CN106391000B - CO dehydrogenation purification reaction Pd (111)/γ-Al2O3Catalyst and preparation method thereof - Google Patents
CO dehydrogenation purification reaction Pd (111)/γ-Al2O3Catalyst and preparation method thereof Download PDFInfo
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- CN106391000B CN106391000B CN201610881704.3A CN201610881704A CN106391000B CN 106391000 B CN106391000 B CN 106391000B CN 201610881704 A CN201610881704 A CN 201610881704A CN 106391000 B CN106391000 B CN 106391000B
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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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- 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
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- C—CHEMISTRY; METALLURGY
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- 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 present invention provides a kind of CO dehydrogenation purification reaction Pd (111)/γ-Al2O3Catalyst and preparation method thereof, the preparation method is that: by Na2PdCl4Pd (111) face nano particle is generated under the action of reducing agent, surfactant；By 80 mesh γ-Al below2O3Carrier, which is placed in the dipping solution of the nano particle containing Pd, to be impregnated, and is filtered, dry, obtains Pd (111)/γ-Al2O3Catalyst.The catalyst is characterized in that the crystal face of active component Pd is Pd (111) face, and the load capacity of Pd is 0.1-5wt.%；Pd is spherical nanoparticle, having a size of 6-10nm.Obtained evaluating catalyst CO is purified into dehydrogenation reaction, obtaining the catalyst can be by the H in coal-ethylene glycol dehydrogenation purification process2Removing completely.
Description
Technical field
The invention belongs to loaded nano crystal catalyst preparation fields, and in particular to a kind of γ-Al2O3The Pd of load
(111) nanocrystalline catalyst and preparation method thereof.
Background technique
Ethylene glycol becomes the basic chemical raw materials of many chemical products as simplest aliphatic dihydroxy alcohol.Such as:
Ethylene glycol, which can be used for into, produces polyester dacron, antifreezing agent, antifreeze, resin etc..The production of ethylene glycol mainly has petroleum and non-stone
Oil circuit line, in conjunction with China's oil starvation, few gas and coal resources relative abundance.Therefore, develop coal-ethylene glycol technology with great
Economic and social benefit.
The main preparation process of coal-ethylene glycol are as follows: the synthesis gas that (i) Coal Gasification obtains makes high-purity CO through dehydrogenation purification；
(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 a large amount of high-purity CO unstripped gas, 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 require H in CO unstripped gas in industrial production2Content be lower than 100ppm.
Currently, removing CO impurities in feed gas H2Maximally efficient method is purified by selective catalytic oxidation.China
Patent CN201110182739.5 report it is a kind of with sol-gal process prepare, active component Pd, carrier be γ-Al2O3,
Chosen property oxidation, purification reaction can make H2It is removed to 100ppm or less；Chinese patent CN103223339A reports a kind of leaching
Stain method, then the Pd/ γ-Al that microwave treatment is prepared2O3It, can be H in catalyst2It is removed to 100ppm or less.At present not yet
It was found that can be by H2Pd/ γ-the Al removed completely2O3The preparation of catalyst.For nanocrystal, pattern and size are to urging
The physico-chemical property of agent has a great impact, especially in the catalysis reaction of structure-sensitive, the crystal face of active component exposure
It is particularly evident to the activity and selectivity of reaction.It can be seen that in CO unstripped gas dehydrogenation purification reaction, a kind of energy of controllable preparation
Enough by H2The nanocrystalline surface catalysis agent of the high activity Pd removed completely is of great significance.
Summary of the invention:
The object of the present invention is to provide a kind of Pd of high activity (111)/γ-Al2O3Catalyst and preparation method thereof, catalysis
Exposure (111) crystal face of main active component Pd selectivity in agent, the catalyst can will be in coal-ethylene glycol dehydrogenation purification processes
H2Removing completely.
Pd provided in the present invention (111)/γ-Al2O3Catalyst, active component Pd are carried in the form of high dispersive
In aluminium oxide, the composition formula of catalyst is indicated are as follows: Pd/ γ-Al2O3, it is characterized in that the crystal face of catalyst activity component Pd is Pd
(111) face, the crystal face is to H2Oxidation has higher activity and selectivity.The mass percentage (load capacity) of Pd is 0.1-
5.%, preferably mass percentage is 0.5-2%.Pd is spherical nanoparticle, having a size of 6-10nm, active component Pd species
It is uniformly dispersed in γ-Al2O3In body phase.
