CN105879863A - Novel carrier loading palladium catalyst applied to acetylene selective hydrogenation - Google Patents
Novel carrier loading palladium catalyst applied to acetylene selective hydrogenation Download PDFInfo
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- CN105879863A CN105879863A CN201410771073.0A CN201410771073A CN105879863A CN 105879863 A CN105879863 A CN 105879863A CN 201410771073 A CN201410771073 A CN 201410771073A CN 105879863 A CN105879863 A CN 105879863A
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Abstract
The invention takes the uniquely treated novel carrier loading palladium metal particle as a catalyst for acetylene selective hydrogenation and causes the metal precursor uniformly react with the carrier surface, so that the problem of deposited carbon migration is solved, the catalyst with nature stability is prepared, the selectivity of the industrial hydrogenation of acetylene is greatly increased and the content of by-product is reduced. The novel hydrogenation catalyst provided by the invention has the advantages that the preparation is easily performed, the controllability is strong, the size control of the palladium metal nano-particle is uniform and the strong acting force between metal particle and carrier is realized, so that the sintering and peeling conditions of the catalyst in the application are greatly reduced, the stability is greatly increased and the selectivity which is key to industry is also greatly increased. In the acetylene hydrogenation industrial simulation reaction, the excellent catalytic stability and high selectivity are exerted.
Description
Technical field
The present invention relates to a kind of novel carriers carried palladium catalyst and be applied to the catalysis process of acetylene selective hydrogenation.Belong to catalysis technical field.
Background technology
Palladium selective catalysis acetylene hydrogenation is the important intermediate step of commercial production polyethylene (ca.50 Megatons/year).Owing to the trace acetylene in ethylene feed has inactivating effect to polyethylene catalysts, so commercial Application needs acetylene content to be less than 1%ppm concentration range.Hydrogenation is removed to the approach of acetylene, i.e. need catalyst can optionally be hydrogenated with acetylene in the gas phase feed that a large amount of ethylene coexist, simultaneously need to acetylene hydrogenation selectivity of product ground controls as ethylene (trace ethane).
Owing to selectivity of catalyst is most important to commercial Application, the factors affecting catalyst choice has been done and has extensively studied in large quantities by scientist, feeds back in the design of catalyst with breaking through to research being understood.Palladium metal does hydrogenation catalyst, mainly utilizes its high activity in a hydrogen atmosphere.But high activity also brings the difficulty in selectivity control.Affecting the selective factor of palladium catalyst more complicated, its reason is that palladium metal persistently occurs dynamic variation under reaction atmosphere, causes catalytic active site constantly to change (Teschner, D.；Borsodi, J.；Wootsch, A.；Revay, Z.；Havecker, M.；Knop-Gericke, A.；Jackson, S.D.；R.Science 2008,320,86.).If concrete attribution, affect carbide (Stachurski, J. that selective factor can be divided into surface and block carburizing to cause；Frackiewicz, A.J.Less Common Met.1985,108,249.), hydride (Neyman, the K.M. formed with hydrogen atom effect；Schauermann, S.Angew.Chem., Int.Ed.2010,49,4743.) and deposition carbon is to palladium and the coating function (Wilde, the M. that support thing surface；Fukutani, K.；Ludwig, W.；Brandt, B.；Fischer, J-H.；Schauermann, S.；Freund, H-J.Angew.Chem., Int.Ed.2008,47,9289.) etc..
As the direct by-product of acetylene hydrogenation reaction, the formation of deposition carbon is determined by reaction condition with composition.The carbon of low carbon to hydrogen ratio starts to be deposited upon palladium surface along with reaction with unbodied form, along with reaction is carried out, is gathered in palladium and the surface supporting thing with the form of high C/Hratio.As a example by acetylene hydrogenation, after reaction continues longer period of time, it is frequently observed deposition carbon and occurs with oily polymer form.Deposition carbon directly participates in reaction, affects the absorption of reactant molecule and palladium surface, and avatar is for participating in composition and affecting active sites.The impact of catalyst choice is then presented as while reaction is carried out, affects absorption (Al-Ammar, the A.S. of reactant and palladium surface；Webb, G.J.J.Chem.Soc., Faraday Trans.I.1978,74,657.).Be first deposited upon the carbon on palladium surface to supporting thing surface migration, the surface coated carbon of such palladium and migrate to support thing surface carbon together with, form a complicated catalyst system and catalyzing coexisted with palladium active surface.
