CN109701552A - A kind of palladium-copper system support type sub-nanometer catalyst and preparation method thereof - Google Patents
A kind of palladium-copper system support type sub-nanometer catalyst and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of unsaturation C4 selective hydrogenation catalysts and its preparation method and application, specially a kind of palladium-copper system support type sub-nanometer catalyst and preparation method thereof, and the catalyst is made of Pd, Cu and carrier.For catalyst of the invention for selecting hydrogenation and removing C4 alkynes and alkadienes, it is butylene that unsaturated C4 molecule, which is passed through hydro-conversion, achievees the purpose that remove unsaturation C4.
Description
Technical field
The present invention relates to a kind of catalyst for C4 selection hydrogenation process and its preparations and application.It specifically, is one
Kind Subnano-class bimetallic catalyst, and the application in unsaturated C4 selective hydrogenation.
Background technique
Low-carbon alkene (the C generated in petroleum catalytic cracking or Pintsch process2-C4) it is important Organic Ingredients, it answers extensively
For polymerization plastics, the synthesis of three big organic materials and the synthesis of fine chemicals.1- butylene, 2- butylene in C4
It is common polymerized monomer with isobutene, however, containing a certain amount of diolefin and alkynes in cracking C 4 fraction, can seriously affects
The polymerization reaction of subsequent monoolefine such as poisons catalyst, influences reaction rate, reduces product quality, endangers production safety etc., because
This needs to carry out raw material of industry gas stringent acetylene removal, de- diolefin processing.In the method for numerous removing unsaturation C4 molecules,
The route methods of selective hydrogenation are simple, and can convert impurity to monoolefine required for reaction, are most commonly in industry
In production.
Pd base catalyst is widely used in industry selection hydrogenation process at present.But your gold is its active component be mainly
Belong to, reserves are few, and at high cost, selectivity is low.In addition, complexing occurs for the eneyne hydrocarbon and diolefin in metal Pd and C4 raw material,
Cause palladium to dissolve and be lost from catalyst carrier, shortens catalyst life.In order to improve the performance of catalyst, usually it is being catalyzed
Second of metal is added in agent to modify Pd, binary bimetallic catalyst is formed, to improve the performance of catalyst.According to document
Report, Pd-Ag (Stud Surf Sci&Catal 1993,75,2305-2308), Pd-Au (CatalLett1997,45 (3-
4), 177-186, Surf Sci 2005,592 (1), 169-181 and J Catal 2013,297 (12), 79-92) and Pd-Sn
(Fuel Process Tech 2014,120 (2), 113-122, J PhysChem C 2018,122 (11), 6005-6013),
The selectivity of alkene can be improved in bimetallic catalyst, however, the addition of most of binary metal is mostly to reduce before activity is
It mentions to improve selectivity, this just correspondingly reduces the catalytic activity of unit mass metal Pd, improves catalyst cost indirectly and (comments
Price card is quasi-: overall cost factor-alpha=unit mass catalyst cost/catalytic activity, Top Catal, and 2015,58,240).Early period
The experimental results showed that modifying Pd base catalyst using Cu, the activity of original Pd catalyst not only can be kept or improve, but also can be big
Width improves its selectivity；The advantage of lower cost of Cu metal simultaneously, therefore PdCu catalyst is the industrial catalyst of great potential.
105727990 A of CN discloses a kind of preparation method of palladium-copper system load hydrogenation catalyst, and this method uses
The organic solution of hydroxyl dipyridyl derivatives impregnates Al2O3It is carrier, it is molten with the mixed-cation of Pd, Cu again after drying
Liquid dipping, the preparation method overcome maceration extract surface tension and solvation effect to the adverse effect of palladium-copper dispersion, preparation
Catalyst, be more conducive to form palladium-copper alloy, catalyst has excellent activity, selectivity and anticoking capability.
CN105727991A/B discloses a kind of palladium-copper system load hydrogenation catalyst, which is alloy-type
Bimetallic catalyst is prepared using method disclosed in 105727990 A of CN.Pd content is 0.01 in the catalyst
~0.5%, Cu content are 0.02~1%, Cu/Pd molar ratio 1~10.