Technical solution of the present invention are as follows: by Na2PdCl4Pd (111) are generated under the action of different reducing agents, surfactant
Face nano particle；By 80 mesh γ-Al below2O3It is placed in the solution of the nano particle containing Pd and stirs dipping, then filter, it is dry.
Obtain Pd (111)/γ-Al2O3Catalyst.Specific preparation process is as follows:
A. surfactant, reducing agent are added to together in deionized water and are uniformly mixed, in 60-120 DEG C of heating 5-
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 maceration extract；Wherein surfactant is based on monomer and Na2PdCl4Molar ratio be 1-10:1, reduction
Agent and Na2PdCl4Molar ratio be 1-10:1；Preferably surfactant and Na2PdCl4Molar ratio be 3-6:1, reducing agent
With Na2PdCl4Molar ratio be 2-6:1.
The 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 or both of sodium borohydride, formaldehyde, ascorbic acid, citric acid；Preferably ascorbic acid；
B. according to maceration extract and γ-Al2O3The volume ratio of carrier is 2-12:1, by γ-Al2O3Dipping of the carrier to step A
It in solution, is stirred at room temperature, collected by suction solid product, is cleaned three times with deionized water, obtain catalyst after impregnating completely
Precursor；
C. catalyst precarsor step B obtained obtains Pd (111)/γ-Al in 118-122 DEG C of drying2O3Nano-catalytic
Agent, wherein the mass percentage of Pd is 0.1-5%；Preferably mass percentage is 0.5-2%.
It is as follows to obtained catalyst characterization result:
Fig. 1 is that 1 step A of embodiment obtains the transmission electron microscope photo of the Pd nano particle in dipping solution, and Fig. 2 is embodiment
γ-the Al that 1 step C is obtained2O3Transmission electron microscope photo after loading Pd nano particle.In conjunction with known in Fig. 1,2: the interplanar of Pd
It is (111) face away from the exposure crystal face for for 0.223nm, illustrating load front and back Pd；The granular size of Pd is 6-10nm, illustrates to load
The particle size of front and back Pd does not occur significant change.
Fig. 3 is the transmission electron microscope picture for the unsupported pure Pd nano particle that 9 step A of embodiment is obtained, and finds Pd load capacity
It is improved by 1.06% to after 1.96%, the particle size of Pd remains as 6-10nm, illustrates that the increase of load capacity does not cause Pd
The variation of particle size.
Fig. 4 is the chromatography figure that catalyst is evaluated when 220 DEG C.The carrier gas of chromatography is Ar, therefore H2Peak should be
1.5min occurs, O2Peak occurs in 2.8min, and the peak CO occurs in 3.4min,.But 1.5min does not occur peak in figure, and
There is corresponding O in 2.8min and 3.4min2Peak and the peak CO.Illustrate the H in product tail gas2Remove completely.
Pd (111)/γ-Al provided by the invention2O3The performance of catalyst passes through synthesis gas dehydrogenation in coal-ethylene glycol technique
Reaction is verified.
Reaction carries out in the miniature evaluating catalyst system of normal pressure, using integral fixedbed reactor, the dosage of catalyst
For 1-2g, it is diluted with isometric quartz sand.The volume ratio of each component is Ar:CO:O in unstripped gas2: H2=50:40:3:
2, gas space velocity 8000-12000h-1, reaction temperature is 220 DEG C, carries out detection point using component of the on-line chromatograph to tail gas
Analysis.
The beneficial effects of the present invention are embodied in: the crystal face that active component Pd has been prepared in the present invention is Pd (111) face
Pd(111)/γ-Al2O3Catalyst is supported on γ-Al2O3On active component Pd be spherical nanoparticle, evenly dispersed, Pd
Having a size of 6-10nm.Obtained catalyst catalytic performance is superior, passes through the O of addition2With the H in unstripped gas2It is anti-that hydrogen-oxygen occurs
It answers, at 220 DEG C by the H in unstripped gas2It is removed to 0~10ppm, CO unstripped gas is net in effective solution carbonylation synthesis industry
Change problem.
