CN104399529B - A kind of alkadienes selective hydrocatalyst and preparation method and application - Google Patents
A kind of alkadienes selective hydrocatalyst and preparation method and application Download PDFInfo
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- CN104399529B CN104399529B CN201410655649.7A CN201410655649A CN104399529B CN 104399529 B CN104399529 B CN 104399529B CN 201410655649 A CN201410655649 A CN 201410655649A CN 104399529 B CN104399529 B CN 104399529B
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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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- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
Abstract
The invention provides a kind of alkadienes selective hydrocatalyst and preparation method thereof.The carrier of this catalyst is the step hole FZIF 8 of carboxyl-functional, and active component is palladium；Gross weight based on catalyst carrier, the content of active component palladium is 0.1 10%.Present invention also offers the preparation method of above-mentioned alkadienes selective hydrocatalyst.Having step pore structure in alkadienes selective hydrocatalyst carrier provided by the present invention, make carboxylic group have accessibility, active component can produce with carboxylic group and interact；Containing carboxylic group in catalyst carrier, it is possible to anchoring activity component, it is achieved the high dispersive of active component, stoping active component reunion in course of reaction and loss, catalyst activity is high simultaneously.This catalyst is applicable to the hydro-upgrading of FCC gasoline, the alkadienes in removing oil product, and reaction condition relaxes, and reaction temperature is low, pressure is low, and selectivity of product hydrogenation is effective.
Description
Technical field
The present invention relates to a kind of alkadienes selective hydrocatalyst and preparation method and application, belong to catalyst and prepare
Technical field.
Background technology
21st century is the New Times of economically developed clean environment, and research and development environment-friendly type cleaning fuel is greenization
One of most important research topic in.
In recent years, air pollution problems inherent becomes increasingly conspicuous, and haze problem is increasingly severe.The haze standard of China is from 2013
On January 1, in is the most tentative, but just from the beginning of 2013, Middle And Eastern China suffers from haze weather in succession, is permitted
It is upper and lower that the PM2.5 concentration in many cities reaches 500 μ g, for 7 times of the 24h mean concentration limit value that Chinese Industrial Standards (CIS) specifies
Left and right.PM2.5 increasingly becomes the focus of public attention.In China's energy-consuming, it is left that coal and oil account for 90%
The right side, everybody generally believes that coal and oil are maximum for the contribution of China's haze.
For environment protection, the environmental regulation of increasingly stringent requires that gasoline becomes eco-friendly oil product.By
FCC gasoline proportion higher (accounting for 75%-80%) in domestic gasoline product, in FCC gasoline, alkene volume contains
Amount generally up to 40%-60%.Alkene is commonly present the alkadienes of trace, although their content is less, but this
A little alkadienes are easily polymerized generation colloid in FCC gasoline hydrogenation restructuring process, and blocking catalyst duct, impact is urged
The agent life-span.Therefore, one of key that home-produced fuel cleans is to reduce the alkadienes in FCC gasoline, and
Reduce the loss of octane number as far as possible.
At present, the removing most economical feasible method of alkadienes is selective hydrogenation technology.Selective hydrocatalyst is mostly
With Pd as main active component.The active component of conventional catalyst is easily reunited in course of reaction and runs off, and causes
Hydrogenation catalyst conversion ratio is the highest, and alkadienes is easily hydrogenated to alkane simultaneously, causes hydrogenation catalyst selectivity the highest,
Cause the generation of a large amount of alkane, cause the heavy losses of octane number.In order to solve these problems, researchers develop
A series of alkadienes selective hydrocatalysts, to improving its hydrogenation while improving catalyst hydrogenation conversion ratio
Selectivity, but effect is not ideal.
Summary of the invention
For solving above-mentioned technical problem, it is an object of the invention to provide a kind of conversion ratio and the best alkadienes of selectivity
Selective hydrocatalyst.
The present invention also aims to provide the preparation method of above-mentioned alkadienes selective hydrocatalyst.
For reaching above-mentioned purpose, present invention firstly provides a kind of alkadienes selective hydrocatalyst, wherein, this is urged
The carrier of agent is the step hole FZIF-8 of carboxyl-functional, and active component is palladium；
Gross weight based on catalyst carrier, the content of active component palladium is 0.1-10%, preferably 0.3%.
