CN109876847A - A kind of heterogeneous core-shell type catalyst and its catalysis process of the Zeolite Entrapped rhodium applied to olefin hydroformylation - Google Patents
A kind of heterogeneous core-shell type catalyst and its catalysis process of the Zeolite Entrapped rhodium applied to olefin hydroformylation Download PDFInfo
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Abstract
A kind of heterogeneous core-shell type catalyst and its catalysis process of the Zeolite Entrapped rhodium applied to olefin hydroformylation, belong to new catalytic material field.The present invention uses submicron order Silicalite-1 (S-1) zeolite molecular sieve crystal grain load rhodium ion for crystal seed; through inducing epitaxial growth S-1 shell; rhodium catalytic activity species are encapsulated in inside S-1 zeolite molecular sieve; core-shell type Rh@S-1 catalyst is formed, and is applied to heterogeneous hydroformylation reaction and synthesizes n-alkanal class.Olefin conversion and aldehyde yield are more than 95%, and the just different ratio of hydroformylation product can reach 1.1-2.0, and catalyst can be recycled.Compared to the homogeneous catalyst system of current industrial application; high energy consumption issues needed for the present invention solves separating catalyst and hydroformylation product; avoid the drawbacks of catalyst is degraded due to the catalytic active component that high temperature distillation process generates during the separation process; to be conducive to recycling for catalyst, have broad application prospects.
Description
Technical field
The invention belongs to new catalytic material fields, and in particular to a kind of applied to novel in hydroformylation of olefin
Heterogeneous core-shell type catalyst, the catalyst are constituted by the way that rhodium nanoparticles are packaged in Silicalite-1 zeolite.
Background technique
As maximum Industrial Catalysis reaction in the world at present, in CO and H2Alkene is converted in atmosphere the hydrogen formyl of aldehyde
During change, usually using the homogeneous rhodium complex containing Phosphine ligands as catalyst.There is such homogeneous catalyst high catalysis to live
Property, high yield object area selectivity (molar ratio of n-alkanal and iso-aldehyde in aldehyde product, i.e., just/different ratio) the advantages of.But pass through
Homogeneous rhodium catalyst and reaction product separation can be consumed mass energy by the processes such as rectifying.In addition, the hot conditions of separation process
It can also make rhodium basigamy mixture catalyst seriously degrade even to inactivate.And compared to homogeneous catalyst, heterogeneous catalysis is due to just
In the separation and recycling the advantages that, it is more suitable the industrial applications of catalysis reaction.But heterogeneous catalysis is in hydrogen formyl
Activity and regioselectivity during change are often not so good as homogeneous catalyst.Therefore, the heterogeneous rhodium of high regioselectivity is developed
Catalyst becomes the key of research.In recent years, many researchers are dedicated to the height that exploitation is more applicable in course of industrialization
The heterogeneous rhodium catalyst of active, high regioselectivity.
Currently, the heterogeneous rhodium catalyst of domestic and foreign literature report is roughly divided into following three kinds:
1) rhodium active component is supported on carrier surface, forms industrial commonly used load type catalyst.Tsing-Hua University is big
Learn Li Yadong seminar [Hou, C., Zhao, G., Ji, Y., et al.Hydroformylation of Alkenes over
Rhodium Supported on the Metal-Organic Framework ZIF-8.Nano Res.2014,7(9),
1364-1369.] rhodium active component is carried on the surface ZIF-8, prepares Rh/ZIF-8 load type catalyst.The catalyst is urged
The hydroformylation for changing different chain type alkene all has preferable reactivity and aldehyde yield.However, due to rhodium nanometer therein
Grain without any modification and processing, so obtained aldehyde product just/it is different relatively low, and there is also conventional load type rhodium activity
The losing issue of component.
