time of repose, further preferred 2～7d, for example 3d, 4d, 5d or 6d;
Preferably, in the said step (4), said oven dry is preferable over 80～120 ℃ of oven dry down; Further preferably put into baking oven in 80～120 ℃ of oven dry; More drying time is preferably 1～36h, more preferably 2～24h, further preferred 4～12h;
Preferably, in the said step (4), said roasting is preferably through Muffle furnace roasting in 300～900 ℃ of air; Preferred 1～the 24h of said roasting time, preferred 2～12h, further preferred 4～6h; Sintering temperature is preferably 300～600 ℃, further preferred 450～550 ℃;
Said citric acid complex method comprises the steps:
(1) the precursor salt with cerium oxide and rare earth metal or transition metal is made into mixed solution, and wherein the molar content of cerium salt is 20～96%;
(2) in mixed solution, add a certain amount of citric acid, the mol ratio of metal ion total amount and citric acid is 0.5～5.0;
(3) under 20～95 ℃ of temperature conditions, stir 0.5～48h;
(4) normal temperature and pressure leaves standstill 0.5～5d;
(5) with the products therefrom oven dry,, obtain said cerium-based composite oxides catalyst in 300～900 ℃ of roastings in air;
Preferably, in the said step (1), at least a or two and above mixture in the preferred cerous chlorate of said cerium salt, cerous nitrate, ammonium ceric nitrate, the cerous sulfate;
Preferably, in the said step (1), said rare earth metal and transition metal salt comprise lanthanum salt, ytterbium salt, zirconates, molysite, mantoquita, further are preferably lanthanum salt; Lanthanum salt is preferably at least a or two and above mixture that comprises in lanthanum nitrate, lanthanum sulfate, lanthanum chloride, lanthana, the lanthanum carbonate;
Preferably, in the said step (3), the preferred 1～40h of said mixing time, further preferred 2～24h, for example 3h, 5h, 10h or 20h;
Preferably, in the said step (4), the preferred 1～4d of said time of repose, for example 2d or 3d;
Preferably, in the said step (5), said oven dry is preferable over 80～120 ℃ of oven dry down; Further preferably put into baking oven in 80～120 ℃ of oven dry; More drying time is preferably 1～36h, more preferably 2～24h, further preferred 4～12h;
Preferably, in the said step (5), said roasting is preferably through Muffle furnace roasting in 300～900 ℃ of air; Preferred 1～the 24h of said roasting time, preferred 2～12h, further preferred 4～6h; Sintering temperature is preferably 300～600 ℃, further preferred 450～550 ℃;
Said hydrothermal synthesis method comprises the steps:
(1) salt with Ce and La is made into mixed solution, and in the said mixed solution, with the molar ratio computing of metallic element, the ratio of cerium and lanthanum is 0.4～30;
(2) stir 0.5～2h at ambient temperature after, solution is moved in the stainless steel cauldron of inner liner polytetrafluoroethylene;
(3) with agitated reactor at 80～200 ℃ of condition held 1～12d;
(4),, obtain said cerium-based composite oxides catalyst in 300～900 ℃ of roastings in air with products therefrom centrifuge washing, oven dry;
Preferably, in the said step (1), at least a or two and above mixture in the preferred cerous chlorate of said cerium salt, cerous nitrate, ammonium ceric nitrate, the cerous sulfate;
Preferably, in the said step (1), said rare earth metal and transition metal salt comprise lanthanum salt, ytterbium salt, zirconates, molysite, mantoquita, further are preferably lanthanum salt; Lanthanum salt is preferably at least a or two and above mixture that comprises in lanthanum nitrate, lanthanum sulfate, lanthanum chloride, lanthana, the lanthanum carbonate;
Preferably, in the said step (3), said standing time preferred 1～12d, further preferred 2～8d, for example 3d, 4d, 5d or 6d;
Preferably, in the said step (4), said oven dry is preferable over 80～120 ℃ of oven dry down; Further preferably put into baking oven in 80～120 ℃ of oven dry; More drying time is preferably 1～36h, more preferably 2～24h, further preferred 4～12h;
Preferably, in the said step (4), said roasting is preferably through Muffle furnace roasting in 300～900 ℃ of air; Preferred 1～the 24h of said roasting time, preferred 2～12h, further preferred 4～6h; Sintering temperature is preferably 300～600 ℃, further preferred 450～550 ℃.
8. according to the described catalyst of claim 1-7, it is characterized in that the carrying method of noble metal is infusion process, the precipitation method, ion-exchange;
Said infusion process need comprise following steps:
(1) with an amount of noble metal salt wiring solution-forming;
(2) an amount of cerium-based composite oxides impregnated in an amount of precious metal salt solution;
(3) oven dry after dipping is accomplished, roasting;
Preferably, in the said step (1), said precious metal salt is preferably rhodium salt, palladium salt, platinum salt, ruthenium salt, iridium salt; Rhodium salt is preferably radium chloride; Palladium salt is preferably palladium bichloride, palladium nitrate; Platinum salt is preferably platinum chloride, platinum nitrate; Ruthenium salt is preferably ruthenic chloride; Iridium salt is preferably iridium chloride, chloro-iridic acid;
Preferably, in the said step (3), said roasting is preferably through Muffle furnace roasting in 300～900 ℃ of air; Preferred 1～the 24h of said roasting time, preferred 2～12h, further preferred 4～6h; Sintering temperature is preferably 300～600 ℃, further preferred 450～550 ℃.
9. according to the described catalyst of claim 1-8, it is characterized in that be applicable to that alcohols and short chain alkanes low temperature produces hydrogen, said alcohol is preferably methyl alcohol, ethanol, propyl alcohol, butanols, glycerine, further is preferably ethanol; Said hydro carbons is methane, ethane, decane, dodecane, further is preferably dodecane; Low temperature is preferably 100～480 ℃, further is preferably 200～450 ℃.
10. the method for a catalyzing manufacturing of hydrogen; Said method uses noble metal as claimed in claim 1 to load on the catalyst on the cerium-based composite oxides, it is characterized in that, said catalyst is mainly used in produces and utilize hydrogen; Also can be used for the elimination of CO; Catalyst slurrying back loading is to various honeycomb ceramic carriers, and the catalyst that is prepared into moulding uses, or through using after the extrusion modling;
Preferably; Catalyst is placed reactor; Spray into mixed raw materials gas at the upper reaches of catalyst; After in reactor, reacting, produce hydrogen, the hydrogen of generation separates through film or other separate modes are purified back or directly feed fuel cell or hydrogen storage material without purifying and be used or store;
Preferably, said hydrogen production process can be the lower alcohols reformation hydrogen production, also can be short chain hydrocarbon compound reformation hydrogen production, also can be the CO vapor reforming hydrogen production; Said hydrogen production process is preferably the ethanol reformation hydrogen production.
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