Alkadienes selective hydrocatalyst provided by the present invention is by introducing carboxylic group on carrier, for grappling
Metal active constituent, makes active component realize high dispersive on a catalyst support, effectively improves catalyst activity component
Reunion in catalytic reaction and losing issue, improve the hydrogenation conversion of catalyst；Carboxyl and active component simultaneously
Strong interaction, change the electron density of active component, significantly improve the hydrogenation selectivity of catalyst.
Present invention also offers the preparation method of above-mentioned alkadienes selective hydrocatalyst, it comprises the following steps:
Sodium hydroxide, cationic surfactant, part are added to the water, stir to after being completely dissolved, add zinc source,
Stirring, obtain mixture, mixing raw material weight ratio is for sodium hydroxide: cationic surfactant: water: part:
: (1-6) zinc source=(15-45): (5-20): 250:(2-8)；
Mixture is carried out crystallization, then crystallization product extracted, be dried, obtain FZIF-8 carrier；
FZIF-8 carrier is joined dissolved with Pd2+Impregnation liquid in palladium-impregnated, then drying, reduction, make institute
State alkadienes selective hydrocatalyst.
In above-mentioned preparation method, it is preferable that the cationic surfactant used is quaternary ammonium salt surface active agent,
Carbon chain lengths is C6-C20, such as cetyl trimethylammonium bromide, CTAB.Cationic surfactant, especially
It is CTAB, in the synthetic system of alkadienes selective hydrocatalyst provided by the present invention, not only acts as template
Effect, the generation of guide step pore structure, and can carrier synthesize during protect carboxylic group not with shape
Become the metallic ion coordination of carrier framework structure.The existence in step hole makes carboxylic group have accessibility, active component
Can produce with carboxylic group and interact.
In above-mentioned preparation method, it is preferable that the part used is 2-methyl isophthalic acid H-imidazole-4,5-dicarboxylic acid.
In above-mentioned preparation method, it is preferable that the zinc source used is Zn (NO3)2·6H2O、
Zn(CH3COO)2·2H2O、ZnCl2In one or more mixture.
In above-mentioned preparation method, it is preferable that the time of crystallization is 12-48 hour, the temperature of crystallization is 80-180
DEG C, described being dried is 80-100 DEG C of process 2-8 hour.
In above-mentioned preparation method, it is preferable that the extract that extraction uses is the one in ethanol, propanol, acetone etc.
Or two or more mixture.
In above-mentioned preparation method, it is preferable that the impregnation liquid used is palladium, Palladous nitrate., Palladous chloride., double second
Nitrile acetone palladium, palladium acetylacetonate solution in one.This solution can be aqueous solution, it is also possible to is acetonitrile solution.
In above-mentioned preparation method, it is preferable that the temperature of reduction is 80-200 DEG C, active component and the weight hundred of carrier
Proportion by subtraction is 0.1%-10%.This condition is the usage ratio limiting FZIF-8 carrier with the Pd in impregnation liquid, ratio
Refer to that active component accounts for the 0.1-10% of carrier quality.
Present invention also offers above-mentioned alkadienes selective hydrocatalyst answering in alkadienes selective hydrogenation
With.
Alkadienes selective hydrocatalyst provided by the present invention has the advantage that
1, having step pore structure in catalyst carrier, make carboxylic group have accessibility, active component can be with
Carboxylic group produces and interacts；
2, containing carboxylic group in catalyst carrier, it is possible to anchoring activity component, it is achieved the high dispersive of active component,
Stoping active component reunion in course of reaction and loss, catalyst activity is high simultaneously；
3, the active component of catalyst produces strong interaction with carboxylic group, improves the electron density of active component,
Significantly improving the selectivity reduction problem that little seed activity component causes due to electron deficiency effect, catalyst is comprehensive
Can be good；
4, this catalyst is applicable to the hydrogenation transformation of the way of FCC gasoline, the alkadienes in removing oil product, and reaction condition delays
With, reaction temperature is low, pressure is low, and selectivity of product hydrogenation is effective.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of the carrier in embodiment 1, embodiment 2, comparative example 1 and comparative example 2；
Urging in Fig. 2 A-Fig. 2 E respectively embodiment 1, embodiment 2, comparative example 1, comparative example 2 and comparative example 3
The palladium particle size distribution figure of agent；
Fig. 3 is that the catalyst in embodiment 1, embodiment 2, comparative example 1, comparative example 2 and comparative example 3 is at diene
Evaluation result in hydrocarbon-selective hydrogenation reaction.
