CN104624204B - Catalyst for CO selective hydrogenation and preparation method and application of catalyst - Google Patents
Catalyst for CO selective hydrogenation and preparation method and application of catalyst Download PDFInfo
- Publication number
- CN104624204B CN104624204B CN201510063696.7A CN201510063696A CN104624204B CN 104624204 B CN104624204 B CN 104624204B CN 201510063696 A CN201510063696 A CN 201510063696A CN 104624204 B CN104624204 B CN 104624204B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- solution
- cobalt
- palladium
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention discloses a catalyst for CO selective hydrogenation and a preparation method and application of the catalyst. The catalyst is prepared through steps of dissolving a compound containing metal M into a solvent, adding a surfactant, and carrying out water thermal treatment under an enclosed condition so as to obtain the catalyst. Specifically, the preparation method of the catalyst comprises the following steps: (1) dissolving the compound containing the meta M into the solvent so as to form a solution A; (2) adding the surfactant into the solution A so as to form a solution B; (3) enclosing the solution B, and carrying out hydrothermal reaction; and (4) washing, separating and drying a precipitation product obtained after hydrothermal reaction in the step (3) so as to obtain the catalyst. The catalyst has a one-dimensional dendritic structure, is good in dispersion, stable in structure, and uniform in morphology and size, exposes the high-activity crystal surface, has the characteristics of relatively high reaction activity and selectivity to CO selectivity hydrogenation, chain growth capacity and the like, and meanwhile has a good industrial application prospect.
Description
Technical field
The present invention relates to a kind of catalyst and its preparation method and application, more particularly to a kind of urging for co selective hydrogenation
Agent and its preparation method and application.
Background technology
Nano material, because of its unique bulk effect, skin effect and quantum size effect, has different from block materials
Electricity, light, power, the performance such as magnetic.And the application of these aspects is closely related with the size and dimension of nano material.In recent years, with
The development of nanotechnology, the nano material of morphology controllable, because its unique physicochemical properties, is increasingly learned by each
The concern of section researchers.So-called pattern is exactly to include two aspects: size and dimension.It is known that the size when material
Little to certain degree when, some of physical parameter can change；And the homogeneous nano material of shape tends to expose
There is the surface of the identical indices of crystallographic plane, be so obtained with knowable surface characteristic.Numerous studies show, the knot of nano material
There is close internal relation between structure and its performance, study the Nature-Understanding for nano material for the appearance structure of nano material
Its application is significant with widening.For example, in catalyticing research field, understand that catalyst surface structure is catalyzed instead with it
Answer the relation between performance, to design and exploitation effective catalyst, there is important directive significance, received with the metal of compound with regular structure
It is to realize above-mentioned target that rice material carries out surface texture-catalytic performance relation and the research of mechanism of catalytic reaction for model catalyst
Approach.
In material science, forming alloy by mixing two or three different metal can make metal generation collaborative
Effect, forms bimetallic (three metals) material.Compare with monometallic, in terms of the composition of material and structural research, bimetallic (three
Metal) composite nano materials have the properties such as the optics of uniqueness, catalysis and magnetic, and this is two kinds (multiple) due to forming alloy
The synergistic result of metal.Due to there are various combinations, thus the exploitation of bimetallic catalyst have huge
Potentiality.The second metal adding can be noble metal or base metal.Performance and its pattern due to bimetal nano material
Closely related, so these unique performances will be realized or obtain the more preferable metal nano material of performance it may first have to realize
The controlledly synthesis of material morphology.But preparation size and pattern (especially novel shape) controlled nanostructured be a difficult problem simultaneously
Great challenge.It has been reported that the bimetal nano particles controlling synthesis focus primarily upon noble metal and noble metal field, such as au-
Belonging to race's (platinum, palladium, nickel) and ib race metal (gold, silver) these metals such as ag, pt-pd, pt-ni, ag-pd more.Noble metal with
The bimetallic material of base metal composition also has correlational study to report, such as pt-ni, ag-ni, pd-cu etc., and your gold of low content
Belong to less with base metal and two kinds of non-noble metal nano materials researches.
In recent years, bimetallic (three metals) nano catalytic material is due in the weight improving the aspect such as catalysis activity and selectivity
Act on and be subject to common concern, carry out regulating and controlling synthetically prepared difference around factors such as bimetallic material composition, microstructures
Bimetallic (three metals) material, study performance in different catalytic reactions for the above-mentioned different bimetallic material it is intended to find
There is the catalyst material of more high activity, selectivity and stability, and attempt exploring new catalytic reaction and catalytic reaction machine
Reason also becomes the hot issue of research.Certainly, research bimetallic (three metals) material morphology controllable synthesis have important
Academic significance and industrial value.