Above the reported PdCu series catalysts and preparation method thereof, are to form Pd-Cu alloy.Pd-Cu alloy pair
The selective promotor action of C4 selection plus hydrogen is limited, and Pd content is higher in alloy, and alloying pellet is larger, and dispersion degree is smaller, right
The influence of catalyst cost (the overall cost factor) is very small.In addition, Pd-Cu series catalysts disclosed in the above patent are mainly answered
For the selective hydrogenation reaction of C2-C3 fraction, molecule involved by the selective hydrogenation reaction of C4 and reaction are more, more complicated,
C2-C3 selective hydrogenation catalyst cannot be directly applied in C4 system.
Summary of the invention
The study found that carrying out selection plus hydrogen to unsaturated C4 molecule in the atmosphere of rich olefins, difficult point is: catalyst
Active constituent need to have high dispersion degree, to improve catalytic efficiency and reduce catalyst cost；What catalyst surface was loaded
Metal needs are highly stable, avoid causing to be lost with reactant generation complex reaction；Catalyst is anti-to the pair of diolefin, alkynes polymerization
Catalytic activity is answered to want low, to improve catalyst life.Based on the above industrial difficult point, the ruler that the present invention passes through reduction active site Pd
It is very little, the dispersion degree of Pd is improved, the combination degree of Pd and Cu is consolidated, and the quantity of polymerization site is greatly decreased, to reduce catalysis
Agent cost improves catalyst life, improves high active of hydrogenation catalysis, improves butylene selectivity.
Specifically, the present invention is directed to prior art situation, provides a kind of method for preparing Pdx/Cu sub-nanometer catalyst, leads to
The size for reducing active site Pd is crossed, the dispersion degree of Pd is improved, improves the utilization rate of noble metal in catalyst, is urged to reduce
The cost of agent；It is combined by Subnano-class Pd with nanoscale Cu, has consolidated the combination degree of Pd and Cu, reduce active component
The probability of loss.A kind of high efficiency, low cost catalyst for adding hydrogen applied to C4 selection is provided simultaneously, due to sub- on the catalyst
Nano Pd particle site shows geometric effect and electronic effect, improves high active of hydrogenation catalysis and fourth that unit mass Pd is shown
Alkene selectivity, and since the reduction of polymerization site quantity, loss of active component probability are small, improve the stability of catalyst.In addition,
Method for preparing catalyst disclosed in this invention is simple and easy, and production line is easily built, and while keeping industrial innovation, does not increase
Add production cost.
Particular content of the present invention is as follows:
It is a kind of for C4 selection plus the PdxCu sub-nanometer catalyst of hydrogen, active component Pd, Cu and catalysis are contained in catalyst
Agent carrier, in terms of total catalyst weight 100%, the content that the content of Pd is 0.02%~0.2%, Cu is 0.19%~3.9%；
Pd/Cu atomic ratio is between 0.051~0.0999；Pd is present in bimetal granule in the form of sub-nanometer.
Heretofore described atomic ratio, i.e. molar ratio.
In a specific embodiment of the invention, Pd/Cu atomic ratio can select but be not limited to 0.057,0.072,
0.091、0.084、0.060、0.052、0.093。
The carrier of the selective hydrocatalyst is Al2O3、SiO2、CeO2、TiO2, activated carbon, carbon nanotube, graphite
One of alkene, nitrogen carbide or multiple combinations.
On the catalyst, Pd is present in bimetal granule in the form of sub-nanometer, bimetallic partial size between 2~18nm it
Between, sub-nanometer Pd particle is between 0.1~2nm.
On the catalyst, Cu is with Cu0Or Cu+Form be present in bimetal granule and on carrier.
The preparation method of the catalyst, using step impregnation method, co-impregnation, Galvanic displacement method or co-precipitation
Method.
The preparation process of the co-impregnation are as follows:
(a) on a catalyst support by the presoma of the presoma of Cu and Pd dipping, the amount of used Pd/Cu presoma
It is calculated between 0.051~0.0999 according to atomic ratio；
(b) after 1~3h ageing, it is dried into 6~20h at 80~120 DEG C；
(c) (b) products therefrom is calcined to 3~6h at 400~600 DEG C.
