CN109806885A - A kind of monatomic catalyst of Pdx/Cu and preparation method thereof adding hydrogen for C4 selection - Google Patents
A kind of monatomic catalyst of Pdx/Cu and preparation method thereof adding hydrogen for C4 selection 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, 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
The monatomic grade bimetallic catalyst of kind, 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
Selection plus hydrogen are carried out to unsaturated C4 molecule in the atmosphere of rich olefins, difficult point is: the active group of catalyst
Part need to have high dispersion degree, to improve catalytic efficiency and reduce catalyst cost；The metal needs that catalyst surface is loaded are non-
Often stablize, avoids causing to be lost with reactant generation complex reaction；Catalyst is catalyzed the side reaction of diolefin, alkynes polymerization and lives
Property wants low, to improve catalyst life.Based on the above industrial difficult point, the present invention is proposed, by reducing the size of active site Pd,
Improve the dispersion degree of Pd, consolidate the combination degree of Pd and Cu, and the quantity of polymerization site is greatly decreased, thus reduce catalyst at
This, 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 the monatomic catalyst of Pdx/Cu, 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 monatomic grade 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 single on the catalyst
The site atom Pd 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 monatomic catalyst of PdxCu 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 0.4%~20%；
Pd/Cu atomic ratio is between 0.005~0.025；Pd is present in bimetal granule in the form of monatomic or nano-cluster.
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 0.007,0.021,
0.017、0.023、0.011、0.005、0.006。
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 monatomic or nano-cluster, and bimetallic partial size is between 2
Between~18nm.
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 0.005~0.024 according to atomic ratio；
(b) after 1~3h ageing, it is dried into 10~20h at 80~120 DEG C；
(c) (b) products therefrom is calcined to 4~8h at 450~550 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 4~8h at 450~550 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 0.005~0.024；
(e) after 1~3h ageing, it is dried into 6~20h at 80~120 DEG C；
(f) (e) products therefrom is calcined to 4~6h at 450~550 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 4~8h at 400~600 DEG C；
(d) (c) products therefrom is restored to 1~2h at 300 DEG C；
(e) (d) products therefrom is subjected to metal displacement reaction in ultrasonic reactor, used Pd/Cu presoma
Amount calculates between 0.005~0.024 according to atomic ratio；
(f) it is dried in vacuo 24~48h at room temperature.
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 monatomic 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 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: 50~200 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 monatomic 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 with monatomic or
The form of nano-cluster exists, and active site is sparse, and unit volume thermal discharge is low, be easily removed heat, control temperature of reactor,
Avoid the generation of hot spot.
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) monatomic Pd and Cu binding force is strong, and turnover rate is low, and stability is high；
(4) surface aggregate site is few, and side reaction occurrence probability is low, 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
Fig. 1 PdCu/Al2O3XPS spectrum figure (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 0.18%, Cu content 15%, specific steps
It is 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 3h at room temperature, the dry 12h at 100 DEG C；
(d) catalyst obtained by (c) is calcined into 5h at 500 DEG C.
After obtained catalyst is restored at 450 DEG C, EXAFS characterization is carried out, data obtained obtain after being fitted
The ligancy (CN, coordination number) for obtaining Pd, after fitting, CN (Pd-Pd)=0, CN (Pd-Cu)=11.2, it was demonstrated that
It is surround around Pd by Cu, is present in catalyst with monatomic form.
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 1.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+。
Carry out the evaluation of 1,3-butadiene selective hydrogenation reaction to catalyst using following experiment condition: hydrogen alkene is than 1.8, temperature
120 DEG C, pressure normal pressure, air speed 12000h-1, conversion ratio 98%, total butylene 100%, 1- of selectivity butylene selectivity 62%.