Content of the invention
The technical problem to be solved in the present invention is to provide a kind of catalyst for co selective hydrogenation and its preparation method and answer
With.This catalyst is a kind of bimetallic (three metals) catalyst with one-dimensional dendritic morphology for co selective hydrogenation, its
Can be prepared by liquid phase reduction (as passed through hydrothermal reduction in dihydroxylic alcohols system) etc., and the operation letter of this preparation method
Single, reaction condition is gentle, product morphology controllable and Stability Analysis of Structures, has a good application prospect.
For solving above-mentioned technical problem, the catalyst for co selective hydrogenation of the present invention, it is following by including
The method of step is preparation-obtained:
By the compound dissolution containing metal m in solvent, add surfactant, through carrying out at hydro-thermal under the conditions of airtight
Reason, obtains described catalyst；
Wherein, the compound containing metal m include following combination one of:
(1) the combining of cobalt source (compound containing cobalt) and copper source (compound of cupric)；
(2) the combining of cobalt source (compound containing cobalt) and palladium source (compound containing palladium)；
(3) combination of cobalt source (compound containing cobalt), copper source (compound of cupric) and palladium source (compound containing palladium).
Described catalyst is the catalyst of a kind of bimetallic with one-dimensional dendritic morphology or three metals, wherein, dendritic knot
Structure includes club shaped structure；The inside of described catalyst is the core of 20nm～200 μm, and surface for diameter in 15～50nm, length is
The one-dimensional dendritic nano-structure of 500nm～2 μm.Periphery as this catalyst has club shaped structure (the one-dimensional branch in 20nm for the diameter
Shape).
In the described compound containing metal m, the mol ratio of copper and cobalt is preferably 1%～30%；The mol ratio of palladium and cobalt is excellent
Elect 0.01%～4% as.
Described cobalt source includes: the salt containing cobalt；Be preferably divalent cobalt, such as this divalent cobalt includes: cobaltous chloride, cobalt nitrate or
One or more of cobalt acetate；It is preferably cobalt acetate (as co (ac)2·4h2O etc.).
Copper source includes: the salt of cupric；Be preferably cupric salt, such as this cupric salt includes: copper chloride, copper nitrate or
One or more of copper acetate；It is preferably copper acetate (as cu (ac)2·h2O etc.).
Described palladium source includes: the salt containing palladium；It is preferably bivalence palladium salt；As this bivalence palladium salt includes: Palladous chloride., Palladous nitrate. or
One or more of palladium acetylacetonate etc.；Preferably Palladous nitrate..
Described solvent includes: dihydroxylic alcohols；This dihydroxylic alcohols includes: in ethylene glycol, propylene glycol, butanediol, pentanediol etc.
Plant or multiple；It is preferably propylene glycol, particularly 1,2-PD.
Described surfactant includes: one of carboxylic acid, amine or a combination thereof (preferably long-chain carboxylic acid, in long-chain amine one
Plant or a combination thereof)；Wherein, carboxylic acid includes: one or more of lauric acid/dodecanoic acid, tetradecylic acid, hexadecylic acid, stearic acid, Oleic acid etc.；Excellent
Elect stearic acid as；Amine includes: one or more of lauryl amine, tetradecy lamine, cetylamine, 18-amine. etc.；It is preferably cetylamine；Separately
Outward it is preferable that the mol ratio (amount of material) of carboxylic acid and amine is 0～2, more preferably (0.8～1.2) carboxylic acid: amine (0.8～1.2),
Most preferably 1:1.
In addition, the present invention also provides a kind of preparation method of above-mentioned catalyst, including step:
1) preparation of reactant liquor
By the above-mentioned compound dissolution containing metal m in above-mentioned solvent, form solution a；
2) add surfactant
Add above-mentioned surfactant in solution a, form solution b；
3) hydrothermal treatment consists
Will be airtight for solution b, and at 140～210 DEG C, hydro-thermal reaction 2～24 hours；
4) by step 3) the precipitated product washing that obtains after hydro-thermal reaction, separate, be dried, obtain catalyst.
Described step 1) in, the cobalt ion molar concentration in solution a is preferably 0.04～0.06mol/l, more preferably
The concentration of 0.04mol/l, copper ion and palladium ion is adjusted according to the ratio with cobalt ion, and the molar concentration of such as copper ion is excellent
Elect 0.0004～0.018mol/l, more preferably 0.0004～0.012mol/l as；The molar concentration of palladium ion is 4 × 10-6~
0.0024mol/l, more preferably 0.0004～0.0016mol/l；
Described step 2) in, the consumption of surfactant is preferably: the mass ratio of carboxylic acid and cobalt source is 0.5～3.
