CN106391000A - Pd(111)/gamma-Al2O3 catalyst for CO dehydrogenation purification reaction and preparation method thereof - Google Patents
Pd(111)/gamma-Al2O3 catalyst for CO dehydrogenation purification reaction and preparation method thereof Download PDFInfo
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- CN106391000A CN106391000A CN201610881704.3A CN201610881704A CN106391000A CN 106391000 A CN106391000 A CN 106391000A CN 201610881704 A CN201610881704 A CN 201610881704A CN 106391000 A CN106391000 A CN 106391000A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2210/00—Purification or separation of specific gases
- C01B2210/0001—Separation or purification processing
- C01B2210/0003—Chemical processing
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2210/00—Purification or separation of specific gases
- C01B2210/0043—Impurity removed
- C01B2210/0053—Hydrogen
Abstract
The invention provides a Pd(111)/gamma-Al2O3 catalyst for a CO dehydrogenation purification reaction and a preparation method thereof. The preparation method comprises the following steps: preparing Pd(111) face nanometer particles from Na2PdCl4 under action of a reducing agent and a surfactant, dipping a gamma-Al2O3 carrier of 80 meshes or less in a Pd nanoparticle-containing dipping solution, and carrying out suction filtration and drying to obtain the Pd(111)/gamma-Al2O3 catalyst. The catalyst is characterized in that the crystal face of the active component Pd is a Pd(111) face, a supported amount of Pd is in a range of 0.1 to 5wt%, and Pd is in a form of a spherical nano-particle and has the size of 6-10nm. An evaluation result of the obtained catalyst in a CO dehydrogenation purification reaction shows that the catalyst can completely remove H2 in the dehydrogenation purification process of glycol preparation from coal.
Description
Technical field
The invention belongs to loaded nano crystal catalyst preparation field is and in particular to a kind of γ-Al2O3The Pd of load
(111) nanocrystalline catalyst and preparation method thereof.
Background technology
Ethylene glycol, as simplest aliphatic dihydroxy alcohol, becomes the basic chemical raw materials of a lot of chemical products.For example：
Ethylene glycol can be used for into product polyester dacron, antifreezing agent, antifreeze, resin etc..The production of ethylene glycol mainly has oil and non-stone
Oil circuit line, in conjunction with China's oil starvation, few gas and coal resources relative abundance.Therefore, development coal-ethylene glycol technology have great
Economic and social benefit.
The main preparation process of coal-ethylene glycol is：I synthesis gas that () Coal Gasification obtains purifies through dehydrogenation and makes high-purity CO；
(ii) CO and methyl nitrite gaseous oxidation preparing oxalate coupling reaction；(iii) hydrogenation of oxalate for preparing obtains ethylene glycol.Wherein (ii) is even
Connection needs high-purity CO unstripped gas in a large number, if the H in CO unstripped gas2Too high levels, can make a large amount of catalyst in this route because of H2
It is poisoned and inactivates, therefore in commercial production, require H in CO unstripped gas2Content be less than 100ppm.
At present, remove CO impurities in feed gas H2Maximally efficient method is to be purified by selective catalytic oxidation.China
Patent CN201110182739.5 reports a kind of sol-gal process preparation, and active component is Pd, and carrier is γ-Al2O3,
Chosen property oxidation, purification reaction can make H2It is removed to below 100ppm；Chinese patent CN103223339A reports one kind leaching
Stain method, the more microwaved Pd/ γ-Al preparing2O3In catalyst, can be H2It is removed to below 100ppm.At present not yet
Discovery can be by H2Pd/ γ-the Al of removing completely2O3The preparation of catalyst.For nanocrystal, its pattern and size are to urging
The physico-chemical property of agent has a great impact, especially in the catalytic reaction of structure-sensitive, the crystal face that active component exposes
Particularly evident to the activity and selectivity of reaction.As can be seen here, purify in reaction in CO unstripped gas dehydrogenation, a kind of energy of controllable standby
Enough by H2The high activity Pd nanocrystalline surface catalysis agent of removing completely is significant.