Embodiment 2
PdCu/CeO is prepared using Galvanic displacement method2Catalyst, wherein Pd content 0.12%, Cu content 3.5% 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 Cu (acac)2Solution drops evenly on a catalyst support dropwise, so that carrier is just saturated absorption and is prepared
Solution；
(c) it is aged 3h, the dry 18h at 80 DEG C；
(d) 4h is calcined at 500 DEG C；
(e) by catalyst reductase 12 h at 300 DEG C obtained by (d)；
(f) catalyst obtained by (e) is subjected to metal displacement reaction in ultrasonic reactor, displacement metallic solution is Pd
(acac)2Solution；
(g) it is dried in vacuo 48h at room temperature.
After obtained catalyst is restored at 450 DEG C, EXAFS characterization is carried out, data obtained obtain after being fitted
Pd ligancy (CN), after fitting, CN (Pd-Pd)=0, CN (Pd-Cu)=9.3, it was demonstrated that surround around Pd by Cu, with list
Atomic form is present in catalyst.
Carry out the evaluation of butine selective hydrogenation reaction to catalyst using following experiment condition: hydrogen alkynes is than 4, and 180 DEG C of temperature, pressure
Power normal pressure, air speed 12000h-1, conversion ratio 99%, total butylene 99.9%, 1- of selectivity butylene selectivity 56%.
Embodiment 3
PdCu/SiO is prepared using step impregnation method2Agent, wherein Pd content 0.12%, Cu content 4.2%, specific steps
It is 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 3h, the dry 18h at 80 DEG C；
(d) 4h is calcined at 450 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 18h at 80 DEG C；
(g) 5h is calcined at 550 DEG C.
After obtained catalyst is restored at 450 DEG C, EXAFS characterization is carried out, data obtained obtain after being fitted
Pd ligancy (CN), after fitting, CN (Pd-Pd)=0, CN (Pd-Cu)=10.6, it was demonstrated that surround around Pd by Cu, with
Monatomic form is present in catalyst.
Carry out the evaluation of vinylacetylene selective hydrogenation reaction to catalyst using following experiment condition: hydrogen alkynes is than 4, temperature 80
DEG C, pressure normal pressure, air speed 12000h-1, conversion ratio 97%, total butylene 99.9%, 1- of selectivity butylene selectivity 60%.
Embodiment 4
PdCu/SiO is prepared using coprecipitation2Catalyst, wherein Pd content 0.06%, Cu content 1.6%, use is following
Experiment condition carries out the evaluation of 1,3-butadiene selective hydrogenation reaction to catalyst: hydrogen alkene is than 2.2, temperature 50 C, pressure normal pressure, empty
Fast 6000h-1, conversion ratio 80%, total butylene 100%, 1- of selectivity butylene selectivity 69%.
Embodiment 5
PdCu/Al is prepared using co-impregnation2O3Catalyst, wherein Pd content 0.18%, Cu content 10%, use is following
Experiment condition carries out the evaluation of 1,3-butadiene selective hydrogenation reaction to catalyst: hydrogen alkene is than 4, and 100 DEG C of temperature, pressure normal pressure is empty
Fast 12000h-1, conversion ratio 99%, total butylene 100%, 1- of selectivity butylene selectivity 46%.
Embodiment 6
PdCu/Al is prepared using co-impregnation2O3Catalyst, wherein Pd content 0.18%, Cu content 20%, use is following
Experiment condition carries out the evaluation of 1,3-butadiene selective hydrogenation reaction to catalyst: hydrogen alkene is than 4, and 160 DEG C of temperature, pressure normal pressure is empty
Fast 12000h-1, conversion ratio 100%, total butylene 99.9%, 1- of selectivity butylene selectivity 36%.
Embodiment 7
PdCu/Al is prepared using co-impregnation2O3Catalyst, wherein Pd content 0.15%, Cu content 12%, use is following
Experiment condition carries out the evaluation of 1,3-butadiene selective hydrogenation reaction to catalyst: hydrogen alkene is than 4, and 190 DEG C of temperature, pressure normal pressure is empty
Fast 12000h-1, conversion ratio 99.99%, total butylene 100%, 1- of selectivity butylene selectivity 26%.
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 monatomic grade 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 total weight 100% is counted, and the content that the content of Pd is 0.02%~0.2%, Cu is 0.4%~20%；Pd/Cu atomic ratio between
Between 0.005~0.025；Pd is present in bimetal granule with monatomic form.