Step 2) in, the method forming solution b includes: by the above-mentioned compound dissolution containing metal m in above-mentioned solvent, 20
～40 DEG C of stirring 30～60min, form solution b.
Described step 3) in it is preferable that at 150～190 DEG C, hydro-thermal reaction 5～24 hours；Water more preferably at 150 DEG C
Thermal response 10 hours or at 190 DEG C hydro-thermal reaction 5 hours.
Described step 4) in, the method for washing includes: deionized water and absolute ethanol washing 4～6 times；Described drying
Condition is vacuum dried 4～8 hours at being preferably 50～60 DEG C, vacuum drying 4～8 hours at more preferably 50 DEG C, particularly preferably
It is vacuum dried 6 hours for 50 times.
Furthermore, the present invention also provides the application of above-mentioned catalyst, and that is, described catalyst is applied to the anti-of co selective hydrogenation
Ying Zhong, wherein, the reaction condition of catalysis is: reaction temperature is 190～280 DEG C, pressure (such as the pressure of synthesis gas, this synthesis gas
May include: h2And co) it is 2～6mpa, co/h2Volume ratio=1:1～1:3, the flow velocity of hydrogen is 600～4000ml/g/h.
In the present invention, by precursor liquid is used as using the certain density solution containing above-mentioned metal m, adds appropriate surface and live
Property agent, mix homogeneously, then will mixed solution move into hydrothermal reaction kettle in, at a certain temperature reaction a period of time, treat
After reactant liquor cooling, separate, washing, vacuum drying, can get the catalyst of the present invention.As under propylene glycol system, stearic acid
With cetylamine as Dual Surfactants, generate cobalt-based bimetal nano bar material using hydrothermal reduction method.
The catalyst of the present invention has one-dimensional dendritic morphology and good dispersion, Stability Analysis of Structures, pattern size are homogeneous and sudden and violent
Reveal high activity crystal face, there is to co selective hydrogenation stronger reactivity and the spy such as good selectivity and chain growing ability
Point, meanwhile, this catalyst has that making is simple, reaction condition is gentle, good stability, product and catalyst are easily separated, be easy to back
Receive utilize, easily-activated the advantages of, thus improving equipment capacity and product quality, bringing big economic benefit, having good
Industrial applications prospect, and this structure nano material (i.e. the catalyst of the present invention) has as template and other are special
The purposes of different nano material, embodies good application prospect.
Brief description
The present invention is further detailed explanation with specific embodiment below in conjunction with the accompanying drawings:
Fig. 1 is sem (scanning electron microscope) collection of illustrative plates of pdco (0.1wt%pd) catalyst；
Fig. 2 is sem (scanning electron microscope) collection of illustrative plates of cuco (10wt%cu) catalyst；
Fig. 3 is sem (scanning electron microscope) collection of illustrative plates of pdcuco (0.1wt%pd, 10wt%cu) catalyst；
Fig. 4 is pdco, pd content that pdco, pd content that pd content is 0.05wt% is 0.1wt% is 1wt%
Pdco, cu content be 1wt% cuco, cu content be 5wt% cuco, cu content be 10wt% cuco (i.e. 0.05%
Pdco, 0.1%pdco, 1%pdco, 1%cuco, 5%cuco, 10%cuco) catalyst xrd (x-ray diffraction) collection of illustrative plates；
Fig. 5 is the products distribution block diagram that pdco, cocu, co are catalyzed co hydrogenation.
Specific embodiment
Embodiment 1
Weigh 0.75g cobalt acetate (co (ac)2·4h2O) it is dissolved in 70ml1, in 2- propylene glycol, form solution a.
Weigh 20mg Palladous nitrate. (pd (no3)2·h2O) it is dissolved in 20ml 1,2-PD, form solution b.
0.5ml solution b is taken to be added to solution a, under normal temperature condition, stirring and dissolving, obtain uniform solution a.
Weigh 1.05g stearic acid again, be added to solution a, 40 DEG C of stirring 30min, mix homogeneously, obtain solution b.
The solution b of gained is added to 100ml politef water heating kettle, in confined conditions and in 190 DEG C of temperature
Under, hydro-thermal reaction 5 hours.Then, close heating, question response temperature is taken out after being cooled to room temperature, and upper strata can be observed and be
Golden yellow colloidal attitude solution, reactor inwall has a certain amount of black solid product, and atrament is scraped, by obtain after hydro-thermal
Product respectively deionized water and absolute ethanol washing 46 times, is separated with carrying out washing, finally by product at 50 DEG C vacuum
It is dried 6 hours, obtain pdco (weight content of pd is 0.1%, i.e. 0.1wt%pd) bimetallic catalyst.