The preparation process of the step impregnation method are as follows:
(a) on a catalyst support by the presoma dipping of Cu；
(b) after 1~3h ageing, it is dried into 6~20h at 80~120 DEG C；
(c) (b) products therefrom is calcined to 3~6h at 400~600 DEG C；
(d) presoma of Pd is immersed on (c) products therefrom, the amount of used Pd/Cu presoma is according to atomic ratio
It is calculated between 0.051~0.0999；
(e) after 1~3h ageing, it is dried into 6~20h at 80~120 DEG C；
(f) (e) products therefrom is calcined to 3~6h at 400~600 DEG C.
The preparation process of the Galvanic displacement method are as follows:
(a) on a catalyst support by the presoma dipping of Cu；
(b) after 1~3h ageing, it is dried into 6~20h at 80~120 DEG C；
(c) (b) products therefrom is calcined to 3~6h at 400~600 DEG C；
(d) (c) products therefrom is restored to 1~2h at 250 DEG C；
(e) (d) products therefrom is subjected to metal displacement reaction in ultrasonic reactor, used Pd/Cu presoma
Amount calculates between 0.051~0.0999 according to atomic ratio；
(f) at room temperature vacuum drying 12~for 24 hours.
It is found in research, when preparing catalyst, the ratio of Pd/Cu influences whether the existence form of metallic particles, this hair
Sub-nanometer and monatomic two kinds of forms are primarily present in bright.Experiment shows to reduce to a certain extent when Pd/Cu ratio, can get more
The Pd particle of dispersion, i.e. monatomic form.Pd/Cu ratio can obtain sub-nanometer Pd in which range, and Experimental Characterization is needed to demonstrate,prove
It is bright, ratio as described above is used in the present invention.
The present invention also provides a kind of selection method of hydrotreating of unsaturation C4 molecule, it is used described in claim 1~6
Catalyst carries out hydrogenation reaction.
The C4 molecule is one of unsaturation C4 molecule, including 1,3-butadiene, butine, vinylacetylene or more
Kind combination.
The reaction condition of the C4 selection plus hydrogen are as follows: 35~100 DEG C of reaction temperature, pressure is 0~3MPa, gas phase air speed
1000~18000h-1, the molar ratio of hydrogen and unsaturation C4 are 1~4.
The method of the present invention prepares Pd-Cu catalyst, and it is higher that sub-nanometer structure is more suitably applied to unsaturated C4 concentration
Working condition.Because C4 hydrogenation reaction is strong exothermal reaction, on traditional Pd catalyst, due to active site comparatively dense, unit bodies
The heat accumulated out is high, is difficult to quickly remove in industrial reactor；According to catalyst of the present invention, Pd is with sub-nanometer
Form exists, and active site is sparse, and unit volume thermal discharge is low, is easily removed heat, controls temperature of reactor, avoids hot spot
Generation.
Compared with prior art, the present invention having the advantage that
(1) precious metals pd utilization rate is high, and the catalysis of units activity is at low cost；
(2) total butylene selectively greatly improves；
(3) sub-nanometer Pd and Cu binding force is strong, and turnover rate is low, and stability is high；
(4) surface aggregate site is few, reduces the generation of side reaction, and catalyst life is long；
(5) active site is sparse, is easily removed the heat released in reaction (C4 hydrogenation reaction is strong exothermal reaction)；
(6) pass through the collective effect of geometric effect and electronic effect, the selectivity of modulation difference butylene；
(7) catalyst preparation process is simple and easy, easily implements in the industrial production.