Migration based on deposition carbon is a universal phenomenon, so the surface supporting thing of impact deposition carbon diffusion and structure just have potential significance to catalytic selectivity.CNT, since within 1991, being found, has caused scientific circles with the one-dimensional hollow structure of its uniqueness and the electricity mechanical property of excellence and has paid close attention to (Iijima, S.Nature.1991,354,56) widely.Do supported carrier noble metal granule with the novel carriers of functionalisation of surfaces to be catalyzed, be possible not only to realize the nano-dispersed of metallic particles, the high forces of metallic particles and novel carriers surface can be realized simultaneously.In order to study the impact (by impact deposition carbon) on reaction selectivity of metal and carrier high forces, improving selectivity under the conditions of specific experiment, we provide a kind of new catalyst to carry out acetylene hydrogenation simultaneously.Experiment condition is elected as and is similar to industry hydroconversion condition, and catalyst is palladium nano-particles load and CNT.Owing to catalyst synthetic operation is simple, repeatability is high, controllability is strong, hydroconversion condition represents meaning to existing commercial Application, so scientific research kinetics and commercial polyethylene production application are had extensively and practical significance by this catalyst.
Summary of the invention
The present invention first has to solve the technical problem that to be the stable catalyst of preparation property.Technical scheme provided by the present invention is:
Specifically include following steps:
1) taking 10 grams of novel carriers and put in beaker, add appropriate concentrated nitric acid, at 90～150 DEG C, oil bath heated and stirred refluxes 1-3 hour.
2) after cooling, add the deionized water of equivalent, after dilution fully, filter.The product of filtration is dispersed in 1000 ml deionized water again, the sonic oscillation 10-50 second, filters.This cleaning step repeats 3-6 time.Filtrate is neutralized to neutrality by alkaline solution and drains.Collect filtration product, be dried 12 hours at 60-150 DEG C.
3) according to the tenor selected, the Pd (NO3) 2 of fixed mixing ratio is dissolved in ethanol, adds the novel carriers of the functionalization of certain proportioning, sonic oscillation 30 minutes to 1 hour, stir to solution evaporation under room temperature.
4) the forerunner's product collected is calcined 2 hours at 100-250 DEG C.Then at 400-700 DEG C, (50-100mL/min) reductase 12 hour is blended with H2 Yu He of fixed mixing ratio, is cooled to room temperature and takes out.
The most important catalytic condition that technical problem is that catalytic bed selects:
5) novel carriers loaded palladium catalyst and boron nitride are mixed mutually and are uniformly placed in acetylene hydrogenation reactor, high activity due to palladium, by empirical value and the reaction conversion ratio that makes repeated attempts (optimum 90%～95%), finally determine response magnitude (Novel ethyne hydrogenation catalyst 0.05-0.2 milligram, boron nitride 100 milligrams).
6) acetylene hydrogenation reactor simulated operation condition: inlet temperature: 0-70 DEG C, pressure 1-7MPa, catalyst 0.1-5% mass fraction new catalyst, gas phase feed 10-60mL/min, hydrogen alkynes is than between for 0.5-2.Constant temperature 200 DEG C continues gas chromatogram and divides 16.5 hours.
It is an advantage of the current invention that: novel carriers loaded palladium catalyst preparation easily operation, controllability is strong, palladium nanoparticle size Control is uniform, metallic particles and carrier realize high forces, cause catalyst to sinter in the application and peeling conditions is greatly reduced, stability is greatly improved, and selectivity vital to commercial Application also increases substantially.Acetylene hydrogenation condition owing to using is simulation commercial Application condition (trace acetylene feeds with a large amount of Ethylene-dopeds, and temperature is Industrial Catalysis temperature range), with business Pd/Al2O3Catalyst is compared, and novel carriers loaded palladium catalyst will play certain effect with catalytic stability and the high selectivity of its excellence in acetylene selective hydrogenation field.
Detailed description of the invention
Embodiment 1
Take the palladium catalyst 0.08 milligram that novel carriers supports to mix with boron nitride 100 milligrams, add in acetylene hydrogenation reactor.Simulation Industrial Catalysis condition, carries out acetylene hydrogenation reaction, inlet temperature: 20 DEG C, pressure 2.0MPa, gas phase feed 10-60mL/min, alkynes volume fraction 0.4%, successive reaction 300h.