Wherein, the sem figure of this catalyst, as shown in Figure 1.In Fig. 1, form diameter 15～50nm, length is 500nm～2 μ
The one-dimensional dendritic nano-structure of m, the distribution of pd and co bimetallic is more uniform.
In addition, above-mentioned catalyst can be applicable in the reaction of co selective hydrogenation.
Embodiment 2
Weigh 0.75g cobalt acetate (co (ac)2·4h2O) it is dissolved in 70ml propylene glycol, form solution a.
Weigh 200mg Palladous nitrate. (pd (no3)2·h2O) it is dissolved in 20ml propylene glycol, form solution b.
0.5ml solution b is taken to be added to solution a, under normal temperature condition, stirring and dissolving obtains uniform solution a.
Weigh 1.05g stearic acid again, be added to solution a, 40 DEG C of stirring 30min, mix homogeneously, obtain solution b.
The solution b of gained is added to 100ml politef water heating kettle, in confined conditions and in 190 DEG C of temperature
Under, hydro-thermal reaction 5 hours.Then, close heating, question response temperature is taken out after being cooled to room temperature, and upper strata can be observed and be
Golden yellow colloidal attitude solution, reactor inwall has a certain amount of black solid product, and atrament is scraped, by obtain after hydro-thermal
Product respectively deionized water and absolute ethanol washing 46 times, is separated with carrying out washing, finally by product at 50 DEG C vacuum
It is dried 6 hours, obtain pdco (1wt%pd) bimetallic catalyst.
In addition, above-mentioned catalyst can be applicable in the reaction of co selective hydrogenation, wherein, the reaction condition of catalysis can be:
Reaction temperature is 200 DEG C, and (this synthesis gas is by h for synthesis gas2With co constitute) pressure be 2.5mpa, the co/h in synthesis gas2Body
Long-pending ratio=1:1, the flow velocity of hydrogen is 2000ml/g/h.
Embodiment 3
Weigh 0.75g cobalt acetate (co (ac)2·4h2O) it is dissolved in 70ml propylene glycol, form solution a.
Weigh 200mg copper acetate (cu (ac)2·h2O) it is dissolved in 20ml propylene glycol, form solution b.
2.5ml solution b is taken to be added to solution a, under normal temperature condition, stirring and dissolving obtains uniform solution a.
Weigh 1.05g stearic acid and 1.05g cetylamine again, be added to solution a, 40 DEG C of stirring 30min, mix homogeneously, obtain
To solution b.
The solution b of gained is added to 100ml politef water heating kettle, in confined conditions and in 190 DEG C of temperature
Under, hydro-thermal reaction 5 hours.Then, close heating, question response temperature is taken out after being cooled to room temperature, and upper strata can be observed and be
Golden yellow colloidal attitude solution, reactor inwall has a certain amount of black solid product, and atrament is scraped, by obtain after hydro-thermal
Product respectively deionized water and absolute ethanol washing 46 times, is separated with carrying out washing, finally by product at 50 DEG C vacuum
It is dried 6 hours, obtain cuco (5wt%cu) bimetallic catalyst.
In addition, above-mentioned catalyst can be applicable in the reaction of co selective hydrogenation, wherein, the reaction condition of catalysis can be:
Reaction temperature is 220 DEG C, and (this synthesis gas is by h for synthesis gas2With co constitute) pressure be 4mpa, the co/h in synthesis gas2Volume
Ratio=1:3, the flow velocity of hydrogen is 3000ml/g/h.
Embodiment 4
Weigh 0.75g cobalt acetate (co (ac)2·4h2O) it is dissolved in 70ml propylene glycol, form solution a.
Weigh 200mg copper acetate (cu (ac)2·h2O) it is dissolved in 20ml propylene glycol, form solution b.
5ml solution b is taken to be added to solution a, under normal temperature condition, stirring and dissolving obtains uniform solution a.
Weigh 1.05g stearic acid and 1.05g cetylamine again, be added to solution a, 40 DEG C of stirring 30min mix homogeneously, obtain
Solution b.
The solution b of gained is added to 100ml politef water heating kettle, in confined conditions and in 190 DEG C of temperature
Under, hydro-thermal reaction 5 hours.Then, close heating, question response temperature is taken out after being cooled to room temperature, and upper strata can be observed and be
Golden yellow colloidal attitude solution, reactor inwall has a certain amount of black solid product, and atrament is scraped, by obtain after hydro-thermal
Product respectively deionized water and absolute ethanol washing 46 times, is separated with carrying out washing, finally by product at 50 DEG C vacuum
It is dried 6 hours, obtain cuco (10wt%cu) bimetallic catalyst.