Detailed description of the invention
The TPR spectrogram of Fig. 1 PdCu
The CO of Fig. 2 PdxCu adsorbs infrared spectrum (data acquisition is in Institute of Analysis, Beijing Institute of Technology)
The XPS spectrum figure of Fig. 3 PdxCu (data acquisition is in Institute of Analysis, Beijing Institute of Technology)
Specific embodiment
Embodiment 1
PdCu/Al is prepared using co-impregnation2O3Catalyst, wherein Pd content 0.025%, Cu content 0.26%, the oxygen
Change alumina supporter is γ-Al2O3, specific surface area 160m2/ g, the specific steps are as follows:
(a) dosage of corresponding presoma copper nitrate and palladium nitrate is calculated, and corresponding according to aluminium oxide incipient impregnation
Liquor capacity configures solution；
(b) solution is dropped evenly on the alumina support dropwise, carrier is made just to be saturated the prepared solution of absorption；
(c) impregnated carrier is aged 1h at room temperature, is dried whole night at 80 DEG C；
(d) catalyst obtained by (c) is calcined into 3h at 450 DEG C.
Catalyst obtained is subjected to TPR table sign, obtains its oxide on surface state, as shown in Figure 1, wherein Pd,
TPR table sign has also been made as object of reference in Cu single-metal reforming catalyst, and bimetallic catalyst is indicated with Pdx/Cu.In bimetallic catalyst
On, occur first reduction peak at 80 DEG C or so, for the Cu particle for being dispersed in carrier surface, is reduced to Cu in carrier surface+；Then, occur second reduction peak at 300 DEG C or so, based on bimetal structure reduction peak, the reduction peak and Cu's
Reduction peak is close, illustrates that main structure shows the property of Cu particle, but the reduction peak shape different from Cu, modifies for Pd
Effect.After carrying out reduction, the Cu on bimetallic catalyst surface is with Cu+Or Cu0In the presence of.
To Pd/Al2O3、Cu/Al2O3The IR Characterization of CO absorption, such as Fig. 2 are carried out with three kinds of catalyst of bimetallic catalyst
It is shown, on bimetallic catalyst, 1915cm-1The body phase adsorption peak for locating Pd disappears, it was demonstrated that Pd is present in double in the form of sub-nanometer
In metallic particles, body phase Pd is not present on this catalyst.
Catalytic evaluation experiment is carried out to prepared bimetallic catalyst, is applied to 1,3-butadiene selective hydrogenation reaction
In, hydrogen alkene is than 2, temperature 60 C, pressure normal pressure, air speed 4000h-1, conversion ratio 90%, total butylene selectivity 100%, 1- butylene choosing
Selecting property 65%.
Embodiment 2
PdCu/SiO is prepared using step impregnation method2Catalyst, silica specific surface area are 230m2/ g, Pd content
0.06%, Cu content 0.5%, the specific steps are as follows:
(a) usage amount of presoma copper chloride and palladium chloride is calculated according to load data, and is soaked in equal volume according to silica
The corresponding volume of stain prepares solution；
(b) copper chloride solution is dropped evenly on a catalyst support dropwise, so that carrier is just saturated absorption prepared
Solution；
(c) it is aged 1h, the dry 5h at 100 DEG C；
(d) 3h is calcined at 500 DEG C；
(e) palladium chloride solution is dropped evenly on a catalyst support dropwise, so that carrier is just saturated absorption prepared
Solution；
(f) it is aged 3h, the dry 8h at 80 DEG C；
(g) 3h is calcined at 400 DEG C.
By catalyst obtained after 450 DEG C of reduction, XPS characterization is carried out, its oxide on surface state is obtained, such as schemed
Shown in 3.XPS spectrum figure is fitted, by matched curve it is found that PdCu bimetallic catalyst surface mainly exists with Cu, Cu is not
Only Cu0Valence state, there is also Cu+.The infrared absorption representation of CO- is carried out to the catalyst, can get similar Fig. 2 spectrogram, the body phase of Pd
Adsorption peak disappears, it was demonstrated that the presence of sub-nanometer Pd.
Carry out the evaluation of 1,3-butadiene selective hydrogenation reaction to catalyst using following experiment condition: hydrogen alkene is than 2.2, temperature
60 DEG C, pressure normal pressure, air speed 8000h-1, conversion ratio 98%, total butylene 100%, 1- of selectivity butylene selectivity 63%.
