CN115282955B - Catalyst for alkyne selective hydrogenation and preparation method thereof - Google Patents
Catalyst for alkyne selective hydrogenation and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 96
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 34
- 150000001345 alkine derivatives Chemical class 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 55
- 229910052751 metal Inorganic materials 0.000 claims abstract description 32
- 239000002184 metal Substances 0.000 claims abstract description 32
- 239000002245 particle Substances 0.000 claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- 230000000694 effects Effects 0.000 claims abstract description 8
- 239000002923 metal particle Substances 0.000 claims abstract description 8
- 238000009826 distribution Methods 0.000 claims abstract description 6
- 150000001336 alkenes Chemical class 0.000 claims abstract description 3
- 101150003085 Pdcl gene Proteins 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 238000011068 loading method Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 239000002041 carbon nanotube Substances 0.000 claims description 9
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 9
- 102000020897 Formins Human genes 0.000 claims description 7
- 108091022623 Formins Proteins 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 6
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 6
- 150000004692 metal hydroxides Chemical class 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 238000012360 testing method Methods 0.000 claims description 5
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 150000001722 carbon compounds Chemical class 0.000 abstract description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 8
- 239000005977 Ethylene Substances 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 8
- 230000008021 deposition Effects 0.000 abstract description 6
- 238000005245 sintering Methods 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000007806 chemical reaction intermediate Substances 0.000 abstract description 2
- 238000003795 desorption Methods 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 239000012266 salt solution Substances 0.000 abstract 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 20
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 20
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 239000000543 intermediate Substances 0.000 description 8
- 238000012546 transfer Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 5
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- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 238000006268 reductive amination reaction Methods 0.000 description 2
- 206010024769 Local reaction Diseases 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium on carbon Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 229910021124 PdAg Inorganic materials 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- -1 aldehyde ketones Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
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- 230000033228 biological regulation Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
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- 150000002576 ketones Chemical class 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
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- 230000001105 regulatory effect Effects 0.000 description 1
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Classifications
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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
- 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
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
- C07C5/09—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds to carbon-to-carbon double bonds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
- C07C2523/44—Palladium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/72—Copper
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention provides a catalyst for selective hydrogenation of alkyne, a preparation method and application thereof. The preparation method adopted by the invention is to impregnate the metal salt solution on the surface of the carrier, and induce the metal salt solution in alkyne hydrogenation reaction environment by utilizing the released heat and reaction intermediates, so that not only can subsurface carbon species be formed on the subsurface of active metal, which is beneficial to desorption of ethylene, but also the released heat of reaction is consumed, local hot spots are avoided, metal particle sintering and carbon deposition are inhibited, and M is obtained e ‑C y s N catalyst. The catalyst is characterized in that the subsurface of the active metal forms carbon species, the electron and the geometric structure of the active metal are modified, C y s The electrons of the active component are transferred to the active metal to enrich the electrons, meanwhile, the generation of subsurface hydrogen species is further inhibited, the active component is highly stably dispersed on the carrier, the size is uniform, the particle size is 1-3nm, and the particle size distribution range is narrow. The catalyst is applied to alkyne selective hydrogenation reaction process, and has high activity, alkene selectivity and long-period stability.
Description
Technical Field
The invention belongs to the fields of petrochemical industry and fine chemical industry, and particularly relates to a catalyst for selective hydrogenation of alkyne and a preparation method thereof.