Embodiment 2
Take the palladium catalyst 0.08 milligram that novel carriers supports to mix with boron nitride 100 milligrams, add in acetylene hydrogenation reactor.Simulation Industrial Catalysis condition, carries out acetylene hydrogenation reaction, inlet temperature: 30 DEG C, pressure 2.0MPa, gas phase feed 10-60mL/min, alkynes volume fraction 0.4%, successive reaction 300h.
Embodiment 3
Take the palladium catalyst 0.08 milligram that novel carriers supports to mix with boron nitride 100 milligrams, add in acetylene hydrogenation reactor.Simulation Industrial Catalysis condition, carries out acetylene hydrogenation reaction, inlet temperature: 40 DEG C, pressure 2.0MPa, gas phase feed 10-60mL/min, alkynes volume fraction 0.4%, successive reaction 300h.
Embodiment 4
Take the palladium catalyst 0.08 milligram that novel carriers supports to mix with boron nitride 100 milligrams, add in acetylene hydrogenation reactor.Simulation Industrial Catalysis condition, carries out acetylene hydrogenation reaction, inlet temperature: 50 DEG C, pressure 2.0MPa, gas phase feed 10-60mL/min, alkynes volume fraction 0.4%, successive reaction 300h.
Comparative example 1
Embodiment 1-4 is every the conversion ratio of a 10h acetylene of detection, in 300h tests, in embodiment 2, concentration of acetylene is minimum, average conversion reaches 93.82%, and embodiment 1 is 90.63%, and embodiment 3 is 92.20%, embodiment 4 is 89.37%, visible, in the case of reactor inlet temperature is 30 DEG C, conversion of alkyne is the highest.
Embodiment 5
Take the palladium catalyst 0.08 milligram that novel carriers supports to mix with boron nitride 100 milligrams, add in acetylene hydrogenation reactor.Simulation Industrial Catalysis condition, carries out acetylene hydrogenation reaction, inlet temperature: 30 DEG C, pressure 2.0MPa, gas phase feed 10-60mL/min, alkynes volume fraction 0.5%, successive reaction 300h.
Embodiment 6
Take the palladium catalyst 0.08 milligram that novel carriers supports to mix with boron nitride 100 milligrams, add in acetylene hydrogenation reactor.Simulation Industrial Catalysis condition, carries out acetylene hydrogenation reaction, inlet temperature: 30 DEG C, pressure 2.0MPa, gas phase feed 10-60mL/min, alkynes volume fraction 0.6%, successive reaction 300h.
Comparative example 2
Embodiment 2, embodiment 5 and 6 detect conversion ratio and the content of ethylene of an acetylene every 10h, in 300h tests, from table one.In embodiment 5, concentration of acetylene is minimum, and average conversion reaches 94.56%, and embodiment 1 is 90.63%, and embodiment 3 is 92.20%, and embodiment 4 is 89.37%, it is seen then that in the case of reactor inlet temperature is 30 DEG C, conversion of alkyne is the highest.It is hereby achieved that optimal Industrial Simulation catalytic condition.
Comparative example 3
Simulation Industrial Catalysis condition, carry out the performance comparison of new catalyst and commercial catalysts, wherein Industrial Catalysis condition is: inlet temperature: 30 DEG C, pressure 2.0MPa, gas phase feed 10-60mL/min, gas ratio is 0.5% alkynes, 5% hydrogen, 50%C2H4,44.5%He, and constant temperature 200 DEG C continues chromatograph and divides 16.5 hours.
16.5 hours response datas of chromatography of gases show: Pd/Al2O3Catalyst activity conversion ratio reduces by 50%, and selectivity is presented as 20%.Comparing, the catalyst activity conversion ratio of novel carriers load reduces by 20%, and selectivity is presented as 35%.Compare business Pd/Al2O3, novel carriers loaded palladium catalyst has had significant raising in selectivity and stability.