Embodiment 3
PdCu/SiO is prepared using Galvanic displacement method2Catalyst, wherein Pd content 0.12%, Cu content 0.8% have
Steps are as follows for body:
(a) usage amount of presoma copper nitrate and palladium nitrate is calculated according to load data；
(b) by copper nitrate incipient impregnation on silica support, specific steps are the same as (b)~(d) in embodiment 2；
(c) catalyst obtained by (b) is restored into 1h at 250 DEG C；
(d) catalyst obtained by (c) is subjected to metal displacement reaction in ultrasonic reactor, displacement metallic solution is palladium nitrate
Solution；
(e) it is dried in vacuo at room temperature for 24 hours.
The infrared absorption representation of CO- is carried out to the catalyst, can get the spectrogram of similar Fig. 2, the body phase adsorption peak of Pd disappears,
Demonstrate the presence of sub-nanometer Pd.EXAFS characterization is carried out to the catalyst, and carries out data fitting, acquisition CN (Pd-Pd)=
For the average coordination number of Pd less than 1, most of is the coordination of Cu around 0.4, CN (Pd-Cu)=6.7, i.e. Pd, directly demonstrates Pd
It is present on catalyst in the form of sub-nanometer.
Carry out the evaluation of butine selective hydrogenation reaction to catalyst using following experiment condition: hydrogen alkynes is than 4, temperature 50 C, pressure
Power normal pressure, air speed 12000h-1, conversion ratio 99%, total butylene 99.9%, 1- of selectivity butylene selectivity 56%.
Embodiment 4
PdCu/C catalyst is prepared using co-impregnation, wherein Pd content 0.18%, Cu content 1.3%, using following reality
Test condition and carry out the evaluation of 1,3-butadiene selective hydrogenation reaction to catalyst: hydrogen alkene is than 4, and 40 DEG C of temperature, pressure normal pressure, air speed
12000h-1, conversion ratio 99.9%, total butylene 100%, 1- of selectivity butylene selectivity 46%.
Embodiment 5
PdCu/CeO is prepared using co-impregnation2Catalyst, wherein Pd content 0.18%, Cu content 1.8%, use is following
Experiment condition carries out the evaluation of vinylacetylene selective hydrogenation reaction to catalyst: hydrogen alkene is than 1.8, and 35 DEG C of temperature, pressure normal pressure is empty
Fast 12000h-1, conversion ratio 98%, total butylene 100%, 1- of selectivity butylene selectivity 75%.
Embodiment 6
PdCu/Al is prepared using co-impregnation2O3Catalyst, wherein Pd content 0.18%, Cu content 2.1%, use is following
Experiment condition carries out the evaluation of 1,3-butadiene selective hydrogenation reaction to catalyst: hydrogen alkene is than 4, and 80 DEG C of temperature, pressure normal pressure, air speed
12000h-1, conversion ratio 99.99%, total butylene 100%, 1- of selectivity butylene selectivity 32%.
Embodiment 7
PdCu/SiO is prepared using co-impregnation2Catalyst, wherein Pd content 0.2%, Cu content 1.3%, use is following
Experiment condition carries out the evaluation of 1,3-butadiene selective hydrogenation reaction to catalyst: hydrogen alkene is than 4, temperature 60 C, pressure normal pressure, air speed
12000h-1, conversion ratio 99.99%, total butylene 100%, 1- of selectivity butylene selectivity 65%.
Following table summarizes each embodiment and traditional catalyst and adds performance in hydrogen in C4, wherein catalytic efficiency refers to
The C4 flow that unit mass Pd can be catalyzed, that is, every gram of Pd can convert completely the C4 of x mL/min.As can be seen from the table, this hair
The bright Subnano-class catalyst, the catalytic efficiency of Pd have the raising of an order of magnitude compared with traditional catalyst, significantly reduce
The dosage for handling the Pd of specific discharge C4, can save catalyst cost.
The catalytic efficiency of 1 Pd of the embodiment of the present invention of table and the comparison of traditional catalyst
*Ref:Journal of Catalysis,2014,316(7):1-10.