2) rhodium presoma is anchored to the carrier surface containing organophosphorus ligand by chemical bond, forms organic carrier
It is anchored loaded catalyst.Ding Yunjie seminar, the Dalian Chemistry and Physics Institute [Wang, Y., Yan, L., Li, C., et al.Highly
Efficient Porous Organic Copolymer Supported Rh Catalysts for Heterogeneous
Hydroformylation of Butenes.Appl.Catal.A Gen.2018,551,98-105.] and Zhejiang University Xiao
Have a good harvest seminar [Sun, Q., Dai, Z., Liu, X., et al.Highly Efficient Heterogeneous
Hydroformylation over Rh-Metalated Porous Organic Polymers:Synergistic Effect
of High Ligand Concentration and Flexible Framework[J].J.Am.Chem.Soc.2015,137
(15), 5204-5209.] it attempts for the precursor solution of rhodium to be anchored to by coordination containing the porous of organophosphorus ligand
Polymer surfaces.Rhodium catalyst catalyzed alkene hydroformylation using the polymer as carrier, since organophosphorus ligand receives rhodium
Rice grain there are certain space confinement and electronics modification, aldehyde product just/it is different than there is raising by a relatively large margin, still,
Cumbersome poromeric preparation process is still a degree of to limit the application prospect of the catalyst, and polymer supported
The not high temperature resistance of body and the reproducibility of monolithic catalyst are also a problem.
3) rhodium of monatomic state is supported on carrier surface.The graduate Zeng Jie seminar of Hefei substance [Wang, L.,
Zhang,W.,Wang,S.,et al.Atomic-Level Insights in Optimizing Reaction Paths for
Hydroformylation Reaction over Rh/CoO Single-Atom Catalyst.Nat.Commun.2016,7,
1-8.] cobalt atom for replacing cobalt oxide surface with rhodium, synthesizes the Rh/CoO catalyst of monatomic state.Due to ambient oxygen atom pair
The confinement of monatomic state rhodium acts on, so that it shows excellent regioselectivity during the hydroformylation of propylene.However
Monatomic catalyst industrialized production relatively difficult to achieve, such catalyst is only limited to the laboratory research stage at present.
Therefore, it develops a kind of with high activity, high regioselectivity and the relatively simple heterogeneous hydrogen first of preparation process
Acylation catalyst is still worth further investigation.
Summary of the invention
The present invention is for office existing for existing homogeneous and heterogeneous hydroformylation catalyst mentioned above in the background art
It is sex-limited, it proposes to form nucleocapsid using a kind of rhodium nanoparticles are packaged in Silicalite-1 (S-1) zeolite molecular sieve crystal
Formula heterogeneous catalysis (Rh@S-1) is applied to olefin hydroformylation processing efficient and synthesizes n-alkanal.
The invention has the characteristics that rhodium nanoparticles are packaged in S-1 zeolite molecular sieve, rhodium nanometer is effectively improved
The anti-agglutinatting property and catalytic activity of grain, and the function of the shape-selective confinement using molecular sieve pore passage, can be improved hydroformylation aldehyde
The regioselectivity of product.Compared to traditional load type catalyst, which both has high yield
Regioselectivity, high temperature sintering resistant stability and the good circulation for being easy to reaction product separation of object, and there is preparation process
It is relatively easy and be not directed to the expensive and synthesis of cumbersome organophosphorus ligand.At the same time, core-shell type according to the present invention is urged
The separation and recovery of catalyst and reaction material liquid only can be realized in agent after hydroformylation reaction by routine simple separation, no
Catalyst structure can be had an impact, convenient for the recycling of catalyst.
Technical scheme is as follows:
The preparation of center shell catalyst of the present invention is using submicron order S-1 crystal grain as crystal seed, 3- mercapto propyl trimethoxy
Base silane carries out sulfydryl modification processing to S-1 crystal seed as coupling agent to be conducive to load fixed Rh3+；It is raw in Zeolite synthesis liquid
Long cladding prepares the heterogeneous core-shell type catalyst of S-1 encapsulation rhodium nanoparticles (Rh@S-1).
Rh@S-1 catalyst in the present invention is applied to the separation of hydroformylation of olefin and catalyst, recycling: taking one
Determine quality Rh@S-1 catalyst be added toluene solvant in, into system be added certain volume linear alkene after be filled with CO and
H2；Reaction after a certain period of time, takes out the mixture of catalyst and feed liquid, using centrifuge separation catalyst and feed liquid；It will isolate
Catalyst be placed in air dry oven dry, recycling is in case catalysis hydroformylation reaction next time.
Concrete operations process of the present invention is as follows:
(1) the sulfhydrylation processing of S-1 crystal seed
A certain amount of S-1 crystal seed is taken to be scattered in ethyl alcohol according to the solid-to-liquid ratio of 1:100g/mL, according still further to 0.143mol/L
Molar concentration be added 3- mercaptopropyl trimethoxysilane, processing obtain after a certain period of time by sulfhydrylation handle S-1 crystal seed.