Comparative example 4
Business is used catalyst Pd/Al2O3Carry out BET detection with new catalyst, respectively obtain their surface area data.There are being conversion ratio and palladium metal surface area (novel carriers loaded palladium catalyst 1.0 ± 0.1m2/g, Pd/Al2O3Catalyst 2.2 ± 0.1m2/ g) while data, the unit palladium surface activity of catalyst can be by calculating Pd/Al2O3(433gC2H2/m2Pdh)
And novel carriers supported palladium (2380gC2H2/m2Pdh).Selectivity before in conjunction with and stability, novel carriers supported palladium not only has the selectivity and stability significantly improved, the most also has activity more higher than business catalyst concurrently.
Comparative example 5
For finding out the reason of new catalyst height selectivity and stability further, business is used catalyst Pd/Al2O3Electron microscopic observation is carried out with new catalyst.Test is learnt, is the difference that causes its catalytic performance of the high forces between functionalization novel carriers and palladium nanoparticle.Owing to active force is strong, palladium metal granule keeps nanoscale dispersion, is supported on securely on novel carriers.The deposition carbon diffusion assembled is to novel carriers surface.Owing to novel carriers has smooth one-dimensional Large ratio surface, the deposition carbon of migration spreads out on novel carriers surface, causes the exposure of palladium particle surface.And business Pd/Al2O3Catalyst, owing to palladium nano-particles and surface are without high forces, adds Al2O3The pore passage structure on surface, to being diffused with inhibition, causes the deposition carbon assembled to migrate nowhere, and massive aggregates is at Al2O3In duct, until with carrier without active force palladium granule release Al2O3Duct.
Accompanying drawing explanation
Fig. 1 (a) is Pd/Al2O3High resolution electron microscopy photo before reaction, palladium granule and Al2O3Duct is high-visible.Fig. 1 (b) is Pd/Al2O3Reacted high resolution electron microscopy photo, the deposition carbon large area of gathering is coated on catalyst surface, and a small amount of palladium granule is pushed out Al2O3Duct.Fig. 1 (c) is Pd/Al2O3Reacted elementary analysis spectrogram, corresponding with Fig. 1 (b), the reacted carbon distribution whole catalyst surface of covering, and aluminum, oxygen, palladium Elemental redistribution is then the most corresponding.
Fig. 2 is Electronic Speculum group figure after the reaction of novel carriers loaded palladium catalyst.With Pd/Al2O3Comparing, palladium nano-particles keeps dispersed on novel carriers, and deposition carbon moves to novel carriers surface from palladium particle surface, and in novel carriers diffusion into the surface, causes part palladium particle surface still to expose.
Fig. 3 (a) is Pd/Al2O3Catalytic performance test figure.Fig. 3 (b) is the catalytic performance figure of novel carriers loaded palladium.Including conversion ratio and selectivity.It can be seen that novel carriers loaded palladium sample significantly improves stability and the selectivity of catalyst.
Claims (9)
1. the methods for making and using same of the novel carriers carried palladium catalyst being applied to acetylene selective hydrogenation, it is characterised in that:
Utilize the carrier of functionalization and the effect of metal cation, make metal precursor and carrier surface stepless action, thus improve catalysis
The stability of agent and selectivity.
Methods for making and using same the most according to claim 1, its process steps is as follows:
I, preparation process
1) take 10 grams of novel carriers and put in beaker, add appropriate concentrated nitric acid, oil bath heated and stirred backflow 1-3 at 90～150 DEG C
Hour.
2) after cooling, add the deionized water of equivalent, after dilution fully, filter.The product of filtration is dispersed in again 1000 millis
Rise in deionized water, the sonic oscillation 10-50 second, filter.This cleaning step repeats 3-6 time.Filtrate is neutralized to by alkaline solution
Neutrality is drained again.Collect filtration product, be dried 12 hours at 60-150 DEG C.
3) according to the tenor selected, the Pd (NO3) 2 of fixed mixing ratio is dissolved in ethanol, adds the functionalization of certain proportioning
Novel carriers, sonic oscillation 30 minutes to 1 hour, stir to solution evaporation under room temperature.
4) the forerunner's product collected is calcined 2 hours at 100-250 DEG C.Then at 400-700 DEG C, with the H2 of fixed mixing ratio
(50-100mL/min) reductase 12 hour is blended with He, is cooled to room temperature and takes out.
II, application process
5) novel carriers loaded palladium catalyst and boron nitride are mixed mutually and are uniformly placed in acetylene hydrogenation reactor, due to the high activity of palladium,
By empirical value and the reaction conversion ratio that makes repeated attempts (optimum 90%～95%), finally determine response magnitude (Novel ethyne hydrogenation catalyst
0.05-0.2 milligram, boron nitride 100 milligrams).