Detailed description of the invention
In order to the technical characteristic of the present invention, purpose and beneficial effect are more clearly understood from, the existing skill to the present invention
Art scheme carries out described further below, but it is not intended that to the present invention can the restriction of practical range.
Embodiment 1
Present embodiments provide a kind of alkadienes selective hydrocatalyst, in terms of the weight of catalyst carrier, activity group
The content dividing palladium is 0.3wt%, is designated as catalyst A.
This catalyst through the following steps that preparation:
Being dissolved in 50 ml deionized water by 3.6 grams of CTAB, 3.0g gram of NaOH, stirring, to being completely dissolved, adds
Enter 1.3 grams of 2-methyl isophthalic acid H-imidazole-4,5-dicarboxylic acids, after dissolving, add 1.2 grams of Zn (NO3)2·6H2O, obtains
Mixed reaction solution；
Reactant liquor is poured in 100 milliliters of politef reactors, 140 DEG C of crystallization 24 hours, after having reacted from
So it is cooled to room temperature, sucking filtration separation solid product, is washed with deionized, extracts CTAB with dehydrated alcohol, then
Centrifugation product, after 100 DEG C dry 12 hours, makes catalyst carrier FZIF-8, its XRD spectra such as Fig. 1
Shown in；
2.0 grams of FZIF-8 are immersed in the acetonitrile solution dissolved with 0.015 gram of Palladous chloride., stir 24 hours under room temperature,
Then being dried in 100 DEG C and remove solvent, dried sample carries out compression molding, broken, and sieve takes the sample of 20-40 mesh
Product high-purity hydrogen reduces 5 hours at 150 DEG C, makes catalyst Pd/FZIF-8, i.e. catalyst A.Palladium granule chi
Very little scattergram is as shown in Figure 2 A.
Embodiment 2
Present embodiments provide a kind of alkadienes selective hydrocatalyst, in terms of the weight of catalyst carrier, activity group
The content dividing palladium is 0.3wt%, is designated as catalyst B.Palladium particle size distribution figure is as shown in Figure 2 B.
Preparation method is same as in Example 1, except that be 2.6 grams by the quantitative change of CTAB.
Comparative example 1
This comparative example provides a kind of alkadienes selective hydrocatalyst, in terms of the weight of catalyst carrier, and activity group
The content dividing palladium is 0.3wt%, is designated as catalyst C.Palladium particle size distribution figure is as shown in Figure 2 C.
This catalyst through the following steps that preparation:
By 8.32 grams of Zn (NO3)2·4H2O, 1.76 grams be dissolved in 100 milliliters of DMFs, then
Reactant liquor is poured in politef reactor in 100 DEG C of crystallization 20 hours；
Naturally cool to room temperature, sucking filtration separation solid product after crystallization is complete, be washed with deionized, make catalysis
Agent carrier MOF-5, its XRD spectra is as shown in Figure 1；
The preparation method of catalyst is same as in Example 1, except that the FZIF-8 in carrier becomes conventional
MOF-5。
Comparative example 2
This comparative example provides a kind of alkadienes selective hydrocatalyst, in terms of the weight of catalyst carrier, and activity group
The content dividing palladium is 0.3wt%, is designated as catalyst D.Palladium particle size distribution figure is as shown in Figure 2 D.