Content of the invention：
It is an object of the invention to provide a kind of highly active Pd (111)/γ-Al2O3Catalyst and preparation method thereof, catalysis
Main active component Pd in agent optionally exposes (111) crystal face, and this catalyst can take off coal-ethylene glycol in hydrogen purification process
H2Remove completely.
Pd (111)/γ-Al provided in the present invention2O3Catalyst, its active component Pd is carried on high dispersive form
In aluminium oxide, the composition formula of catalyst is expressed as：Pd/γ-Al2O3, it is characterized in that the crystal face of this catalyst activity component Pd is Pd
(111) face, this crystal face is to H2Oxidation has higher activity and selectivity.The weight/mass percentage composition (load capacity) of Pd is 0.1-
5.%, preferably weight/mass percentage composition is 0.5-2%.Pd is spherical nanoparticle, a size of 6-10nm, active component Pd species
It is uniformly dispersed in γ-Al2O3In body phase.
Technical solution of the present invention is：By Na2PdCl4Pd (111) is generated in the presence of different reducing agents, surfactant
Face nano-particle；By the γ-Al below 80 mesh2O3It is placed in stirring dipping in the solution containing Pd nano-particle, then sucking filtration, be dried.
Obtain Pd (111)/γ-Al2O3Catalyst.Concrete preparation process is as follows：
A. surfactant, reducing agent are added to mix homogeneously in deionized water together, heat 5- in 60-120 DEG C
30min；It is preferable over 80-120 DEG C of heating 10-20min；Add the Na that concentration is 0.01-1mol/L2PdCl4Aqueous solution, in 60-
120 DEG C of heating 2-8h obtain impregnation liquid；Wherein surfactant is based on monomer and Na2PdCl4Mol ratio be 1-10：1, reduction
Agent and Na2PdCl4Mol ratio be 1-10:1；Preferably surfactant and Na2PdCl4Mol ratio be 3-6：1, reducing agent
With Na2PdCl4Mol ratio be 2-6:1.
Described surfactant be one of cetyl trimethylammonium bromide, Polyvinylpyrrolidone, Oleic acid or
Two kinds；Preferably molecular weight is 10000-100000 Polyvinylpyrrolidone, and preferably molecular weight is 40000-60000；Institute
The reducing agent stated is one of sodium borohydride, formaldehyde, ascorbic acid, citric acid or two kinds；Preferably ascorbic acid；
B. according to impregnation liquid and γ-Al2O3The volume ratio of carrier is 2-12:1, by γ-Al2O3Carrier is to the dipping of step A
In solution, it is stirred at room temperature, the completely rear collected by suction solid product of dipping, deionized water is cleaned three times, obtains catalyst
Precursor；
C. the catalyst precarsor obtaining step B, in 118-122 DEG C of drying, obtains Pd (111)/γ-Al2O3Nano-catalytic
The weight/mass percentage composition of agent, wherein Pd is 0.1-5%；Preferably weight/mass percentage composition is 0.5-2%.
As follows to the catalyst characterization result obtaining：
Fig. 1 obtains the transmission electron microscope photo of the Pd nano-particle in dipping solution for embodiment 1 step A, and Fig. 2 is embodiment
γ-the Al that 1 step C obtains2O3Transmission electron microscope photo after load P d nano-particle.Understand in conjunction with Fig. 1,2：The interplanar of Pd
Before and after for 0.223nm, illustrating to load, the exposure crystal face of Pd is (111) face；The granular size of Pd is 6-10nm, illustrates to load
Significant change in the particle size of Pd in front and back.
The transmission electron microscope picture of the unsupported pure Pd nano-particle that Fig. 3 obtains for embodiment 9 step A, finds Pd load capacity
Improved to after 1.96% by 1.06%, the particle size of Pd remains as 6-10nm, illustrate that the increase of load capacity does not cause Pd
The change of particle size.