6) acetylene hydrogenation reactor simulated operation condition: inlet temperature: 0-70 DEG C, pressure 1-7MPa, catalyst 0.1-5% mass
Mark new catalyst, gas phase feed 10-60mL/min, hydrogen alkynes is than between for 0.5-2.Constant temperature 200 DEG C continues gas chromatogram
Divide 16.5 hours.
3. according to the preparation method in claim 2, described step 1) in novel carriers be CNT, Graphene, carbonization
Any one or several combinations in silicon.
4. according to the preparation method in claim 2, described step 1) in the amount of concentrated nitric acid taken be 500-1000ml, oil
What bath was heated temperature is 90-150 DEG C, and the time being stirred at reflux is 1-3 hour.
5. according to the preparation method in claim 2, described step 2) in add deionized water after, the time of ultrasonic wave concussion
For the 10-50 second, cleaning step repeats 3-6 time, and the alkaline solution being used for neutralizing is the one in NaOH, NaHCO3, Na2CO3
Or several combinations, baking temperature is 60-150 DEG C.
6. according to the preparation method in claim 2, described step 3) in the concentration of Pd (NO3) 2 be 0.1-8mol/L,
Metal is 1-10% with the vector contg of functionalization, and the ultrasonic wave concussion time is 0.5-1h.
7. according to the preparation method in claim 2, described step 4) in calcining heat be 100250 DEG C, be blended with gas
Temperature is 400-700 DEG C, and hydrogen is 1: 3～1: 1 with the ratio of helium, and the speed being passed through gas is 50-100mL/min.
8. according to the preparation method in claim 2, described step 5) in catalyst mix with boron nitride after false feelings such as acetylene add
In hydrogen reactor, but Boron nitride is 100 milligram hours, and catalyst amount is 0.05-0.2 milligram.
9. according to the preparation method in claim 2, described step 6) in inlet temperature: 0-70 DEG C, pressure 1-7MPa,
Catalyst 0.1-5% mass fraction new catalyst, gas phase feed 10-60mL/min, hydrogen alkynes is than for acetylene hydrogenation between 0.5-2
Reaction conversion ratio is the highest.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106902820A (en) * | 2017-02-27 | 2017-06-30 | 北京神雾环境能源科技集团股份有限公司 | A kind of synthesis of graphene-based catalyst of high concentration preparation of ethylene through selective hydrogenation of acetylene and application process |
| CN106944070A (en) * | 2017-02-27 | 2017-07-14 | 北京神雾环境能源科技集团股份有限公司 | A kind of synthesis of non-precious metal catalyst of high concentration preparation of ethylene through selective hydrogenation of acetylene and application process |
| CN108607587A (en) * | 2018-03-22 | 2018-10-02 | 江苏金聚合金材料有限公司 | A kind of preparation of big hole silicon carbide/graphene mixed carrier loaded palladium catalyst |
| CN116116442A (en) * | 2023-02-20 | 2023-05-16 | 常州大学 | Preparation method and application of low-load sub-nanometer noble metal catalyst |
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2014
- 2014-12-10 CN CN201410771073.0A patent/CN105879863A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106902820A (en) * | 2017-02-27 | 2017-06-30 | 北京神雾环境能源科技集团股份有限公司 | A kind of synthesis of graphene-based catalyst of high concentration preparation of ethylene through selective hydrogenation of acetylene and application process |
| CN106944070A (en) * | 2017-02-27 | 2017-07-14 | 北京神雾环境能源科技集团股份有限公司 | A kind of synthesis of non-precious metal catalyst of high concentration preparation of ethylene through selective hydrogenation of acetylene and application process |
| CN108607587A (en) * | 2018-03-22 | 2018-10-02 | 江苏金聚合金材料有限公司 | A kind of preparation of big hole silicon carbide/graphene mixed carrier loaded palladium catalyst |
| CN116116442A (en) * | 2023-02-20 | 2023-05-16 | 常州大学 | Preparation method and application of low-load sub-nanometer noble metal catalyst |
| CN116116442B (en) * | 2023-02-20 | 2023-12-22 | 常州大学 | Preparation method and application of low-load sub-nanometer noble metal catalyst |
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Application publication date: 20160824 |