This catalyst through the following steps that preparation:
By 1.05 grams of ZnCl2, 0.3 gram of 2-methylimidazole be dissolved in 90 milliliters of DMFs, then
Reactant liquor is poured in 100 milliliters of politef reactors in 140 DEG C of crystallization 24 hours；
Naturally cool to room temperature, sucking filtration separation solid product after crystallization is complete, be washed with deionized, make catalysis
Agent carrier ZIF-8, its XRD spectra is as shown in Figure 1；
The preparation method of catalyst is same as in Example 1, except that the FZIF-8 in carrier becomes conventional
ZIF-8。
Comparative example 3
This comparative example provides a kind of alkadienes selective hydrocatalyst, in terms of the weight of catalyst carrier, and activity group
The content dividing palladium is 0.3wt%, is designated as catalyst E.Palladium particle size distribution figure is as shown in Figure 2 E.
This catalyst through the following steps that preparation:
The aluminum isopropylate. solution of preparation 2mol/L, hydrolyzes at 85 DEG C, stirs 1 hour；
HNO is added in gained serosity3Plastic, colloidal sol refluxes 12 hours at 95 DEG C；
Then colloidal sol is dried 48 hours at 40 DEG C；Then by the colloidal sol after red drying in Muffle furnace in 600 DEG C
Lower calcining 4 hours, makes the carrier γ-Al of catalyst2O3；
The preparation method of catalyst is same as in Example 1, except that the FZIF-8 in carrier is become γ-Al2O3。
The active component data of the catalyst of embodiment 1-2 and comparative example 1-3 are as shown in table 1.
The sign data of the active component of each catalyst of table 1
| Catalyst | Palladium content (%) | Palladium particle mean size (nm) | Palladium particle dispersion (%) |
| A | 0.3 | 3.5 | 85 |
| B | 0.3 | 4 | 82 |
| C | 0.3 | 16.5 | 20 |
| D | 0.3 | 13 | 24 |
| E | 0.3 | 15 | 22 |
Alkadienes selective hydrocatalyst activity rating
The catalyst preparing embodiment 1,2 and comparative example 1-3 carries out alkadienes selective hydrogenation catalytically active assessment.
This alkadienes selective hydrogenation evaluation is moved at high pressure continuous flow and is carried out on fixed-bed micro-devices, concrete steps
As follows: loading in reaction tube after being diluted by the quartz sand of the particle diameters such as catalyst use, reaction condition is: 1.0-4.0MPa,
40-120 DEG C, air speed 8-20h-1, hydrogen-oil ratio (volume) 2-6, after stable reaction 24-72h sampling be analyzed.
Model gasoline comprise 85% (mass fraction) normal heptane, 5% isoprene, 10% iso-amylene (2-methyl-2-butene:
90%, 2-methyl-1-butene alkene: 10%).
Using di-olefins rate (X) and monoolefine selectivity (S) as evaluation index, its computing formula is as follows:
Wherein, X is di-olefins rate, and S is monoolefine selectivity.
The concrete evaluation result of each catalyst is as shown in Figure 3.
As seen from Figure 3, although other conditions are the most identical, with use catalyst Pd/ZIF-8, Pd/MOF-5 and
Pd/Al2O3Compare, use catalyst Pd/FZIF-8 to present higher di-olefins rate and monoolefine selectivity.
Owing to the dispersion of supported palladium granule is the highest, particle size is the least, the conversion ratio of isoprene is the highest, therefore best result
The Pd/FZIF-8 dissipated has the highest di-olefins rate, and Pd/FZIF-8 has the monoolefine selectivity of optimum simultaneously,
This is because palladium granule produces strong interaction with the carboxyl in Pd/FZIF-8, cause the electron density liter of palladium granule
High, it is possible to avoid because the monoolefine selectivity that the electron deficiency effect of small size palladium granule causes reduces problem.
Although the dispersion of palladium nano-particles is the highest in Pd/MOF-5, but live owing to MOF-5 having Lewis acid
The ligand unsatuated metal point of property, this metal coordination site can promote that isoprene is hydrogenated to isopentane further, therefore
Although di-olefins rate can reach 95% on Pd/MOF-5 catalyst, but monoolefine selectivity only has 70%.
Pd/ZIF-8 and Pd/Al2O3Di-olefins rate and monoolefine selectivity the highest, this be due to Pd/ZIF-8 and
Pd/Al2O3The reunion of middle Pd nano-particle result in the selectivity not having enough catalytic active sites for isoprene
Hydrogenation and iso-amylene are hydrogenated into isopentane further.