Under identical air speed, conversion ratio is higher, and the utilization efficiency of unit mass noble metal (Pd) is higher；Total butylene is selectively got over
It is high better.1- butylene is the monomer for producing polybutene, and the selectivity of 1- butylene the high more is conducive to polybutene route；2- butylene is
The target product of alkylate oil route, the selectivity of 2- butylene the high more is conducive to the production of alkylate oil.It is proposed by the invention
Sub-nanometer catalyst, can be in the selectivity of modulation 1- butylene, 2- butylene under different formulations.
Claims (10)
1. a kind of palladium-copper system support catalysts, Pd, Cu and catalyst carrier are contained in catalyst, it is characterised in that: with catalysis
Agent gross mass is 100% meter, and the content that the content of Pd is 0.02%~0.2%, Cu is 0.19%~3.9%；Pd/Cu atomic ratio
Between 0.051~0.0999；Pd is present in bimetal granule in the form of sub-nanometer.
2. catalyst according to claim 1, which is characterized in that catalyst carrier Al2O3、SiO2、CeO2、TiO2, activity
One of carbon, carbon nanotube, graphene, nitrogen carbide or multiple combinations.
3. catalyst according to claim 1, which is characterized in that bimetal granule partial size is between 2~18nm, wherein
Pd is between 0.1~2nm.
4. catalyst according to claim 1, which is characterized in that Cu is with Cu0Or Cu+Form exist.
5. catalyst according to claim 1, which is characterized in that levied using TPR table, gone back respectively in about 80 DEG C, 300 DEG C
Parent peak.
6. catalyst according to claim 1, which is characterized in that the IR Characterization adsorbed using CO, in about 1915cm-1Locate nothing
The body phase adsorption peak of Pd.
7. the preparation method of catalyst described in claim 1~6 any one, it is characterised in that: soaked using co-impregnation, substep
Stain method or Galvanic displacement method prepare catalyst.
8. preparation method according to claim 7, which is characterized in that the preparation process of the co-impregnation are as follows:
(a) on a catalyst support by the presoma of the presoma of Cu and Pd dipping, the amount of used Pd/Cu presoma according to
Atomic ratio calculates between 0.051~0.0999；
(b) after 1~3h ageing, it is dried into 6~20h at 80~120 DEG C；
(c) (b) products therefrom is calcined to 3~6h at 400~600 DEG C；
The preparation process of the step impregnation method are as follows:
(a) on a catalyst support by the presoma dipping of Cu；
(b) after 1~3h ageing, it is dried into 6~20h at 80~120 DEG C；
(c) (b) products therefrom is calcined to 3~6h at 400~600 DEG C；
(d) presoma of Pd is immersed on (c) products therefrom, the amount of used Pd/Cu presoma according to atomic ratio between
It is calculated between 0.051~0.0999；
(e) after 1~3h ageing, it is dried into 6~20h at 80~120 DEG C；
(f) (e) products therefrom is calcined to 3~6h at 400~600 DEG C；
The preparation process of the Galvanic displacement method are as follows:
(a) on a catalyst support by the presoma dipping of Cu；
(b) after 1~3h ageing, it is dried into 6~20h at 80~120 DEG C；
(c) (b) products therefrom is calcined to 3~6h at 400~600 DEG C；
(d) (c) products therefrom is restored to 1~2h at 250 DEG C；
(e) (d) products therefrom is subjected to metal displacement reaction in ultrasonic reactor, the amount of used Pd/Cu presoma is pressed
It is calculated between 0.051~0.0999 according to atomic ratio；
(f) at room temperature vacuum drying 12~for 24 hours.
9. a kind of selection method of hydrotreating of unsaturation C4 molecule, which is characterized in that it uses catalysis described in claim 1~6
Agent carries out hydrogenation reaction；Further, the unsaturated C4 molecule, including in 1,3-butadiene, butine, vinylacetylene
One or more combinations.
10. method of hydrotreating according to claim 9, which is characterized in that the reaction condition of the selection method of hydrotreating are as follows: anti-
35~100 DEG C of temperature are answered, pressure is 0~3MPa, 1000~18000h of gas phase air speed-1, mole of hydrogen and unsaturation C4 molecule
Than being 1~2.
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