Background
The chemical industry today involves a catalyst process that increases the rate and selectivity of the reaction during production. However, as the industrial production time increases, the catalytic activity and selectivity decrease, so that the deactivation of the catalyst becomes a serious problem in the current industrial production process. In order to reduce the production cost, improve the environmental benefit and improve the stability of the catalyst, the method has important significance. The intrinsic mechanisms of catalyst deactivation include poisoning, sintering, coking, etc., with the most common being the deposition of deleterious carbon species and the thermal sintering of metal particles. Notably, for alkyne selective hydrogenation reactions, coking and metal agglomeration are observed even though the external compensation temperature (i.e., the average reaction temperature) is relatively low, since unsaturated carbon-carbon triple bond selective hydrogenation is a strongly exothermic reaction in which the heat evolved by the reaction varies in a nonlinear exponential fashion, and the heat transfer rate of the system is proportional to the heat transfer area and temperature gradient, thus varying linearly, resulting in a nonlinear match between the heat release of the reaction and the heat transfer of the system. The phenomenon of mismatch of heat generation and heat transfer causes instantaneous accumulation of heat generated in the exothermic process, forming local reaction hot spots, thereby providing energy for C-C bond breakage, carbon chain growth and metal atom migration. Therefore, in addition to optimization of reaction systems such as condensate, reactor type, heat transfer area, etc., it is also important to implement rapid heat transfer to avoid side reactions by designing the catalyst structure on a microscopic scale. Recently, miao et al, in Array modified molded alumina supported PdAg catalyst for selective acetylene hydrogenation: intrinsic kinetics enhancement and thermal effect optimization, ind. Eng. Chem. Res.2021,60,8362-8374 explored the effect of the support structure on the exothermic reaction of selective hydrogenation of acetylene, found that the construction of an alumina array significantly increased the number of active sites, thereby effectively reducing the local heat generation rate and avoiding the formation of hot spots in the catalyst. The above results indicate that the accumulation of reaction heat can be reduced by adjusting the microstructure of the catalyst.
According to the d-band center theory, the change of the d-band electron cloud density of the active metal can obviously influence the hydrogenation activity and selectivity of acetylene. Based on the difference of the interaction of s orbitals of the adsorption gas on the surface of the catalyst and the d orbitals of the active metal, the institute of Chinese academy of sciences, zhang Tao, team at Highly selective and robust single-atom catalyst Ru 1 in/NC for reductive amination of aldehydes/ketones, nat. Commun.2021,12,3295, use is made of the reaction atmosphere NH in the reductive amination of aldehyde ketones 3 Treatment of Ru/N-C catalyst, found NH at high temperature 3 Inducing, and regulating and controlling Ru with definite coordination structure under the condition of keeping Ru monoatomic dispersion state 1 -N 3 Electron density of active center to make it have moderate H 2 The activation ability, and thus exhibits excellent activity and primary amine selectivity. From this, it can be seen thatThe regulation and control of the active metal structure can be realized through atmosphere induction. Li Dianqing teaches the subject group exposing Pd nanoparticles to C in Adsorbate-induced structural evolution of Pd catalyst for selective hydrogenation of acetylene, ACS Catal.2020,10,15048 2 H 2 In the hydrogenation reaction, it was found that C was produced without significant change in Pd particle size 2 H x The intermediate forms an amorphous carbon layer on the Pd surface, thereby promoting partial surface carbon atoms to enter the subsurface of Pd particles. The formation of subsurface carbon species facilitates selectivity enhancement, however, the surface-covered amorphous carbon layer limits to some extent the possibility of reactant molecules approaching the active center, thereby affecting catalytic activity.
In a catalytic process, if at least one product of reaction a is a reactant in reaction b, and reaction b is present such that reaction a can proceed, this may be referred to as a coupling process. More importantly, the heat released by the exothermic reaction drives the endothermic reaction to occur, so that the energy emission can be further reduced, and the environmental protection of the catalytic process is realized. For example, chen et al in Coupling N 2 and CO 2 in H 2 O to synthesize urea under ambient conditions, nat.chem.2020,12,717-724 uses the advantages of the coupling reaction described above to convert N under normal temperature conditions 2 And CO 2 At H 2 Coupling in O to prepare urea in TiO 2 The nanosheet-supported PdCu alloy nanoparticle undergoes a thermomechanical spontaneous reaction with CO by forming a C-N bond, n=n. However, there are few reports on the use of thermal coupling processes in the reaction process to induce the preparation of highly efficient selective hydrogenation catalysts.
Considering that the hydrogenation of acetylene to generate ethylene is an exothermic process and the dissociation of acetylene to generate carbon atoms is an endothermic process, the invention provides a method for utilizing heat generated in the reaction process to enable acetylene molecules of reactants to be dissociated and adsorbed to generate intermediates, and treating the catalyst, so that the C atoms are controllably and directionally induced to enter the active metal subsurface on the basis of keeping the surface of the catalyst without generating carbon deposition, and the novel subsurface carbon species modified supported metal catalyst is prepared, so that the heat emitted by the reaction can be consumed, the occurrence of local hot spots is avoided, the sintering and carbon deposition of metal particles are inhibited, and the carbon atoms are also induced to be generated, thereby simultaneously improving the activity, the selectivity and the stability of the catalyst.