More than test result indicate that: the alkadienes selective hydrocatalyst that the present invention provides is lived by carboxylic group grappling
Property component, the palladium particle dispersion of catalyst is high, and palladium granule and carboxyl produce strong interaction changes palladium granule
Electron density, improve the conversion ratio of alkadienes and the selectivity of monoolefine simultaneously, significantly improve catalyst
Hydrogenation reaction performance.
Claims (9)
1. an alkadienes selective hydrocatalyst, wherein, the carrier of this catalyst is the step of carboxyl-functional
Hole FZIF-8, active component is palladium；Further, carboxylic group not with formed carrier framework structure metallic ion coordination；
Gross weight based on catalyst carrier, the content of active component palladium is 0.1-10%；
Wherein, described carboxyl-functional step hole FZIF-8 through the following steps that preparation: by sodium hydroxide,
Cationic surfactant, part are added to the water, and stir to after being completely dissolved, add zinc source, stir, obtain
Mixture, mixing raw material weight ratio is for sodium hydroxide: cationic surfactant: water: part: zinc source=(15-45):
(5-20):250:(2-8):(1-6)；Mixture is carried out crystallization, then crystallization product extracted, be dried,
To FZIF-8 carrier.
2. the preparation method of the alkadienes selective hydrocatalyst described in claim 1, it comprises the following steps:
Sodium hydroxide, cationic surfactant, part are added to the water, stir to after being completely dissolved, add zinc source,
Stirring, obtain mixture, mixing raw material weight ratio is for sodium hydroxide: cationic surfactant: water: part:
: (1-6) zinc source=(15-45): (5-20): 250:(2-8)；Described part is 2-methyl isophthalic acid H-imidazoles-4,5-dicarboxylic acids；
Mixture is carried out crystallization, then crystallization product extracted, be dried, obtain FZIF-8 carrier；
FZIF-8 carrier is joined dissolved with Pd2+Impregnation liquid in palladium-impregnated, then drying, reduction, make institute
State alkadienes selective hydrocatalyst.
3. preparation method as claimed in claim 2, wherein, described cationic surfactant is quaternary ammonium salt table
Face activating agent, carbon chain lengths is C6-C20。
4. preparation method as claimed in claim 2, wherein, described zinc source is Zn (NO3)2·6H2O、
Zn(CH3COO)2·2H2O、ZnCl2In one or more mixture.
5. preparation method as claimed in claim 2, wherein, the time of described crystallization is 12-48 hour, crystallization
Temperature be 80-180 DEG C, described be dried be 80-100 DEG C process 2-8 hour.
6. preparation method as claimed in claim 2, wherein, the extract that described extraction uses be ethanol, propanol,
One or more mixture in acetone.
7. preparation method as claimed in claim 2, wherein, described impregnation liquid is palladium, Palladous nitrate., chlorination
Palladium, double acetonitrile and acetone palladium, palladium acetylacetonate solution in one.
8. preparation method as claimed in claim 2, wherein, the temperature of described reduction is 80-200 DEG C, activity group
Dividing the percentage by weight with carrier is 0.1%-10%.
9. alkadienes selective hydrocatalyst as claimed in claim 1 is in alkadienes selective hydrogenation
Application.
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| CN201410655649.7A CN104399529B (en) | 2014-11-18 | 2014-11-18 | A kind of alkadienes selective hydrocatalyst and preparation method and application |
| PCT/CN2015/075640 WO2016078286A1 (en) | 2014-11-18 | 2015-04-01 | Selective hydrogenation catalyst for alkadiene, preparation method therefor, and uses thereof |
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| CN102896001B (en) * | 2012-10-16 | 2015-03-18 | 中国石油大学(北京) | Preparation method for cascade porous ZIFs and hydrogen desulfurization catalyst |
| CN102921469B (en) * | 2012-10-16 | 2014-10-15 | 中国石油大学(北京) | Preparation method for novel gasoline hydrodesulfurization catalyst |
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