Wherein, the sem figure of this catalyst, as shown in Figure 2.As shown in Figure 2, cu and co forms bimetallic nano rod structure,
, in 20nm, at 1～2 μm, nanorod structure is homogeneous for length for the diameter of nanometer rods, the similar Hemicentrotus seu Strongylocentrotuss shape structure of nanometer rods composition.
In addition, above-mentioned catalyst can be applicable in the reaction of co selective hydrogenation.
Embodiment 5
Weigh 0.75g cobalt acetate (co (ac)2·4h2O) it is dissolved in 70ml propylene glycol, form solution a.
Weigh 200mg copper acetate (cu (ac)2·h2O) it is dissolved in 20ml propylene glycol, form solution b.
10ml solution b is taken to be added to solution a, under normal temperature condition, stirring and dissolving obtains uniform solution a.
Weigh 1.05g stearic acid and 1.05g cetylamine again, be added to solution a, 30 DEG C of stirring 50min mix homogeneously, obtain
Solution b.
The solution b of gained is added to 100ml politef water heating kettle, in confined conditions and in 160 DEG C of temperature
Under, hydro-thermal reaction 15 hours.Then, close heating, question response temperature is taken out after being cooled to room temperature, and upper strata can be observed and be
Golden yellow colloidal attitude solution, reactor inwall has a certain amount of black solid product, and atrament is scraped, by obtain after hydro-thermal
Product respectively deionized water and absolute ethanol washing 46 times, is separated with carrying out washing, finally by product at 55 DEG C vacuum
It is dried 5 hours, obtain cuco (20wt%cu) bimetallic catalyst.
In addition, above-mentioned catalyst can be applicable in the reaction of co selective hydrogenation, wherein, the reaction condition of catalysis can be:
Reaction temperature is 250 DEG C, and (this synthesis gas is by h for synthesis gas2With co constitute) pressure be 5mpa, the co/h in synthesis gas2Volume
Ratio=1:2.5, the flow velocity of hydrogen is 2500ml/g/h.
Embodiment 6
Weigh 0.75g cobalt acetate (co (ac)2·4h2O) it is dissolved in 70ml propylene glycol, form solution a.
Weigh 200mg acid chloride (cu (ac)2·h2O) it is dissolved in 20ml propylene glycol, form solution b.
5ml solution b is taken to be added to solution a.
Weigh 20mg Palladous nitrate. (pd (no3)2·h2O) it is dissolved in 20ml propylene glycol, form solution c.
0.5ml solution c is taken to be added to solution a under normal temperature condition, agitating solution obtains uniform solution a.
Weigh 1.05g stearic acid and 1.05g cetylamine again, be added to solution a, 40 DEG C of stirring 30min mix homogeneously, obtain
Solution b.
The solution b of gained is added to 100ml politef water heating kettle, in confined conditions and in 190 DEG C of temperature
Under, hydro-thermal reaction 5 hours.Then, close heating, question response temperature is taken out after being cooled to room temperature, and upper strata can be observed and be
Golden yellow colloidal attitude solution, reactor inwall has a certain amount of black solid product, and atrament is scraped, by obtain after hydro-thermal
Product respectively deionized water and absolute ethanol washing 46 times, is separated with carrying out washing, finally by product at 50 DEG C vacuum
It is dried 6 hours, obtain pdcuco (0.1wt%pd, 10wt%cu) ternary metallic catalyst.
Wherein, the sem figure of this catalyst, as shown in Figure 3.In Fig. 3, forming diameter 15～50nm length is 500nm～2 μm
One-dimensional dendritic nano-structure, pd, cu, co tri- Metal Distribution is more uniform.One-dimentional structure assumes radial structure.
In addition, above-mentioned catalyst can be applicable in the reaction of co selective hydrogenation, wherein, the reaction condition of catalysis can be:
Reaction temperature is 270 DEG C, and (this synthesis gas is by h for synthesis gas2With co constitute) pressure be 4.5mpa, the co/h in synthesis gas2Body
Long-pending ratio=1:1.5, the flow velocity of hydrogen is 3500ml/g/h.
The xrd detection of embodiment 7 catalyst
To the catalyst of embodiment 1-4, pd content be the pdco catalyst of 0.05wt%, cu content be the cuco of 1wt%
Catalyst carries out xrd detection, and result is as shown in Figure 4.Wherein, the preparation method of the pdco catalyst for 0.05wt% for the pd content can
Reference implementation example 1, cu content is that the preparation method of the cuco catalyst of 1wt% refers to embodiment 3.