Detailed description of the invention
Fig. 1 is the transmission electron microscope of pure Pd (111) crystal face obtained after the maceration extract that 1 step A of embodiment is obtained is centrifugated
Picture.
Fig. 2 is the Pd/ γ-Al of 1 step C of embodiment preparation2O3The transmission electron microscope picture of nanocatalyst.
Fig. 3 is the transmission electron microscope picture for the unsupported pure Pd nano particle that 9 step A of embodiment is obtained.
Fig. 4 is the Pd/ γ-Al of 1 step C of embodiment preparation2O3Nanocatalyst reaction temperature in dehydrogenation purification reaction is
The chromatography figure of tail gas at 220 DEG C.
Specific embodiment
Embodiment 1
A. it takes 525mg polyvinylpyrrolidone and 300mg ascorbic acid to be dissolved in water, forms 40ml aqueous solution.By this solution
It is placed in 100ml flask, heats 10min in 80 DEG C of water-baths with continuous stirring.Take the Na of 285mg2PdCl4Water is dissolved in be formed
This solution, is rapidly added in flask and in 80 DEG C of continuation agitating and heating 3h by 15ml aqueous solution with pipette, is subsequently cooled to room
It is warm to obtain maceration extract.
B. 10g γ-Al is taken2O3It is added in above-mentioned solution, then magnetic agitation 2h at room temperature, stands 10h.
C. it filters, wash, drying, obtaining target product.Find out that Pd granular size is 6-10nm by transmission electron microscope picture, passes through
Plasma emission spectroscopy test learns that the load capacity of Pd in catalyst is 1.06%.
The above-mentioned catalyst grinding being prepared is screened out into 20-40 mesh, takes 1g and isometric quartz sand to mix, is packed into not
The middle and upper part of rust steel reaction tube, upper layer preheating section load 6ml quartz sand.The volume ratio of each component is N in unstripped gas2: CO:O2: H2
=57.7:40:1.25:1.05, gas phase air speed are 10000h-1, reaction temperature is 220 DEG C.Product is analyzed by on-line chromatograph, is obtained
To the H 220 DEG C when2Removing (H in tail gas completely2Content is 0) H2Conversion ratio reach 100%.
Embodiment 2
The reaction temperature of step A in embodiment 1 is promoted into 100 DEG C of oil baths and is heated, 1 phase of remaining step and embodiment
Together.Pd granular size is 6-10nm.
It is tested for the property according to the method for embodiment 1, as a result are as follows: the H in tail gas at 220 DEG C2Content is 0ppm, conversion
Rate 100%.
Embodiment 3
Reducing agent ascorbic acid in 1 step A of embodiment is changed to citric acid, the amount or 300mg of citric acid, reaction temperature
80 DEG C of degree, remaining reaction condition is same as Example 1.
It is tested for the property according to the method for embodiment 1, as a result are as follows: the H in tail gas at 220 DEG C2Content is 6ppm, conversion
Rate 99.999%.
Embodiment 4
Reducing agent ascorbic acid in 1 step A of embodiment is changed to citric acid and ascorbic acid mixture, citric acid and anti-
The amount of bad hematic acid is respectively 150mg, and 80 DEG C of reaction temperature, remaining reaction condition is same as Example 1.
It is tested for the property according to the method for embodiment 1, as a result are as follows: the H in tail gas at 220 DEG C2Content is 9ppm, conversion
Rate 99.999%.
Embodiment 5
Surfactant polyvinylpyrrolidone in 1 step A of embodiment is changed to cetyl trimethylammonium bromide, ten
The amount or 525mg of six alkyl trimethyl ammonium bromides, 80 DEG C of reaction temperature, remaining reaction condition is same as Example 1.
It is tested for the property according to the method for embodiment 1, as a result are as follows: the H in tail gas at 220 DEG C2Content is 7ppm, conversion
Rate 99.999%.
Embodiment 6
By the surfactant polyvinylpyrrolidone in 1 step A of embodiment 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.