The chromatography figure that Fig. 4 evaluates when 220 DEG C for catalyst.The carrier gas of chromatograph is Ar, therefore H2Peak should be
1.5min occurs, O2Peak occurs in 2.8min, and CO peak occurs in 3.4min,.But in figure 1.5min does not occur peak, and
2.8min and 3.4min occurs in that corresponding O2Peak and CO peak.H in product tail gas is described2Remove completely.
Pd (111)/γ-Al that the present invention provides2O3The performance of catalyst passes through synthesis gas dehydrogenation in coal-ethylene glycol technique
Reaction is verified.
Reaction is carried out, using integral fixedbed reactor, the consumption of catalyst in normal pressure miniature evaluating catalyst system
For 1-2g, it is diluted with isopyknic quartz sand.In unstripped gas, the volume ratio of each component is Ar：CO：O2：H2=50：40：3：
2, gas space velocity is 8000-12000h-1, reaction temperature be 220 DEG C, using on-line chromatograph the component of tail gas is carried out detection point
Analysis.
Beneficial effects of the present invention are embodied in：The crystal face that the present invention has prepared active component Pd is Pd (111) face
Pd(111)/γ-Al2O3Catalyst, is supported on γ-Al2O3On active component Pd be spherical nanoparticle, dispersed, Pd
A size of 6-10nm.Obtained catalyst catalytic performance is superior, by the O adding2With the H in unstripped gas2Occur hydrogen-oxygen anti-
Should, at 220 DEG C by the H in unstripped gas2Be removed to 0～10ppm, effectively solve oxo process industry in CO unstripped gas net
Change problem.
Brief description
Fig. 1 is the transmission electron microscope of pure Pd (111) crystal face obtaining after the impregnation liquid centrifugation that embodiment 1 step A obtains
Picture.
Fig. 2 is the Pd/ γ-Al of embodiment 1 step C preparation2O3The transmission electron microscope picture of nanocatalyst.
Fig. 3 is the transmission electron microscope picture of the unsupported pure Pd nano-particle that embodiment 9 step A obtains.
Fig. 4 is the Pd/ γ-Al of embodiment 1 step C preparation2O3Nanocatalyst purifies reaction temperature in reaction in dehydrogenation
The chromatography figure of tail gas when 220 DEG C.
Specific embodiment
Embodiment 1
A. take 525mg Polyvinylpyrrolidone and 300mg ascorbic acid to be dissolved in water, form 40ml aqueous solution.By this solution
It is placed in 100ml flask, heat 10min with continuous stirring in 80 DEG C of water-baths.Take the Na of 285mg2PdCl4It is dissolved in water to be formed
15ml aqueous solution, with pipet, this solution is rapidly added in flask and continues agitating heating 3h in 80 DEG C, be subsequently cooled to room
Warm impregnation liquid.
B. take 10g γ-Al2O3It is added in above-mentioned solution, then magnetic agitation 2h at room temperature, stand 10h.
C. sucking filtration, washing, drying, obtain target product.Find out that Pd granular size is 6-10nm by transmission electron microscope picture, pass through
Plasma emission spectroscopy test learns that the load capacity of Pd in catalyst is 1.06%.
The above-mentioned catalyst preparing is ground and screens out 20-40 mesh, take 1g and the mixing of equal-volume quartz sand, load not
The middle and upper part of rust steel reaction tube, upper strata preheating section loads 6ml quartz sand.In unstripped gas, the volume ratio of each component is N2：CO：O2：H2
=57.7：40：1.25：1.05, gas phase air speed is 10000h-1, reaction temperature be 220 DEG C.By on-line chromatograph assay products, obtain
To H when 220 DEG C2Removing (H in tail gas completely2Content is 0), H2Conversion ratio reach 100%.
Embodiment 2
The reaction temperature of step A in embodiment 1 is risen to heating, remaining step and embodiment 1 phase in 100 DEG C of oil baths
With.Pd granular size is 6-10nm.