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 bimetallic partial size is between 3~18nm.
4. catalyst according to claim 1, which is characterized in that Cu is with Cu0Or Cu+Form exist.
5. the preparation method of catalyst described in Claims 1 to 4 any one, it is characterised in that: use step impregnation method, total immersion
Stain method or Galvanic displacement method prepare catalyst.
6. preparation method according to claim 5, 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 0.005~0.024；
(b) after 1~3h ageing, it is dried into 10~20h at 80~120 DEG C；
(c) (b) products therefrom is calcined to 4~8h at 450~550 DEG C.
7. preparation method according to claim 5, which is characterized in that 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 4~8h at 450~550 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 0.005~0.024；
(e) after 1~3h ageing, it is dried into 6~20h at 80~120 DEG C；
(f) (e) products therefrom is calcined to 4~6h at 450~550 DEG C.
8. preparation method according to claim 5, which is characterized in that 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 4~8h at 400~600 DEG C；
(d) (c) products therefrom is restored to 1~2h at 300 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 0.005~0.024 according to atomic ratio；
(f) it is dried in vacuo 24~48h at room temperature.
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 C4 molecule is one of 1,3-butadiene, butine, vinylacetylene or more
Kind combination.
10. according to selection method of hydrotreating described in claim 9, which is characterized in that the reaction condition of the selection method of hydrotreating
Are as follows: 50~200 DEG C of reaction temperature, pressure is 0~3MPa, 1000~18000h of gas phase air speed-1, mole of hydrogen and unsaturation C4
Than being 1~4.
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| CN111841533A (en) * | 2020-08-18 | 2020-10-30 | 江南大学 | Supported metal diatom catalyst and preparation method and application thereof |
| CN113209985A (en) * | 2021-04-08 | 2021-08-06 | 西南化工研究设计院有限公司 | Catalyst for removing trace olefin in dimethyl ether through hydrogenation, preparation method and application |
| CN113856750A (en) * | 2021-11-02 | 2021-12-31 | 江南大学 | Supported bimetallic monatomic catalyst and preparation method and application thereof |
| WO2022089250A1 (en) | 2020-10-26 | 2022-05-05 | 中国石油化工股份有限公司 | Method for selective hydrogenation of butadiene extraction tail gas and selective hydrogenation apparatus |
| CN114618518A (en) * | 2020-12-10 | 2022-06-14 | 中国科学院大连化学物理研究所 | Supported bimetallic catalyst and preparation and application thereof |
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| CN111841533A (en) * | 2020-08-18 | 2020-10-30 | 江南大学 | Supported metal diatom catalyst and preparation method and application thereof |
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| WO2022089250A1 (en) | 2020-10-26 | 2022-05-05 | 中国石油化工股份有限公司 | Method for selective hydrogenation of butadiene extraction tail gas and selective hydrogenation apparatus |
| CN114618518A (en) * | 2020-12-10 | 2022-06-14 | 中国科学院大连化学物理研究所 | Supported bimetallic catalyst and preparation and application thereof |
| CN114618518B (en) * | 2020-12-10 | 2023-01-17 | 中国科学院大连化学物理研究所 | Supported bimetallic catalyst and preparation and application thereof |
| CN113209985A (en) * | 2021-04-08 | 2021-08-06 | 西南化工研究设计院有限公司 | Catalyst for removing trace olefin in dimethyl ether through hydrogenation, preparation method and application |
| CN113209985B (en) * | 2021-04-08 | 2022-04-26 | 西南化工研究设计院有限公司 | Catalyst for removing trace olefin in dimethyl ether through hydrogenation, preparation method and application |
| CN113856750A (en) * | 2021-11-02 | 2021-12-31 | 江南大学 | Supported bimetallic monatomic catalyst and preparation method and application thereof |
| WO2023077872A1 (en) * | 2021-11-02 | 2023-05-11 | 江南大学 | Supported bimetallic single-atom catalyst, and preparation method therefor and application thereof |
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Application publication date: 20190528 |