As shown in Figure 4 it is shown that the 41.5 of face-centred cubic structure co of catalyst °, 44.6 °, 47.3 °, 62.4 °, 75.8 °
The peak of (100), (002), (101), (102) and (110) crystal face corresponding to, in the case that the content of cu brings up to 10%,
Two peaks of 43.692 ° and 50.976 ° appearance of display, respectively co can be clearly showed that0.52cu0.48(111) and (200) crystal face,
Meet jcpsd-50-1452.
Embodiment 8 catalytic effect is tested
Catalyst sample: pdco (content of pd is 0.1wt%) catalyst (the i.e. copd of embodiment 10.001)；Embodiment 4
Cocu (content of cu be 10wt%) catalyst (i.e. cocu0.1)；And monometallic co catalyst.
Catalytic reaction condition:
Weigh 2g above-mentioned catalyst sample to mix with 40～60 mesh quartz sands, be loaded on fixed bed flat-temperature zone, with 1 DEG C/min liter
Temperature is to 300 DEG C, in h2/n2(h2With n2Volume ratio be 1:9) under the conditions of with reductase 12 h under the gas flow rate of 200ml/min, afterwards
It is reduced to 190 DEG C, switch to that synthesis gas is standby to be pressed onto the 6mpa (n being wherein, 3% containing volumetric concentration in synthesis gas2As interior
Mark, remaining co and h2Volume ratio be 1:2), synthesis gas flow rate set be 100ml/min, at 190 DEG C react 24h, afterwards will
Cold-trap and the emptying of hot trap liquid.Start since then to react, use the chromatographic determination gas-phase product of tcd and fid detector online, take afterwards
Liquid phase, liquid phase is divided into aqueous phase, oil phase, waxen imagen, beats chromatograph respectively, carries out mass balance.Wherein, measure a temperature within every 24 hours
Degree point, collects and detection gas phase and liquid product, carries out mass balance.Temperature spot rises 10 DEG C every time, reacts always to 280
℃.Result is as shown in Figure 5.
Wherein, show in Fig. 5 that copd bimetal nano catalyst shows good catalytic effect, have stronger chain to increase
Ability, is beneficial to the wax phase forming high carbon number.And cuco bimetal nano catalyst then can form the alcohol aqueous phase of more height ratio.
In addition, the catalytic reaction condition of embodiment 8 is also applied for the catalyst of embodiment 2-3,5-6 preparation.
Claims (12)
1. a kind of catalyst for co selective hydrogenation has one-dimensional dendritic knot it is characterised in that described catalyst is one kind
The bimetallic of structure or the catalyst of three metals；Described catalyst is preparation-obtained by the method that comprises the following steps:
By the compound dissolution containing metal m in solvent, add surfactant, through carrying out hydrothermal treatment consists under the conditions of airtight, obtain
To described catalyst；Described surfactant is: one of carboxylic acid, amine or a combination thereof；Described carboxylic acid includes: lauric acid/dodecanoic acid, ten
One or more of tetracid, hexadecylic acid, stearic acid, Oleic acid；Described amine includes: lauryl amine, tetradecy lamine, cetylamine, 18-amine.
One or more of；
Wherein, the compound containing metal m include following combination one of:
(1) the combining of cobalt source and copper source；
(2) the combining of cobalt source and palladium source；
(3) combination of cobalt source, copper source and palladium source.
2. catalyst as claimed in claim 1 it is characterised in that: in the described compound containing metal m, the mol ratio of copper and cobalt
For 1%～30%；The mol ratio of palladium and cobalt is 0.01%～4%；
Described dendritic morphology includes club shaped structure.
3. catalyst as claimed in claim 1 it is characterised in that: the inside of described catalyst be 20nm～200 μm core, table
Face is diameter is the one-dimensional dendritic nano-structure of 500nm～2 μm in 15～50nm, length.
4. catalyst as claimed in claim 2 it is characterised in that: the inside of described catalyst be 20nm～200 μm core, table
Face is diameter is the one-dimensional dendritic nano-structure of 500nm～2 μm in 15～50nm, length.
5. the catalyst as described in any one of Claims 1 to 4 it is characterised in that: described cobalt source includes: the salt containing cobalt；
Copper source includes: the salt of cupric；
Described palladium source includes: the salt containing palladium；
Described solvent includes: dihydroxylic alcohols.
6. catalyst as claimed in claim 5 it is characterised in that: the described salt containing cobalt be divalent cobalt；
The salt of described cupric is cupric salt；
The described salt containing palladium is bivalence palladium salt；
Described dihydroxylic alcohols include: one or more of ethylene glycol, propylene glycol, butanediol, pentanediol；
The mol ratio of described carboxylic acid and amine is 0～2.