Method according to embodiment 1 carries out performance test, and result is：H in the tail gas when 220 DEG C2Content is 0ppm, conversion
Rate 100%.
Embodiment 3
Reducing agent ascorbic acid in embodiment 1 step A is changed to citric acid, the amount of citric acid or 300mg, reaction temperature
80 DEG C of degree, remaining reaction condition is same as Example 1.
Method according to embodiment 1 carries out performance test, and result is：H in the tail gas when 220 DEG C2Content is 6ppm, conversion
Rate 99.999%.
Embodiment 4
Reducing agent ascorbic acid in embodiment 1 step A is changed to citric acid and ascorbic acid mixture, citric acid and anti-
The amount of bad hematic acid is respectively 150mg, 80 DEG C of reaction temperature, and remaining reaction condition is same as Example 1.
Method according to embodiment 1 carries out performance test, and result is：H in the tail gas when 220 DEG C2Content is 9ppm, conversion
Rate 99.999%.
Embodiment 5
Surfactant Polyvinylpyrrolidone in embodiment 1 step A is changed to cetyl trimethylammonium bromide, ten
The amount of six alkyl trimethyl ammonium bromides or 525mg, 80 DEG C of reaction temperature, remaining reaction condition is same as Example 1.
Method according to embodiment 1 carries out performance test, and result is：H in the tail gas when 220 DEG C2Content is 7ppm, conversion
Rate 99.999%.
Embodiment 6
By the surfactant Polyvinylpyrrolidone in embodiment 1 step A be changed to cetyl trimethylammonium bromide and
The amount of the mixture of Polyvinylpyrrolidone, cetyl trimethylammonium bromide and Polyvinylpyrrolidone is respectively 262.5mg,
80 DEG C of reaction temperature, remaining reaction condition is same as Example 1.
Method according to embodiment 1 carries out performance test, and result is：H in the tail gas when 220 DEG C2Content is 0ppm, conversion
Rate 100%.
Embodiment 7
The amount of the reducing agent ascorbic acid in embodiment 1 step A is changed to 200mg, 80 DEG C of reaction temperature, remaining reaction bar
Part is same as Example 1.
Method according to embodiment 1 carries out performance test, and result is：H in the tail gas when 220 DEG C2Content is 4ppm, conversion
Rate 99.999%.
Embodiment 8
The amount of the surfactant Polyvinylpyrrolidone in embodiment 1 step A is changed to 400mg, 80 DEG C of reaction temperature,
Remaining reaction condition is same as Example 1.
Method according to embodiment 1 carries out performance test, and result is：H in the tail gas when 220 DEG C2Content is 2ppm, conversion
Rate 99.9999%.
Embodiment 9
γ-Al will be added in embodiment 1 step B2O3Amount be changed to 5g.Remaining reaction condition is same as Example 1.By throwing
Penetrating its Pd granular size of electron microscopy observation is 6-10nm, and obtaining Pd load capacity according to plasma emission spectroscopy test result is
1.96% Pd/ γ-Al2O3Catalyst.
Method according to embodiment 1 carries out performance test, and result is：H in the tail gas when 220 DEG C2Content is 0ppm, conversion
Rate 100%.