It is tested for the property according to the method for embodiment 1, as a result are as follows: the H in tail gas at 220 DEG C2Content is 0ppm, conversion
Rate 100%.
Embodiment 7
The amount of reducing agent ascorbic acid in 1 step A of embodiment is changed to 200mg, 80 DEG C of reaction temperature, remaining reaction item
Part is same as Example 1.
It is tested for the property according to the method for embodiment 1, as a result are as follows: the H in tail gas at 220 DEG C2Content is 4ppm, conversion
Rate 99.999%.
Embodiment 8
The amount of surfactant polyvinylpyrrolidone in 1 step A of embodiment is changed to 400mg, 80 DEG C of reaction temperature,
Remaining reaction condition is same as Example 1.
It is tested for the property according to the method for embodiment 1, as a result are as follows: the H in tail gas at 220 DEG C2Content is 2ppm, conversion
Rate 99.9999%.
Embodiment 9
γ-Al will be added in 1 step B of embodiment2O3Amount be changed to 5g.Remaining reaction condition is same as Example 1.By throwing
It is 6-10nm that radio mirror, which observes its Pd granular size, and obtaining Pd load capacity according to plasma emission spectroscopy test result is
1.96% Pd/ γ-Al2O3Catalyst.
It is tested for the property according to the method for embodiment 1, as a result are as follows: the H in tail gas at 220 DEG C2Content is 0ppm, conversion
Rate 100%.
Claims (3)
1. a kind of CO dehydrogenation purification reaction Pd (111)/γ-Al2O3The preparation method of catalyst, the specific steps are as follows:
A. by surfactant, reducing agent be added to together in deionized water be uniformly mixed, in 60-120 DEG C heating 5-30 minutes；Again
The Na that concentration is 0.01-1mol/L is added2PdCl4Aqueous solution obtains maceration extract in heating 2-8 hours in 60-120 DEG C；Wherein table
Face activating agent is based on monomer and Na2PdCl4Molar ratio be 1-10:1, reducing agent and Na2PdCl4Molar ratio be 1-10:1；Institute
The surfactant stated is one or both of cetyl trimethylammonium bromide, polyvinylpyrrolidone, oleic acid；Described
Reducing agent is one or both of sodium borohydride, formaldehyde, ascorbic acid, citric acid；
B. according to maceration extract and γ-Al2O3The volume ratio of carrier is 2-12:1, by γ-Al2O3Carrier is added to the dipping of step A
It in solution, is stirred at room temperature, collected by suction solid product, is cleaned three times with deionized water, obtain catalyst after impregnating completely
Precursor；
C. catalyst precarsor step B obtained obtains Pd (111)/γ-Al in 100-120 DEG C of drying2O3Nanocatalyst；
The crystal face of catalyst activity component Pd is Pd (111) face, and the mass percentage of Pd is 0.1-5%；Pd is ball shaped nano
Grain, having a size of 6-10nm.
2. CO dehydrogenation purification reaction according to claim 1 Pd (111)/γ-Al2O3The preparation method of catalyst,
Be characterized in surfactant described in step A, after reducing agent mixing in 80-120 DEG C heating 10-20 minutes, the described surface work
Property agent and Na2PdCl4Molar ratio be 3-6:1, reducing agent and Na2PdCl4Molar ratio be 2-6:1；The surfactant
Be molecular weight be 10000-100000 polyvinylpyrrolidone；The reducing agent is ascorbic acid.
3. CO dehydrogenation purification reaction according to claim 1 Pd (111)/γ-Al2O3The preparation method of catalyst,
Surfactant described in being characterized in is that molecular weight is 40000-60000 polyvinylpyrrolidone.
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| CN107308962B (en) * | 2017-06-13 | 2019-03-08 | 中国科学院福建物质结构研究所 | A kind of CO dehydrogenation purification Pd-Cl/CeOCl catalyst and preparation method |
| CN107456999B (en) * | 2017-07-17 | 2019-03-08 | 中国科学院福建物质结构研究所 | A kind of nano Pd catalyst and preparation method thereof of porous manganese organic frame load |
| 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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