Disclosure of Invention
The invention aims to provide a highly dispersed and active metal M-times surface carbon species modified supported M e -C y s N catalyst and its preparation method. The catalyst is mainly used for alkyne selective hydrogenation reaction, and has the characteristics of high activity, selectivity and stability.
The catalyst provided by the invention is a supported metal catalyst, and is expressed as M e -C y s N, wherein M is an active metal, M-C y s Is an active metal particle with a subsurface containing carbon atoms, M e Represents electron-rich active metals, C y s S represents the secondary surface, y represents the molar ratio of carbon atoms to M atoms, y=0.05-0.13, and N is a carrier; the M is one of Pd, cu, co, fe, the loading of M is 0.03-10.00 wt%, preferably M is Pd or Fe, and the loading is 0.05-5.00 wt%; the specific surface area of N is 300-500m 2 The high specific surface area carrier per gram is one of carbon nano tube, alumina, pseudo-boehmite and MgAl-composite metal hydroxide. The catalyst is structurally characterized in that: m is M e -C y s Stably dispersed on a carrier N, M is in an electron-rich state, the particle size is 1-3nm, and the particle size distribution range is narrow and the dispersion is uniform.
The preparation method of the alkyne selective hydrogenation catalyst provided by the invention comprises the following specific steps:
A. dissolving soluble M metal salt in deionized water to prepare an impregnating solution with the concentration of 55-100 mmol/L.
The M metal salt is Na 2 PdCl 4 、Pd(NH 3 ) 2 Cl 2 、Pd(NO 3 ) 2 、C 10 H 16 O 4 Pd、Cu(NO)·3H O、Co(NO 3 ) 2 ·6H 2 O、Fe(NO 3 ) 3 One of them, preferably Na 2 PdCl 4 、C 10 H 16 O 4 Pd or Fe (NO) 3 ) 3 . The M metal salt functions to provide the active metal M.
B. Dispersing the carrier N into the impregnating solution prepared in the step A under the condition of continuous stirring at room temperature, wherein the adding amount of the carrier N and the volume of the impregnating solution are determined according to the preset loading amount of M; continuously stirring for 1.0-2.5H, drying in a constant temperature dryer at 60-80 ℃ for 16-18H, and then drying in 10% H 2 /N 2 The mixture is mixed at 5-10 ℃ for min -1 The temperature is raised to 200-450 ℃ for reduction for 1-4 h, and the M/N catalyst is obtained.
The carrier N is one of carbon nano tube, alumina, pseudo-boehmite and MgAl-composite metal hydroxide, preferably the specific surface values of the carrier N and the carrier N are all 300-500m 2 /g。
C. Placing the M/N catalyst obtained in the step B into a fixed bed reactor, introducing alkyne hydrogenation reaction atmosphere, and controlling the gas space velocity to be 10000-240000h -1 Heating to drive reaction to take place, wherein the initial reaction temperature is 30-50deg.C, the temperature interval is 25deg.C, each temperature point is kept for 5h, the highest temperature is 250-260 deg.C, then the temperature is kept for 5h, cooling to room temperature, and taking out to obtain M with high dispersion and enriched M electrons e -C y s N catalyst.
The alkyne hydrogenation reaction atmosphere is 0.6 percent C 2 H 2 /5.4％C 2 H 4 /1.2％H 2 /92.8％N 2 。
The reaction mechanism of the step is as follows: the intermediate generated by the reaction and the released heat induce the active metal M to induce the generation of subsurface carbon species, promote the electron transfer of subsurface C species to M to enrich the electron to obtain M e -C y s /N，M e The method is beneficial to the desorption of olefin during application, improves the selectivity of the product, can consume the heat released by the reaction, avoids local hot spots, inhibits the sintering and carbon deposition of metal particles, and improves the service life and stability of the catalyst.
FIGS. 1-7 show the results of characterization and use of the catalysts prepared according to the present invention
From the HRTEM photograph of fig. 1, it can be seen that the active metal component is uniformly dispersed on the surface of the support, and the particle size ranges from 1 to 3nm, and the average particle diameter is 1.6nm.
It can be seen from fig. 2 that the highly dispersed catalyst can disperse the heat of reaction evolved at individual sites and that as the temperature increases, the rate of exotherm at individual sites of the catalyst increases.
From the HRTEM photograph of fig. 3, it can be seen that the active metal component is uniformly dispersed on the surface of the support, the particle size range is 1 to 3nm, the average particle diameter is 1.8nm, and no significant difference from the reduced catalyst is found, indicating good dispersion structure stability.
From the XRD pattern of fig. 4, it can be seen that the characteristic diffraction peak of Pd (111) shifts to low angles, indicating the formation of subsurface C species.
From the XPS spectrum of FIG. 5, the d-band center of the active metal Pd was seen to shift down, indicating Pd-rich electrons.
As can be seen from FIG. 6, the conversion of acetylene was nearly 100% and the ethylene selectivity was 93% at a reaction temperature of 250 ℃.
From FIG. 7, it can be seen that the catalyst was continuously reacted for 50 hours, once every 5 hours, with an acetylene conversion of 76%, an ethylene selectivity of 85% + -2% and no significant change.
The invention has the beneficial effects that:
the preparation method provided by the invention is characterized in that: the noble metal active component M is highly dispersed on a carrier N with high specific surface area to prepare the M/N catalyst. Introducing alkyne hydrogenation reaction atmosphere to induce the generated reaction intermediate and heat released by the reaction to form carbon species on the subsurface of the active metal nano particles to obtain M e -C y s N catalyst.
The prepared catalyst has the advantages that the active metal particles are highly and stably dispersed, the particle size distribution is 1-3nm, and the active metal subsurface forms carbon species with controllable quantity, so that the problems of metal particle sintering, carbon deposition and the like caused by poor selectivity of acetylene and heat released by reaction are solved.
The catalyst can be applied to the alkyne selective hydrogenation reaction process, the olefin bond selectivity is up to 93%, the long-period stability is high, the catalytic performance is outstanding, and the catalyst is easy to recycle and reuse.
Description of the drawings:
FIG. 1 is a High Resolution Transmission Electron Microscope (HRTEM) photograph and particle size distribution diagram of the hydrogen reduced catalyst of example 1.
FIG. 2 is a graph showing the exotherm of the catalyst prepared in example 1 at various temperatures, a being the exotherm of the catalyst reaction, and b being the exotherm at a single site.
FIG. 3 is a High Resolution Transmission Electron Microscope (HRTEM) photograph and particle size distribution diagram of the reaction atmosphere induced catalyst of example 1.
Fig. 4 is an X-ray diffraction pattern (XRD) of the catalyst prepared in example 1.
FIG. 5 is an X-ray photoelectron spectrum of a catalyst, B is the catalyst prepared in example 1, and a is Pd/CNF obtained in step B of example 1.
FIG. 6 is a plot of the performance of the catalyst prepared in example 1, acetylene selectivity hydrogenation, a for acetylene conversion and ethylene selectivity versus reaction temperature, and b for ethylene selectivity versus reaction temperature and space velocity.
FIG. 7 is a bar graph of the selective hydrogenation stability of acetylene as a catalyst prepared in example 1.
The specific embodiment is as follows:
example 1
A. 1.0640g PdCl was weighed 2 And 0.7010g NaCl are dissolved in deionized water and the volume is fixed to 100mL to prepare 60mmol/L Na 2 PdCl 4 A solution.
B. The specific surface area is 300-500m under the condition of continuous stirring at room temperature according to the loading amount of 1.00 wt% 2 6.32g of carbon nano tube per gram is fully dispersed to 10mL of Na prepared in the step A 2 PdCl 4 Stirring was continued for 2.0h in the solution and then dried in a thermostatic dryer at 60℃for 17h. Then at 10% H 2 /N 2 The mixture is heated at 10 ℃ for min -1 And (3) raising the temperature to 250 ℃ and reducing for 4 hours to obtain the Pd/CNF catalyst.
C. Placing the Pd/CNF catalyst obtained in the step B into a fixed bed reactor, and introducingAcetylene hydrogenation atmosphere, i.e. 0.6% C 2 H 2 /5.4％C 2 H 4 /1.2％H 2 /92.8％N 2 In-situ induction of gas at 50-250 deg.c and reaction gas space velocity of 240000 hr -1 Driving the reaction to take place, using intermediate C produced during the reaction 2 H x And the released heat is used for treating the catalyst, and after 50 hours of reaction, the catalyst is cooled to room temperature, thus obtaining Pd with high dispersion and subsurface carbon species modification e -C 0.13 s CNF catalyst, wherein Pd comprises 1.00wt.% of the catalyst. Calculation formula of y (0.13):wherein a is Pd-C y Is determined by XRD; a, a 0 Lattice parameter +.>
The catalyst prepared above was used in acetylene selective hydrogenation experiments:
0.02g of catalyst was weighed and mixed with 1.9mL of quartz sand having a particle size of 20 to 40 mesh, and then charged into a quartz reaction tube having a diameter of 7 mm. The gas component in the reaction raw material gas is 0.6 percent C 2 H 2 /5.4％C 2 H 4 /1.2％H 2 /92.8％N 2 Space velocity of 240000h -1 The test pressure was 1bar. The catalyst is tested from 50 ℃, the interval of 25 ℃ is one test point, each test point is insulated for 5 hours, the point is taken 1 time every 0.5 hour, and the change relation of acetylene conversion rate and ethylene selectivity along with the temperature is analyzed on line by utilizing gas chromatography. The test results showed that the acetylene conversion was approximately 100% and the ethylene selectivity was 93% at 250 ℃.
Example 2
A. 1.0640g PdCl was weighed 2 And 0.7010g NaCl are dissolved in deionized water and the volume is fixed to 100mL to prepare 60mmol/L Na 2 PdCl 4 A solution.
B. Under the condition of continuous stirring at room temperature, the specific surface area is 300-500m 2 12.62g of carbon nanotubes per gram, according to 0.05wt.%Load capacity, fully dispersed to 10mL Na prepared in step A 2 PdCl 4 Stirring the solution for 2.0H, and drying in a constant temperature dryer at 60deg.C for 17H, then at 10% H 2 /N 2 The mixture is heated at 10 ℃ for min -1 And (3) raising the temperature to 250 ℃ for reduction, and maintaining for 4 hours to obtain the Pd/CNF catalyst.
C. Placing the Pd/CNF catalyst obtained in the step B into a fixed bed reactor, introducing acetylene hydrogenation reaction atmosphere, and controlling the temperature to be 50-250 ℃ and the airspeed to be 240000h -1 Driving the reaction to take place, using intermediate C produced during the reaction 2 H x And the released heat is used for treating the catalyst for 50 hours, then the catalyst is cooled to room temperature and taken out, and the Pd with high dispersion and subsurface carbon species modification is obtained e -C 0.13 s CNF catalyst, wherein Pd comprises 0.05wt.% of the catalyst.
Example 3
A. 1.0640g PdCl was weighed 2 And 0.7010g NaCl are dissolved in deionized water and the volume is fixed to 100mL to prepare 60mmol/L Na 2 PdCl 4 A solution.
B. 6.32g of the mixture is stirred continuously at room temperature with the specific surface area of 300 to 500m 2 Per gram of alumina, at a loading of 1.00wt.% well dispersed to 10mL of Na prepared in step A 2 PdCl 4 Stirring the solution for 2.0H, and drying in a constant temperature dryer at 60deg.C for 17H, then at 10% H 2 /N 2 The mixture is heated at 10 ℃ for min -1 Is heated to 250 ℃ for reduction and is kept for 4 hours to obtain Pd/Al 2 O 3 A catalyst.
C. Pd/Al obtained in the step B 2 O 3 Placing the catalyst in a fixed bed reactor, introducing acetylene hydrogenation reaction atmosphere, and controlling the temperature to be 50-250 ℃ and the airspeed to be 240000h -1 Driving the reaction to take place, using intermediate C produced during the reaction 2 H x And the released heat is used for treating the catalyst for 50 hours, then the catalyst is cooled to room temperature and taken out, and the Pd with high dispersion and subsurface carbon species modification is obtained e -C 0.13 s /Al 2 O 3 Catalyst, wherein Pd comprises 1.00 wt% of the catalyst by mass fraction。
Example 4
A. 1.0640g PdCl was weighed 2 And 0.7010g NaCl are dissolved in deionized water and the volume is fixed to 100mL to prepare 60mmol/L Na 2 PdCl 4 A solution.
B. 6.32g of the mixture with a high specific surface area of 300-500m is stirred continuously at room temperature 2 Per gram of carbon nanotubes, fully dispersed to 10mL of Na prepared in step A at a loading of 1.00wt.% 2 PdCl 4 Stirring the solution for 2.0H, and drying in a constant temperature dryer at 60deg.C for 17H, then at 10% H 2 /N 2 The mixture is heated at 10 ℃ for min -1 And (3) raising the temperature to 250 ℃ for reduction, and maintaining for 4 hours to obtain the Pd/CNF catalyst.
C. Placing the Pd/CNF catalyst obtained in the step B into a fixed bed reactor, introducing acetylene hydrogenation reaction atmosphere, and controlling the temperature to be 50-250 ℃ and the airspeed to be 240000h -1 Driving the reaction to take place, using intermediate C produced during the reaction 2 H x And the released heat is used for treating the catalyst for 30 hours, then the catalyst is cooled to room temperature and taken out, and the Pd with high dispersion and subsurface carbon species modification is obtained e -C 0.09 s CNF catalyst, wherein Pd comprises 1.00wt.% of the catalyst.
Example 5
A. 1.800g Cu (NO) was weighed out 3 ) 2 Dissolving in deionized water and fixing the volume to 100mL to prepare an impregnating solution with the concentration of 100 mmol/L.
B. Under the condition of continuous stirring at room temperature, 1.264g of the mixture with the specific surface of 300-500m 2 Per gram of alumina support, at a loading of 5.00wt.%, was well dispersed to 10mL of Cu (NO) prepared in step A 3 ) 2 In solution, stirring was continued for 1.0H and dried in a constant temperature dryer at 90℃for 24H, then at 10% H 2 /N 2 The mixture is heated at 10 ℃ for min -1 Is heated to 400 ℃ for reduction and is kept for 4 hours to obtain Cu/Al 2 O 3 A catalyst.
C. C, cu/Al obtained in the step B is processed 2 O 3 The catalyst is placed in a fixed bed reactor, acetylene hydrogenation reaction atmosphere is introduced, and the temperature is 50 to the upper200 ℃ and space velocity of 10000h -1 Driving the reaction to take place, using intermediate C produced during the reaction 2 H x And the released heat is used for treating the catalyst for 30 hours, then the catalyst is cooled to room temperature and taken out, and the Cu with high dispersion and subsurface carbon species modification is obtained e -C 0.09 s /Al 2 O 3 The catalyst, wherein Cu comprises 5.00wt.% of the catalyst.
Claims (4)
1. The preparation method of the catalyst for selective hydrogenation of alkyne comprises the following specific preparation steps:
A. dissolving soluble M metal salt in deionized water to prepare an impregnating solution with the concentration of 55-100 mmol/L;
the M metal salt is Na 2 PdCl 4 、Pd(NH 3 ) 2 Cl 2 、Pd(NO 3 ) 2 、C 10 H 16 O 4 Pd、Cu(NO 3 ) 2 ·3H 2 O、Co(NO 3 ) 2 ·6H 2 O、Fe(NO 3 ) 3 One of the following;
B. dispersing the carrier N into the impregnating solution prepared in the step A under the condition of continuous stirring at room temperature, wherein the adding amount of the carrier N and the volume of the impregnating solution are determined according to the preset loading amount of M; continuously stirring for 1.0-2.5H, drying in a constant temperature dryer at 60-80 ℃ for 16-18H, and then drying in 10% H 2 /N 2 The mixture is mixed at 5-10 ℃ for min -1 Heating to 200-450 ℃ for 1-4 h to obtain an M/N catalyst;
the carrier is one of carbon nano tube, alumina, pseudo-boehmite and MgAl-composite metal hydroxide;
C. placing the M/N catalyst obtained in the step B into a fixed bed reactor, introducing alkyne hydrogenation reaction atmosphere, and controlling the gas space velocity to be 10000-240000h -1 Heating to drive reaction to take place, wherein the initial reaction temperature is 30-50deg.C, the temperature interval is 25deg.C, each temperature point is kept for 5h, the highest temperature is 250-260 deg.C, then the temperature is kept for 5h, cooling to room temperature, and taking out to obtain M with high dispersion and enriched M electrons e -C y s N catalyst, its preparation method and useWherein M is metal activity, M-C y s Is an active metal particle with a subsurface containing carbon atoms, M e Represents electron-rich active metals, C y s For carbon atoms of M secondary surfaces, s represents the secondary surface, y represents the molar ratio of carbon atoms to M atoms, y=0.05-0.13;
the M is one of Pd, cu, co, fe, the load amount is 0.03-10.00 wt%, and the specific surface area of N is 300-500M 2 The high specific surface area carrier of/g is one of carbon nano tube, alumina, pseudo-boehmite and MgAl-composite metal hydroxide;
the alkyne hydrogenation reaction atmosphere is 0.6 percent C 2 H 2 /5.4％C 2 H 4 /1.2％H 2 /92.8％N 2 ；
The catalyst is structurally characterized in that: m is M e -C y s Stably dispersed on a carrier N, M is in an electron-rich state, the particle size is 1-3nm, and the particle size distribution range is narrow and the dispersion is uniform.
2. The method for preparing the catalyst for selective hydrogenation of alkyne according to claim 1, which is characterized in that: the metal salt in the step A is Na 2 PdCl 4 、C 10 H 16 O 4 Pd、Fe(NO 3 ) 3 One of the following; the carrier in the step B is one of carbon nano tube, alumina and MgAl-composite metal hydroxide, and the reduction temperature is 250-400 ℃; the airspeed in step C is 180000-240000h -1 。
3. The process for preparing catalyst for selective hydrogenation of alkyne as claimed in claim 1, wherein said catalyst M e -C y s In N, M is Pd or Fe with a loading of 0.05-5.00wt.%; the carrier is one of carbon nano tube, alumina and MgAl-composite metal hydroxide.
4. The use of the supported metal catalyst prepared according to the method of claim 1 for preparing alkene by catalyzing alkyne, characterized in thatThe catalyst loading is 0.02-0.3g, the reaction temperature is 30-250 ℃, and H in the reaction raw material gas 2 /C n H 2n-2 The ratio is 1.5/1-20/1, the test pressure is 1-4bar, and the airspeed is 5000-240000h -1 。
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| CN106732567A (en) * | 2016-11-16 | 2017-05-31 | 北京化工大学 | A kind of metal composite oxide supported active metals catalyst and preparation method thereof |
| CN109939710A (en) * | 2019-04-09 | 2019-06-28 | 浙江工业大学 | A kind of Pd/MC of Pd redispersexLoaded catalyst and its preparation method and application |
| CN110270375A (en) * | 2019-07-01 | 2019-09-24 | 北京化工大学 | A kind of unsaturation carbon-carbon triple bond selective hydrocatalyst and preparation method thereof |
| CN111437852A (en) * | 2020-04-14 | 2020-07-24 | 大连理工大学 | Copper-based catalyst for selective hydrogenation of acetylene and preparation method thereof |
| CN111517906A (en) * | 2019-02-04 | 2020-08-11 | 国家能源投资集团有限责任公司 | Hydrocarbon conversion process using metal carbide nanomaterial catalyst |
| CN113976153A (en) * | 2021-11-17 | 2022-01-28 | 中国科学院大连化学物理研究所 | Ternary new phase Pd3ZnCxPreparation of catalyst and application thereof in selective hydrogenation reaction of acetylene |
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| CN106732567A (en) * | 2016-11-16 | 2017-05-31 | 北京化工大学 | A kind of metal composite oxide supported active metals catalyst and preparation method thereof |
| CN111517906A (en) * | 2019-02-04 | 2020-08-11 | 国家能源投资集团有限责任公司 | Hydrocarbon conversion process using metal carbide nanomaterial catalyst |
| CN109939710A (en) * | 2019-04-09 | 2019-06-28 | 浙江工业大学 | A kind of Pd/MC of Pd redispersexLoaded catalyst and its preparation method and application |
| CN110270375A (en) * | 2019-07-01 | 2019-09-24 | 北京化工大学 | A kind of unsaturation carbon-carbon triple bond selective hydrocatalyst and preparation method thereof |
| CN111437852A (en) * | 2020-04-14 | 2020-07-24 | 大连理工大学 | Copper-based catalyst for selective hydrogenation of acetylene and preparation method thereof |
| CN113976153A (en) * | 2021-11-17 | 2022-01-28 | 中国科学院大连化学物理研究所 | Ternary new phase Pd3ZnCxPreparation of catalyst and application thereof in selective hydrogenation reaction of acetylene |
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