Claims (5)
1. a kind of CO dehydrogenation purifies reaction Pd (111)/γ-Al2O3The preparation method of catalyst, comprises the following steps that：
A. surfactant, reducing agent are added to mix homogeneously in deionized water together, heat 5-30 minute in 60-120 DEG C；Again
Add the Na that concentration is 0.01-1mol/L2PdCl4Aqueous solution, obtains impregnation liquid in 60-120 DEG C of heating 2-8 hour；Wherein surface
Activating agent is based on monomer and Na2PdCl4Mol ratio be 1-10：1, reducing agent and Na2PdCl4Mol ratio be 1-10:1；Described
Surfactant be one of cetyl trimethylammonium bromide, Polyvinylpyrrolidone, Oleic acid or two kinds；Described goes back
Former dose is one of sodium borohydride, formaldehyde, ascorbic acid, citric acid or two kinds；
B. according to impregnation liquid and γ-Al2O3The volume ratio of carrier is 2-12:1, by γ-Al2O3Carrier is to the dipping solution of step A
In, it is stirred at room temperature, the completely rear collected by suction solid product of dipping, deionized water is cleaned three times, obtains catalyst precarsor；
C. the catalyst precarsor obtaining step B, in 100-120 DEG C of drying, obtains Pd (111)/γ-Al2O3Nanocatalyst.
2. CO dehydrogenation according to claim 1 purifies reaction Pd (111)/γ-Al2O3The preparation method of catalyst, it is special
Levying is that surfactant described in step A, reducing agent mixing heat 10-20 minute after 80-120 DEG C, described surface activity
Agent and Na2PdCl4Mol ratio be 3-6：1, reducing agent and Na2PdCl4Mol ratio be 2-6:1；Described surfactant is
Molecular weight is 10000-100000 Polyvinylpyrrolidone；Described reducing agent is ascorbic acid.
3. CO dehydrogenation according to claim 1 purifies reaction Pd (111)/γ-Al2O3The preparation method of catalyst, it is special
Levy the surfactant being described be molecular weight be 40000-60000 Polyvinylpyrrolidone.
4. a kind of CO dehydrogenation of method preparation according to claim 1 purifies reaction Pd (111)/γ-Al2O3Catalyst,
The crystal face that it is characterized in that this catalyst activity component Pd is Pd (111) face, and the weight/mass percentage composition of Pd is 0.1-5%；Pd is ball
Shape nano-particle, a size of 6-10nm.
5. CO dehydrogenation according to claim 4 purifies reaction Pd (111)/γ-Al2O3Catalyst, in its feature catalyst
The weight/mass percentage composition of Pd is 0.5-2%.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107308962A (en) * | 2017-06-13 | 2017-11-03 | 中国科学院福建物质结构研究所 | A kind of CO dehydrogenations purification Pd Cl/CeOCl catalyst and preparation method |
| CN107456999A (en) * | 2017-07-17 | 2017-12-12 | 中国科学院福建物质结构研究所 | A kind of nano Pd catalyst of porous manganese organic frame load and preparation method thereof |
| CN109395714A (en) * | 2017-08-16 | 2019-03-01 | 王学彬 | A kind of catalyst and preparation method thereof prepared using jasmine flower extract |
| CN113600183A (en) * | 2021-09-07 | 2021-11-05 | 长春工业大学 | Preparation method and application of Pd-based catalyst |
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| CN102513101A (en) * | 2011-12-14 | 2012-06-27 | 中国科学院福建物质结构研究所 | Nano Pd catalyst used for preparing oxalic ester by CO gas phase oxidation coupling and its preparation method |
| CN102974344A (en) * | 2012-10-30 | 2013-03-20 | 大连凯特利催化工程技术有限公司 | Dehydrogenation catalyst applicable to raw gas rich in carbon monoxide, and preparation and application thereof |
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| CN107308962A (en) * | 2017-06-13 | 2017-11-03 | 中国科学院福建物质结构研究所 | A kind of CO dehydrogenations purification Pd Cl/CeOCl catalyst and preparation method |
| CN107456999A (en) * | 2017-07-17 | 2017-12-12 | 中国科学院福建物质结构研究所 | A kind of nano Pd catalyst of porous manganese organic frame load and preparation method thereof |
| CN109395714A (en) * | 2017-08-16 | 2019-03-01 | 王学彬 | A kind of catalyst and preparation method thereof prepared using jasmine flower extract |
| CN113600183A (en) * | 2021-09-07 | 2021-11-05 | 长春工业大学 | Preparation method and application of Pd-based catalyst |
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