7. catalyst as claimed in claim 6 it is characterised in that: described divalent cobalt includes: cobaltous chloride, cobalt nitrate or acetic acid
One or more of cobalt；
Described cupric salt includes: one or more of copper chloride, copper nitrate or copper acetate；
Described bivalence palladium salt includes: one or more of Palladous chloride., Palladous nitrate. or palladium acetylacetonate；
The mol ratio of described carboxylic acid and amine is 0.8～1.2:0.8～1.2.
8. a kind of preparation method of catalyst as claimed in claim 1 is it is characterised in that include step:
1) by the compound dissolution containing metal m in solvent, form solution a；
2) add surfactant in solution a, form solution b；
3) will be airtight for solution b, and at 140～210 DEG C, hydro-thermal reaction 2～24 hours；
4) by step 3) the precipitated product washing that obtains after hydro-thermal reaction, separate, be dried, obtain catalyst.
9. method as claimed in claim 8 it is characterised in that: described step 1) in, the cobalt ion molar concentration in solution a is
0.04～0.06mol/l；The molar concentration of copper ion is 0.0004～0.018mol/l；The molar concentration of palladium ion is 4 × 10-6
～0.0024mol/l；
Described step 2) in, surfactant is carboxylic acid, and the mass ratio of carboxylic acid and cobalt source is 0.5～3；
Step 2) in, the method forming solution b includes: by the compound dissolution containing metal m in solvent, 20～40 DEG C of stirrings 30
～60min, forms solution b；
Described step 3) in, at 150～190 DEG C, hydro-thermal reaction 5～24 hours；
Described step 4) in, the method for washing includes: deionized water and absolute ethanol washing 4～6 times；The condition of described drying
For being vacuum dried 4～8 hours at 50～60 DEG C.
10. method as claimed in claim 9 it is characterised in that: described step 1) in, cobalt ion molar concentration in solution a
For 0.04mol/l；The molar concentration of copper ion is 0.0004～0.012mol/l；The molar concentration of palladium ion be 0.0004～
0.0016mol/l；
Described step 3) in, at 150 DEG C hydro-thermal reaction 10 hours or at 190 DEG C hydro-thermal reaction 5 hours；
Described step 4) in, the condition being dried is for being vacuum dried 4～8 hours at 50 DEG C.
A kind of 11. applications of the catalyst as described in claim 1 or 2 or 3 or 4 or 6 or 7 it is characterised in that: described catalyst
It is applied in the reaction of co selective hydrogenation；
Wherein, the condition of reaction is: reaction temperature is 190～280 DEG C, and pressure is 2～6mpa, co/h2Volume ratio=1:1～
1:3, the flow velocity of hydrogen is 600～4000ml/g/h.
A kind of 12. applications of catalyst as claimed in claim 5 it is characterised in that: described catalyst is applied to co selectivity
In the reaction of hydrogenation；
Wherein, the condition of reaction is: reaction temperature is 190～280 DEG C, and pressure is 2～6mpa, co/h2Volume ratio=1:1～
1:3, the flow velocity of hydrogen is 600～4000ml/g/h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510063696.7A CN104624204B (en) | 2015-02-06 | 2015-02-06 | Catalyst for CO selective hydrogenation and preparation method and application of catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510063696.7A CN104624204B (en) | 2015-02-06 | 2015-02-06 | Catalyst for CO selective hydrogenation and preparation method and application of catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104624204A CN104624204A (en) | 2015-05-20 |
| CN104624204B true CN104624204B (en) | 2017-02-01 |
Family
ID=53203727
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510063696.7A Active CN104624204B (en) | 2015-02-06 | 2015-02-06 | Catalyst for CO selective hydrogenation and preparation method and application of catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104624204B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105081308A (en) * | 2015-08-24 | 2015-11-25 | 中国科学院上海高等研究院 | Curved-surface Pt-based nanometer bimetallic material with and preparation method and application thereof |
| CN105413709B (en) * | 2015-12-11 | 2018-01-30 | 中国科学院上海高等研究院 | A kind of platinum cobalt nanometer bi-metal catalyst of more cubes of dendritic morphologies and its preparation method and application |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010010026A2 (en) * | 2008-07-23 | 2010-01-28 | Construction Research & Technology Gmbh | Method for producing metal nanoparticles in polyols |
| DE102009015470A1 (en) * | 2008-12-12 | 2010-06-17 | Byk-Chemie Gmbh | Process for the preparation of metal nanoparticles and metal nanoparticles obtained in this way and their use |