(2) load of rhodium precursor solution
The S-1 crystal seed of the processing of sulfhydrylation obtained in step (1) is dispersed to deionized water by the solid-to-liquid ratio of 1:100g/mL
In, obtain the sulfhydrylation S-1 crystal seed liquid A of certain content；Then RhCl is taken3Powder, which is dissolved in deionized water, obtains 1.9mmol/L-
The RhCl of 4.8mmol/L3Solution matches to obtain solution B.Solution B is added in above-mentioned crystal seed liquid A, processing 4h is stirred at room temperature, obtains
S-1 crystal seed (the Rh of rhodium ion load3+/S-1)
(3)Rh3+/ S-1 epitaxial growth S-1 shell forms core-shell type Rh@S-1 catalyst
According to TEOS:TPAOH:H2O=40:10:(10000~20000) molar ratio S-1 shell Synthesis liquid, will
Rh obtained in step (2)3+/ S-1 crystal seed is added in Synthesis liquid, is aged 2h at room temperature.After ageing, by the Synthesis liquid
It is fitted into the synthesis reactor with polytetrafluoroethyllining lining, 130-170 DEG C of hydrothermal synthesis 8-24h, preferably 170 DEG C in rotation baking oven
Hydrothermal synthesis is for 24 hours.After the completion of synthesis, by mixed liquor after supercentrifuge is centrifuged, solid product is taken to be dried, and in Muffle
With 550 DEG C of roasting 6h in furnace, the core-shell type catalyst Rh@S-1 of zeolite molecular sieve encapsulation rhodium nanoparticles is finally prepared.
Another object of the present invention is the Rh@S-1 nucleocapsid that above-mentioned S-1 zeolite molecular sieve encapsulation rhodium nanoparticles are claimed
Application of the formula heterogeneous catalysis in hydroformylation.Concrete operations process is as follows:
Weigh metal rhodium and Rh@S-1 catalysis that linear alkene molar ratio that carbon number is 6~10 is 1:4200~1:12800
Agent and olefin reactant, catalyst and solvent solid-to-liquid ratio are that 11~18.3mg/mL is scattered in a certain amount of toluene solvant.With 1:
The CO and H of 1 volume ratio2As reaction gas, under the pressure of 1~5MPa, 60~100 DEG C of reaction 12h.After reaction, will
By centrifuge separation recovery processing is dried to solid catalyst, product liquid is examined using gas-chromatography in catalyst and feed liquid
Survey result.
Compared with prior art, the beneficial effects of the present invention are: the preparation process of catalyst provided by the invention is relatively simple
It is single and at low cost.There is regioselectivity, the high temperature sintering resistant stability of high product using the catalyst of the method for the present invention preparation
With the good circulation for being easy to reaction product and separating, in olefin conversion and aldehyde yield more than 95%, hydroformylation product
It is just different than reachable 1.1-2.0.At the same time, core-shell type catalyst according to the present invention only passes through after hydroformylation reaction
The separation of catalyst and reaction material liquid can be realized in centrifugation, will not have an impact to catalyst structure, which can be multiple
It is recycled, it is with good stability.
Detailed description of the invention
Fig. 1 is the scanning electron microscopic picture (SEM) of Rh@S-1 catalyst；
Fig. 2 is the scanning transmission electron microscope picture (STEM) of Rh@S-1 catalyst；
Fig. 3 is the x-ray diffractogram of powder (XRD) of Rh@S-1 catalyst；
Fig. 4 is the reaction result that Rh@S-1 catalysis 1- hexene hydroformylation is recycled 6 times.
Specific embodiment
The present invention is described in detail below by the drawings and specific embodiments, but is not limited the scope of the invention.Such as without special
Illustrate, experimental method of the present invention is conventional method, and experiment equipment used, material, reagent etc. can be from business ways
Diameter obtains.
Embodiment 1
(1) the sulfhydrylation processing of S-1 crystal seed
Taking the homemade size of 0.2g is about 150nm S-1 crystal seed, is dispersed in the ethyl alcohol of 20mL, and mole is added dropwise and is
The 3- mercaptopropyl trimethoxysilane of 2.86mmol.By the crystal seed suspension at 60 DEG C stir process 6h, obtain by sulfydryl
Change the S-1 crystal seed of processing.Any known method preparation in this field, such as China can be used in homemade S-1 crystal seed in the step
The preparation of S-1 crystal seed mentioned in application for a patent for invention CN107442155A.
(2) load of rhodium precursor solution
The S-1 crystal seed of the processing of sulfhydrylation obtained in step (1) is dispersed in 15mL deionized water, mixture A is matched to obtain；
Take the RhCl of 0.005g3Powder is dissolved in 5mL deionized water, matches to obtain solution B.B is added in A, processing 4h is stirred at room temperature, obtains
S-1 crystal seed (the Rh of rhodium ion load3+/S-1)。
(3)Rh3+/ S-1 epitaxial growth S-1 shell
According to TEOS:TPAOH:H2The molar ratio S-1 shell Synthesis liquid of O=40:10:10000, will be in step (2)
Obtained Rh3+/ S-1 crystal seed is added in Synthesis liquid, is aged 2h at room temperature.After ageing, Synthesis liquid loading is had
In the synthesis reactor of polytetrafluoroethyllining lining, with the revolving speed of 3r/min in rotation baking oven, 170 DEG C of hydrothermal synthesis are for 24 hours.Synthesis is completed
Afterwards, solid product is taken to be dried after supercentrifuge is centrifuged the mixed liquor in polytetrafluoroethyllining lining, and in Muffle furnace
In with 550 DEG C of roasting 6h, finally prepare the core-shell type catalyst Rh@S-1 of S-1 zeolite molecular sieve encapsulation rhodium nanoparticles.It urges
The pattern of agent is as shown in Figure 1；Rhodium nanoparticles are as shown in Figure 2 in catalyst；The crystallinity of catalyst is as shown in Figure 3.
(4) application of Rh@S-1 core-shell type catalyst during hydroformylation
Metal rhodium and 1- hexene molar ratio are weighed as the Rh@S-1 catalyst and reactant of 1:4200, is dispersed in the first of 6mL
In benzene solvent.With the CO and H of 1:1 volume ratio2As reaction gas, after being purged 4 times to reaction unit, under the pressure of 5MPa,
80 DEG C of reaction 12h.After reaction, catalyst and feed liquid are centrifugated, recovery processing, liquid is dried to solid catalyst
Body product uses gas-chromatography (chromatographic column: SE-30, FID) testing result.
Embodiment 2
(1) the sulfhydrylation processing of S-1 crystal seed is in the same manner as in Example 1.
(2) load of rhodium precursor solution is in the same manner as in Example 1.
(3)Rh3+/ S-1 epitaxial growth S-1 shell
According to TEOS:TPAOH:H2The molar ratio S-1 shell Synthesis liquid of O=40:10:20000, will be in step (2)
Obtained Rh3+/ S-1 crystal seed is added in Synthesis liquid, is aged 2h at room temperature.After ageing, Synthesis liquid loading is had
In the synthesis reactor of polytetrafluoroethyllining lining, with the revolving speed of 3r/min in rotation baking oven, 170 DEG C of hydrothermal synthesis are for 24 hours.Synthesis is completed
Afterwards, solid product is taken to be dried after supercentrifuge is centrifuged the mixed liquor in polytetrafluoroethyllining lining, and in Muffle furnace
In with 550 DEG C of roasting 6h, finally prepare the core-shell type catalyst Rh@S-1 of S-1 zeolite molecular sieve encapsulation rhodium nanoparticles.
(4) application of Rh@S-1 core-shell type catalyst during hydroformylation
Metal rhodium and 1- hexene molar ratio are weighed as the Rh@S-1 catalyst and reactant of 1:6400, is dispersed in the first of 6mL
In benzene solvent.With the CO and H of 1:1 volume ratio2As reaction gas, after being purged 4 times to reaction unit, under the pressure of 5MPa,
80 DEG C of reaction 12h.After reaction, catalyst and feed liquid are centrifugated, recovery processing, liquid is dried to solid catalyst
Body product uses gas-chromatography (chromatographic column: SE-30, FID) testing result.It is carried out 6 times using the catalyst of embodiment preparation
It is catalyzed 1- hexene hydroformylation, reaction result is as shown in Figure 4, which has good cyclicity.
Embodiment 3
(1) the sulfhydrylation processing of S-1 crystal seed is in the same manner as in Example 1.
(2) load of rhodium precursor solution is in the same manner as in Example 1.
(3)Rh3+/ S-1 epitaxial growth S-1 shell is in the same manner as in Example 2.
(4) application of Rh@S-1 core-shell type catalyst during hydroformylation
Metal rhodium and 1- hexene molar ratio are weighed as the Rh@S-1 catalyst and reactant of 1:6400, is dispersed in the first of 8mL
In benzene solvent.With the CO and H of 1:1 volume ratio2As reaction gas, after being purged 4 times to reaction unit, under the pressure of 5MPa,
80 DEG C of reaction 12h.After reaction, catalyst and feed liquid are centrifugated, recovery processing, liquid is dried to solid catalyst
Body product uses gas-chromatography (chromatographic column: SE-30, FID) testing result.
Embodiment 4
(1) the sulfhydrylation processing of S-1 crystal seed is in the same manner as in Example 1.
(2) load of rhodium precursor solution is in the same manner as in Example 1.
(3)Rh3+/ S-1 epitaxial growth S-1 shell is in the same manner as in Example 2.
(4) application of Rh@S-1 core-shell type catalyst during hydroformylation
Metal rhodium and 1- hexene molar ratio are weighed as the Rh@S-1 catalyst and reactant of 1:6400, is dispersed in the first of 10mL
In benzene solvent.With the CO and H of 1:1 volume ratio2As reaction gas, after being purged 4 times to reaction unit, under the pressure of 5MPa,
80 DEG C of reaction 12h.After reaction, catalyst and feed liquid are centrifugated, recovery processing, liquid is dried to solid catalyst
Body product uses gas-chromatography (chromatographic column: SE-30, FID) testing result.
Embodiment 5
(1) the sulfhydrylation processing of S-1 crystal seed is in the same manner as in Example 1.
(2) load of rhodium precursor solution is in the same manner as in Example 1.
(3)Rh3+/ S-1 epitaxial growth S-1 shell is in the same manner as in Example 2.
(4) application of Rh@S-1 core-shell type catalyst during hydroformylation
Metal rhodium and 1- octene molar ratio are weighed as the Rh@S-1 catalyst and reactant of 1:6400, is dispersed in the first of 6mL
In benzene solvent.With the CO and H of 1:1 volume ratio2As reaction gas, after being purged 4 times to reaction unit, under the pressure of 5MPa,
80 DEG C of reaction 12h.After reaction, catalyst and feed liquid are centrifugated, recovery processing, liquid is dried to solid catalyst
Body product uses gas-chromatography (chromatographic column: SE-30, FID) testing result.
Embodiment 6
(1) the sulfhydrylation processing of S-1 crystal seed is in the same manner as in Example 1.
(2) load of rhodium precursor solution is in the same manner as in Example 1.
(3)Rh3+/ S-1 epitaxial growth S-1 shell is in the same manner as in Example 2.
(4) application of Rh@S-1 core-shell type catalyst during hydroformylation
Metal rhodium and 1- octene molar ratio are weighed as the Rh@S-1 catalyst and reactant of 1:6400, is dispersed in the first of 10mL
In benzene solvent.With the CO and H of 1:1 volume ratio2As reaction gas, after being purged 4 times to reaction unit, under the pressure of 5MPa,
80 DEG C of reaction 12h.After reaction, catalyst and feed liquid are centrifugated, recovery processing, liquid is dried to solid catalyst
Body product uses gas-chromatography (chromatographic column: SE-30, FID) testing result.
Embodiment 7
(1) the sulfhydrylation processing of S-1 crystal seed is in the same manner as in Example 1.
(2) load of rhodium precursor solution is in the same manner as in Example 1.
(3)Rh3+/ S-1 epitaxial growth S-1 shell is in the same manner as in Example 2.
(4) application of Rh@S-1 core-shell type catalyst during hydroformylation
Metal rhodium and 1- decene molar ratio are weighed as the Rh@S-1 catalyst and reactant of 1:6400, is dispersed in the first of 6mL
In benzene solvent.With the CO and H of 1:1 volume ratio2As reaction gas, after being purged 4 times to reaction unit, under the pressure of 5MPa,
80 DEG C of reaction 12h.After reaction, catalyst and feed liquid are centrifugated, recovery processing, liquid is dried to solid catalyst
Body product uses gas-chromatography (chromatographic column: SE-30, FID) testing result.
Embodiment 8
(1) the sulfhydrylation processing of S-1 crystal seed is in the same manner as in Example 1.
(2) load of rhodium precursor solution is in the same manner as in Example 1.
(3)Rh3+/ S-1 epitaxial growth S-1 shell is in the same manner as in Example 2.
(4) application of Rh@S-1 core-shell type catalyst during hydroformylation
Metal rhodium and 1- decene molar ratio are weighed as the Rh@S-1 catalyst and reactant of 1:6400, is dispersed in the first of 10mL
In benzene solvent.With the CO and H of 1:1 volume ratio2As reaction gas, after being purged 4 times to reaction unit, under the pressure of 5MPa,
80 DEG C of reaction 12h.After reaction, catalyst and feed liquid are centrifugated, recovery processing, liquid is dried to solid catalyst
Body product uses gas-chromatography (chromatographic column: SE-30, FID) testing result.
Embodiment 9
(1) the sulfhydrylation processing of S-1 crystal seed is in the same manner as in Example 1.
(2) load of rhodium precursor solution is in the same manner as in Example 1.
(3)Rh3+/ S-1 epitaxial growth S-1 shell is in the same manner as in Example 2.
(4) application of Rh@S-1 core-shell type catalyst during hydroformylation
Metal rhodium and 1- hexene molar ratio are weighed as the Rh@S-1 catalyst and reactant of 1:6400, is dispersed in the first of 10mL
In benzene solvent.With the CO and H of 1:1 volume ratio2As reaction gas, after being purged 4 times to reaction unit, under the pressure of 3MPa,
80 DEG C of reaction 12h.After reaction, catalyst and feed liquid are centrifugated, recovery processing, liquid is dried to solid catalyst
Body product uses gas-chromatography (chromatographic column: SE-30, FID) testing result.
Embodiment 10
(1) the sulfhydrylation processing of S-1 crystal seed is in the same manner as in Example 1.
(2) load of rhodium precursor solution is in the same manner as in Example 1.
(3)Rh3+/ S-1 epitaxial growth S-1 shell is in the same manner as in Example 2.
(4) application of Rh@S-1 core-shell type catalyst during hydroformylation
Metal rhodium and 1- hexene molar ratio are weighed as the Rh@S-1 catalyst and reactant of 1:6400, is dispersed in the first of 10mL
In benzene solvent.With the CO and H of 1:1 volume ratio2As reaction gas, after being purged 4 times to reaction unit, under the pressure of 5MPa,
100 DEG C of reaction 12h.After reaction, catalyst and feed liquid are centrifugated, recovery processing are dried to solid catalyst,
Product liquid uses gas-chromatography (chromatographic column: SE-30, FID) testing result.
When being different solvents dosage as shown in Table 1, Rh@S-1 and conventional load type Rh/S-1 catalyst 1- octene and
The reaction result of 1- decene hydroformylation compares.
Table 1 is catalyzed reaction result comparison
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art within the technical scope of the present disclosure, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (2)
1. a kind of Rh@S-1 core-shell type heterogeneous catalysis of zeolite molecular sieve encapsulation rhodium nanoparticles is used for olefin hydroformylation
The method of catalysis, which is characterized in that specific as follows:
Weigh metal rhodium and zeolite molecular sieve encapsulation that linear alkene molar ratio that carbon number is 6~10 is 1:4200~1:12800
The core-shell type Rh@S-1 catalyst and olefin reactant of rhodium nanoparticles, be dispersed in catalyst and solvent solid-to-liquid ratio be 11~
In the toluene solvant of 18.3mg/mL, with the CO and H of 1:1 volume ratio2As reaction gas, under the pressure of 1~5MPa, 60~
100 DEG C of reaction 12h after reaction, catalyst Rh@S-1 and feed liquid are separated, recycling is dried to solid catalyst
In case being catalyzed hydroformylation reaction next time, product liquid uses gas chromatographic detection result for processing.
2. the method as described in claim 1, which is characterized in that the Rh@S-1 of the zeolite molecular sieve encapsulation rhodium nanoparticles
Core-shell type heterogeneous catalysis the preparation method is as follows:
(1) the sulfhydrylation processing of S-1 crystal seed
Taking size is that the S-1 crystal seed of 100-200nm is scattered in ethyl alcohol according to the solid-to-liquid ratio of 1:100g/mL, by 0.143mol/
3- mercaptopropyl trimethoxysilane is added dropwise in the molar concentration of L, through handling the S-1 crystal seed for obtaining handling by sulfhydrylation；
(2) load of rhodium precursor solution
By the S-1 crystal seed of the processing of sulfhydrylation obtained in step (1), it is dispersed in deionized water by the solid-to-liquid ratio of 1:100g/mL
Obtain sulfhydrylation crystal seed aqueous solution；Then the certain rhodium load capacity of catalyst is pressed, the RhCl of 1.9mmol/L-4.8mmol/L is taken3It is molten
Liquid is added in above-mentioned sulfhydrylation crystal seed aqueous solution, and processing is stirred at room temperature, obtains Rh3+/ S-1 crystal seed；
(3)Rh3+/ S-1 epitaxial growth S-1 shell obtains core-shell type Rh@S-1 catalyst
According to TEOS:TPAOH:H2O=40:10:(10000~20000) molar ratio S-1 shell Synthesis liquid, by step
(2) Rh obtained in3+/ S-1 crystal seed is added in Synthesis liquid, is aged at room temperature.After ageing, which is packed into and is synthesized
In kettle, in rotation baking oven in 130-170 DEG C of hydrothermal synthesis 8-24h, after the completion of synthesis, mixed liquor through separation take out solid product into
Row drying, and with 550 DEG C of roasting 6h, the final core-shell type catalysis for obtaining zeolite molecular sieve encapsulation rhodium nanoparticles in Muffle furnace
Agent Rh@S-1.
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| CN111686795A (en) * | 2020-06-15 | 2020-09-22 | 大连理工大学 | One-pot preparation method of sulfur-doped KL molecular sieve packaged rhodium nanoparticle core-shell catalyst and application of sulfur-doped KL molecular sieve packaged rhodium nanoparticle core-shell catalyst in catalyzing selective hydrogenation of phenol |
| CN114163318A (en) * | 2020-09-10 | 2022-03-11 | 中国科学院大连化学物理研究所 | Application of supported Rh monatomic catalyst in olefin hydroformylation reaction |
| CN115108899A (en) * | 2022-07-18 | 2022-09-27 | 浙江大学 | Method for preparing aldehyde compound by catalyzing hydroformylation of olefin through hydrophilic molecular sieve |
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| CN111686795B (en) * | 2020-06-15 | 2022-10-14 | 大连理工大学 | One-pot preparation method of sulfur-doped KL molecular sieve packaged rhodium nanoparticle core-shell catalyst and application of sulfur-doped KL molecular sieve packaged rhodium nanoparticle core-shell catalyst in catalyzing selective hydrogenation of phenol |
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| CN114163318B (en) * | 2020-09-10 | 2023-04-18 | 中国科学院大连化学物理研究所 | Application of supported Rh monatomic catalyst in olefin hydroformylation reaction |
| CN115739146A (en) * | 2021-09-03 | 2023-03-07 | 中国石油天然气股份有限公司 | Hydroformylation catalyst and preparation method and application thereof |
| CN115108899A (en) * | 2022-07-18 | 2022-09-27 | 浙江大学 | Method for preparing aldehyde compound by catalyzing hydroformylation of olefin through hydrophilic molecular sieve |
| CN115108899B (en) * | 2022-07-18 | 2024-05-10 | 浙江大学 | Method for preparing aldehyde compound by catalyzing olefin hydroformylation through hydrophilic molecular sieve |
| CN115646547A (en) * | 2022-11-22 | 2023-01-31 | 中国石油大学(华东) | High-carbon olefin hydroformylation carbon-supported rhodium-cobalt single-atom alloy catalyst and preparation and application methods thereof |
| CN115646547B (en) * | 2022-11-22 | 2024-01-30 | 中国石油大学(华东) | Rhodium-cobalt loaded monoatomic alloy catalyst for hydroformylation of high-carbon olefin and preparation and application methods thereof |
| CN115999629A (en) * | 2023-02-03 | 2023-04-25 | 中国科学院山西煤炭化学研究所 | Heterogeneous catalyst for preparing aldehyde by hydroformylation of alpha-olefin, preparation method and application thereof |
| CN117160518A (en) * | 2023-09-01 | 2023-12-05 | 南京工业大学 | Zeolite molecular sieve loaded platinum monoatomic cluster catalyst and its preparation method and use |
| CN117899920A (en) * | 2024-02-04 | 2024-04-19 | 河南能源集团研究总院有限公司 | 1, 4-Succinonitrile hydrogenation catalyst and preparation method thereof |
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