| CN101773853B (en) * | 2009-01-14 | 2012-02-29 | 中国科学院大连化学物理研究所 | Non-supported catalyst pulp, preparation method and application thereof |
| CN102107137A (en) * | 2009-12-28 | 2011-06-29 | 中国科学院大连化学物理研究所 | Preparation method of platinum-palladium bimetallic catalyst |
| IT1397394B1 (en) * | 2009-12-29 | 2013-01-10 | Qid S R L | PROCEDURE FOR PREPARATION OF BIMETALLIC COMPOSITIONS OF CO / PD AND COMPOSITIONS OBTAINED THROUGH IT |
| CN102500374B (en) * | 2011-12-02 | 2014-02-26 | 上海中科高等研究院 | Copper-based nano catalyst for preparing high-carbon alcohol from synthetic gas as well as preparation method and application thereof |
| CN103877995B (en) * | 2014-03-31 | 2016-02-17 | 陕西师范大学 | Montmorillonite loading nano Pd/Cu catalyst and original position one kettle way Synthesis and applications thereof |
| CN104028286B (en) * | 2014-07-01 | 2016-03-02 | 青岛科技大学 | The preparation method of copper-based catalysts |
-
2015
- 2015-02-06 CN CN201510063696.7A patent/CN104624204B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN104624204A (en) | 2015-05-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Loghmani et al. | Hydrogen generation as a clean energy through hydrolysis of sodium borohydride over Cu-Fe-B nano powders: Effect of polymers and surfactants | |
| Yao et al. | Highly efficient hydrogen release from formic acid using a graphitic carbon nitride-supported AgPd nanoparticle catalyst | |
| Lu et al. | Co3O4/CuMoO4 hybrid microflowers composed of nanorods with rich particle boundaries as a highly active catalyst for ammonia borane hydrolysis | |
| CN109304476A (en) | Carbon coating transition metal nanocomposite and its preparation method and application | |
| Ding et al. | Co3O4–CuCoO2 nanomesh: An interface-enhanced substrate that simultaneously promotes CO adsorption and O2 activation in H2 purification | |
| Jiang et al. | A facile surfactant-free synthesis of Rh flower-like nanostructures constructed from ultrathin nanosheets and their enhanced catalytic properties | |
| Zhao et al. | Monodisperse metal–organic framework nanospheres with encapsulated core–shell nanoparticles Pt/Au@ Pd@{Co2 (oba) 4 (3-bpdh) 2} 4H2O for the highly selective conversion of CO2 to CO | |
| CN109908903A (en) | A kind of high-specific surface area Lignin-Based Activated Carbon is nickel-base catalyst and its preparation and application of carrier | |
| Iqbal et al. | Tailored design of mesoporous PdCu nanospheres with different compositions using polymeric micelles | |
| CN107486245B (en) | NH for catalyzing ammonia borane hydrolysis to produce hydrogen 2-MI L-125 supported silver-cobalt alloy nano catalyst | |
| CN104493193A (en) | Hydro-thermal synthetic method and application of Pt-Ru bimetal nanoparticles | |
| Shen et al. | Size control and catalytic activity of highly dispersed Pd nanoparticles supported on porous glass beads | |
| CN108671964A (en) | A kind of MIL-53 (Al) the load ruthenium cobalt alloy nanocatalysts and preparation method of catalysis production hydrogen | |
| CN109731579A (en) | A kind of mesoporous lanthanum oxide catalyst of nickel load and preparation method thereof | |
| Cao et al. | Ternary CoAgPd nanoparticles confined inside the pores of MIL-101 as efficient catalyst for dehydrogenation of formic acid | |
| Fiuza et al. | Supported AuCu alloy nanoparticles for the preferential oxidation of CO (CO-PROX) | |
| CN104624204B (en) | Catalyst for CO selective hydrogenation and preparation method and application of catalyst | |
| Kusada et al. | Chemical Synthesis, Characterization, and Properties of Multi‐Element Nanoparticles | |
| Dang‐Bao et al. | Metal nanoparticles in polyols: bottom‐up and top‐down syntheses and catalytic applications | |
| Wang et al. | AgPdCo hollow nanospheres electrocatalyst with high activity and stability toward the formate electrooxidation | |
| CN104689820A (en) | Cobalt-based bimetallic catalyst with cylindrical structure as well as preparation method and application of cobalt-based bimetallic catalyst | |
| Fujitsuka et al. | Hydrogen Production from formic acid using Pd/C, Pt/C, and Ni/C catalysts prepared from Ion-exchange resins | |
| Hu et al. | Activity and stability of monometallic and bimetallic catalysts for high-temperature catalytic HI decomposition in the iodine–sulfur hydrogen production cycle | |
| Sun et al. | Cobalt-nickel bimetal carbon sphere catalysts for efficient hydrolysis of sodium borohydride: The role of synergy and confine effect | |
| Liu et al. | Multicomponent (Ce, Cu, Ni) oxides with cage and core–shell structures: tunable fabrication and enhanced CO oxidation activity |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |