CN114768799B - Selective catalytic hydrogenation supported metal catalyst and preparation method and application thereof - Google Patents
Selective catalytic hydrogenation supported metal catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN114768799B CN114768799B CN202210545559.7A CN202210545559A CN114768799B CN 114768799 B CN114768799 B CN 114768799B CN 202210545559 A CN202210545559 A CN 202210545559A CN 114768799 B CN114768799 B CN 114768799B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- carrier
- catalytic hydrogenation
- selective catalytic
- supported metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 97
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 53
- 239000002184 metal Substances 0.000 title claims abstract description 53
- 238000009903 catalytic hydrogenation reaction Methods 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 235000009470 Theobroma cacao Nutrition 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 4
- 150000003624 transition metals Chemical class 0.000 claims abstract description 4
- 238000007598 dipping method Methods 0.000 claims abstract description 3
- 244000240602 cacao Species 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 26
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000005984 hydrogenation reaction Methods 0.000 claims description 17
- 239000012065 filter cake Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000002244 precipitate Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 150000001299 aldehydes Chemical class 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- STZPMOIAPWTLNJ-UHFFFAOYSA-N 5-methyl-2-propan-2-ylhexanal Chemical compound CC(C)CCC(C=O)C(C)C STZPMOIAPWTLNJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 claims 1
- -1 aldehyde compounds Chemical class 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 11
- 229920006395 saturated elastomer Polymers 0.000 abstract description 3
- 208000012839 conversion disease Diseases 0.000 abstract description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 54
- 229910052763 palladium Inorganic materials 0.000 description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 239000000843 powder Substances 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 239000003622 immobilized catalyst Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 244000299461 Theobroma cacao Species 0.000 description 7
- 238000010304 firing Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- KSMVZQYAVGTKIV-UHFFFAOYSA-N decanal Chemical compound CCCCCCCCCC=O KSMVZQYAVGTKIV-UHFFFAOYSA-N 0.000 description 4
- 238000006356 dehydrogenation reaction Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 150000002085 enols Chemical class 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002082 metal nanoparticle Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- BHPDSAAGSUWVMP-UHFFFAOYSA-N 3,3-bis(methoxymethyl)-2,6-dimethylheptane Chemical compound COCC(C(C)C)(COC)CCC(C)C BHPDSAAGSUWVMP-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- IOLQAHFPDADCHJ-UXBLZVDNSA-N 2-isopropyl-5-methyl-2-hexenal Chemical compound CC(C)C\C=C(/C=O)C(C)C IOLQAHFPDADCHJ-UXBLZVDNSA-N 0.000 description 1
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
- B01J23/38—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
- B01J23/42—Platinum
-
- 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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a selective catalytic hydrogenation supported metal catalyst, a preparation method and application thereof, and particularly relates to the field of catalysts. The method comprises the steps of pretreating a carrier needing to be loaded with transition metal, and forming to obtain a carrier compound; dipping the active precursor, and then dropwise adding the active precursor onto the carrier compound to form a dipped material; and drying and roasting the impregnated material to obtain the selective catalytic hydrogenation supported metal catalyst. The catalyst comprises a shaped support and an active precursor. The selective catalytic hydrogenation supported metal catalyst is applied as a catalyst for catalytic hydrogenation of unsaturated aldehyde compounds. The selective catalytic hydrogenation supported metal catalyst prepared by the invention can selectively hydrogenate double bonds to form saturated aldehyde compounds for unsaturated aldehyde compounds such as cocoa aldehyde, the selectivity can reach more than 90%, and the reaction conversion rate can reach more than 90%.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a selective catalytic hydrogenation supported metal catalyst and a preparation method and application thereof.
Background
Unsaturated aldehydes such as cocoa aldehyde contain both C = C bond and C = O bond in the molecule, so that during the hydrogenation process, whether H is added to C = C bond to become saturated aldehyde or C = O bond to become unsaturated alcohol or acid is uncertain in the chemical reaction, so how to control the hydrogenation process, the directional addition of H to the double bond is the key point of the research on the hydrogenation catalyst.
In the existing catalytic hydrogenation reaction of alpha, beta-unsaturated aldehyde compounds, in order to generate directional selective compounds, most of the existing researches adopt metal oxide supported metal nanoparticle catalysts. The catalyst prepared by using the transition metal oxide as a carrier and loading various metal nano-particles or a mixture of a plurality of metal nano-particles on the surface of the oxide has good catalytic activity,
the palladium catalyst produced in China mainly comprises Pd/A for hydrogen peroxide produced by Riming chemical research institute 2 O 3 The catalyst comprises a catalyst and a palladium catalyst for gas purification, wherein the palladium-containing mass fraction produced by a first large organic chemical plant is more than or equal to 59 percent, the palladium catalyst for hydrogenation is Q1060.84, the palladium/carbon catalyst produced by a large chemical and physical research institute, the palladium/carbon catalyst and the palladium chloride catalyst produced by Shanghai petrochemical industry and general factories, the platinum-palladium series DH type dehydrogenation catalyst, CH dehydrogenation catalyst and DO type high-efficiency deoxidizer produced by Lanzhou compounds of the Chinese academy and the like, the lowest content of palladium metal in the catalysts is also more than 5 percent, the palladium content is lower than 5 percent, and the catalysts can hardly play a catalytic effect.
The existing catalyst for catalytic hydrogenation on the market generally has the content of at least 10% of noble metal, is easy to deactivate, has large solvent amount, is easy to hydrogenate excessively and has low selectivity.
Disclosure of Invention
Therefore, the invention provides a selective catalytic hydrogenation supported metal catalyst, and a preparation method and application thereof, and aims to solve the problems of excessive hydrogenation of compounds and the like caused by high metal content and easy inactivation in the existing catalyst.
In order to achieve the above purpose, the invention provides the following technical scheme:
according to a first aspect of the present invention, there is provided a method for preparing a selective catalytic hydrogenation supported metal catalyst, the method comprising the steps of:
step one, pretreating a carrier needing to be loaded with transition metal, and forming to obtain a carrier compound;
after dipping the active precursor, dropwise adding the active precursor onto a carrier compound to form a dipped material; and drying and roasting the impregnated material to obtain the selective catalytic hydrogenation supported metal catalyst.
Further, the carrier is an active carbon carrier or macroporous Al 2 O 3 And (3) a carrier.
Further, the method for pretreating the activated carbon carrier comprises the steps of soaking the activated carbon carrier in nitric acid, washing the activated carbon carrier with distilled water until filtrate is neutral, calcining, and grinding to 100-150 meshes to obtain the activated carbon carrier.
Further, the macroporous Al 2 O 3 The carrier is pretreated by adding Al (NO) 3 ) 3 ·9H 2 Dissolving O in water to obtain Al (NO) 3 ) 3 Heating the solution in water bath, and adding Al (NO) 3 ) 3 Slowly adding ammonia water into the solution while vigorously stirring to obtain precipitate, aging the precipitate, vacuum filtering, washing the filter cake with ethanol for several times, and firing to obtain macroporous Al 2 O 3 And (3) a carrier.
Further, the active precursor is a soluble salt solution of Pd or Pt.
Palladium metal catalysts are commonly used for C = C selective hydrogenation under mild conditions, and show low catalytic activity for C = O double bonds, and are good catalysts for selective catalytic hydrogenation of C = C bonds in α, β -unsaturated aldehyde compounds.
According to a second aspect of the present invention, there is provided a selective catalytic hydrogenation supported metal catalyst prepared by the above method.
Further, the catalyst comprises a shaped support and an active precursor.
Furthermore, the metal catalyst contains 0.2 to 0.8 percent of metal.
The use of the above-mentioned selective catalytic hydrogenation supported metal catalyst as a catalyst for the catalytic hydrogenation of unsaturated aldehyde compounds is provided according to a third aspect of the present invention.
Unsaturated aldehyde compounds, such as 2-isopropyl-5-methylhexanal, which is a selective reduction product of cocoa aldehyde, can be used as an intermediate of a diether electron donor, 2-isopropyl-2-isoamyl-1,3-dimethoxypropane (CN 102432439A), and a plurality of documents describe that the 2-isopropyl-2-isoamyl-1,3-dimethoxypropane can obtain excellent catalytic performance as an electron donor of an olefin polymerization catalyst.
The invention has the following advantages:
the metal content of the selective catalytic hydrogenation supported metal catalyst is low and is not higher than 0.8 percent; and only the reactant is needed to be used as a solvent, the post-treatment is simple, the catalyst can be repeatedly utilized, and the production cost is reduced.
The selective catalytic hydrogenation supported metal catalyst prepared by the invention can selectively hydrogenate double bonds to form saturated aldehyde compounds for unsaturated aldehyde compounds such as cocoa aldehyde, the selectivity can reach more than 90%, and the reaction conversion rate can reach more than 90%.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It should be apparent that the drawings in the following description are merely exemplary, and that other embodiments can be derived from the drawings provided by those of ordinary skill in the art without inventive effort.
The structures, the proportions, the sizes, and the like shown in the specification are only used for matching with the contents disclosed in the specification, so that those skilled in the art can understand and read the present invention, and do not limit the conditions for implementing the present invention, so that the present invention has no technical essence, and any modifications of the structures, changes of the proportion relation, or adjustments of the sizes, should still fall within the scope of the technical contents disclosed in the present invention without affecting the efficacy and the achievable purpose of the present invention.
FIG. 1 is a flow chart of the preparation of a selective catalytic hydrogenation supported metal catalyst provided in example 1 of the present invention;
fig. 2 is characterization data-STEM diagram of a selective catalytic hydrogenation supported metal catalyst provided in example 1 of the present invention, wherein (a) and (b) are electron micrographs of different positions of the catalyst prepared in example 2.
Detailed Description
The present invention is described in terms of particular embodiments, other advantages and features of the invention will become apparent to those skilled in the art from the following disclosure, and it is to be understood that the described embodiments are merely exemplary of the invention and that it is not intended to limit the invention to the particular embodiments disclosed. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
This example illustrates the preparation of a selective catalytic hydrogenation supported metal catalyst using the preparation scheme of the selective catalytic hydrogenation supported metal catalyst as shown in FIG. 1:
step one, pretreatment of an activated carbon carrier: immersing the pretreated activated carbon in nitric acid (3 mol/L) for 24 hours, washing with distilled water until the filtrate is neutral, calcining at 300 ℃ for 2 hours, and grinding to 100-150 meshes for later use.
Step two, preparation of the immobilized catalyst: mixing 6g of Pd (NO) 3 ) 2 Dissolving in 100ml of 0.2mol/LHCl solution, slowly dripping the solution on 550g of carrier, standing the impregnated material at room temperature for 12h, drying at 120 ℃ for 6h, cooling to room temperature to obtain loose powder, and roasting at 350-400 ℃ for 4h to obtain the catalyst with the metal mass content of 0.5%.
Example 2
This example is a method for preparing a supported metal catalyst for selective catalytic hydrogenation:
macroporous gamma-Al 2 O 3 Pretreatment of a carrier: measured Al (NO) 3 ) 3 ·9H 2 O is prepared into 0.5mol/L solution, 2.5mol/L ammonia water is slowly dripped under the condition of water bath at 85 ℃, the mixture is vigorously stirred while being dripped until precipitate is obtained, and the mixture is aged for 24 hours at 70 DEG CFiltering, washing the filter cake with a certain amount of ethanol for 3 times, transferring to a crucible, placing in a muffle furnace, and igniting at 550 ℃ for 4h to obtain gamma-Al 2 O 3 And (3) a carrier.
Step two, preparation of the immobilized catalyst: 5g of Pd (NO) 3 ) 2 Dissolving in 100ml of 0.2mol/LHCl solution, slowly dripping the solution on 550g of carrier, standing the impregnated material at room temperature for 12h, drying at 120 ℃ for 6h, cooling to room temperature to obtain loose powder, and roasting at 350-400 ℃ for 4h to obtain the catalyst with the metal mass content of 0.5%.
The electron micrograph of the solid catalyst prepared in this example is shown in fig. 2, wherein (a) and (b) are photographs taken of different positions of the solid supported catalyst under the same conditions, respectively, and it can be seen from (a) and (b) in fig. 1 that the white dots distributed relatively uniformly are metallic palladium, and it can also be seen approximately that the particle size of the palladium metallic catalyst is about 1 to 3 nanometers.
Example 3
This example is a method for preparing a supported metal catalyst for selective catalytic hydrogenation:
macroporous gamma-Al 2 O 3 Pretreatment of a carrier: measured Al (NO) 3 ) 3 ·9H 2 Preparing 0.5mol/L solution of O, slowly dripping 2.5mol/L ammonia water under the condition of 85 ℃ water bath, violently stirring while dripping until precipitate is obtained, aging the mixture at 70 ℃ for 24 hours, then carrying out suction filtration, washing a filter cake for 3 times by using a certain amount of ethanol, transferring the filter cake into a crucible, placing the crucible into a muffle furnace, and firing at 550 ℃ for 4 hours to obtain the gamma-Al 2 O 3 And (3) a carrier.
Step two, preparation of the immobilized catalyst: 5g of H 2 PtCl 6 ·6H 2 Dissolving O in 100ml of 0.2mol/L HCl solution, slowly dripping the solution on 380g of carrier, standing the impregnated material at room temperature for 12h, drying at 110 ℃ for 6h, cooling to room temperature to obtain loose powder, and roasting at 350-400 ℃ for 4h to obtain the catalyst with the metal mass content of 0.5%.
Example 4
This example is a method for preparing a supported metal catalyst for selective catalytic hydrogenation:
macroporous gamma-Al 2 O 3 Pretreatment of a carrier: measured Al (NO) 3 ) 3 ·9H 2 Preparing 0.5mol/L solution of O, slowly dripping 2.5mol/L ammonia water under the condition of 85 ℃ water bath, violently stirring while dripping until precipitate is obtained, aging the mixture at 70 ℃ for 24 hours, then carrying out suction filtration, washing a filter cake for 3 times by using a certain amount of ethanol, transferring the filter cake into a crucible, placing the crucible into a muffle furnace, and firing at 550 ℃ for 4 hours to obtain the gamma-Al 2 O 3 And (3) a carrier.
Step two, preparation of the immobilized catalyst: 2.4g of Pd (NO) 3 ) 2 Dissolving in 100ml of 0.2mol/LHCl solution, slowly dripping the solution on 550g of carrier, standing the impregnated material at room temperature for 12h, drying at 120 ℃ for 6h, cooling to room temperature to obtain loose powder, and roasting at 350-400 ℃ for 4h to obtain the catalyst with the metal mass content of 0.2%.
Example 5
This example is a method for preparing a supported metal catalyst for selective catalytic hydrogenation:
macroporous gamma-Al 2 O 3 Pretreatment of a carrier: measured Al (NO) 3 ) 3 ·9H 2 Preparing 0.5mol/L solution of O, slowly dripping 2.5mol/L ammonia water under the condition of 85 ℃ water bath, violently stirring while dripping until precipitate is obtained, aging the mixture at 70 ℃ for 24 hours, then carrying out suction filtration, washing a filter cake for 3 times by using a certain amount of ethanol, transferring the filter cake into a crucible, placing the crucible into a muffle furnace, and firing at 550 ℃ for 4 hours to obtain the gamma-Al 2 O 3 And (3) a carrier.
Step two, preparation of the immobilized catalyst: 9.5g of Pd (NO) 3 ) 2 Dissolving in 100ml of 0.2mol/LHCl solution, slowly dripping the solution on 550g of carrier, standing the impregnated material at room temperature for 12h, drying at 120 ℃ for 6h, cooling to room temperature to obtain loose powder, and roasting at 350-400 ℃ for 4h to obtain the catalyst with the metal mass content of 0.8%.
Comparative example 1
The comparative example is a preparation method of a selective catalytic hydrogenation supported metal catalyst:
macroporous gamma-Al 2 O 3 Pretreatment of a carrier: measured Al (NO) 3 ) 3 ·9H 2 Preparing 0.5mol/L solution of O, slowly dripping 2.5mol/L ammonia water under the condition of water bath at 85 ℃, vigorously stirring while dripping to obtain a precipitate, aging the mixture at 70 ℃ for 24 hours, carrying out suction filtration, washing a filter cake for 3 times by using a certain amount of ethanol, transferring the filter cake into a crucible, placing the crucible into a muffle furnace, and firing at 550 ℃ for 4 hours to obtain the gamma-Al 2 O 3 And (3) a carrier.
Step two, preparation of the immobilized catalyst: 12g of Pd (NO) 3 ) 2 Dissolving in 100ml of 0.2mol/LHCl solution, slowly dripping the solution on 550g of carrier, standing the impregnated material at room temperature for 12h, drying at 120 ℃ for 6h, cooling to room temperature to obtain loose powder, and roasting at 350-400 ℃ for 4h to obtain the catalyst with the metal mass content of 1%.
Comparative example 2
The comparative example is a preparation method of a selective catalytic hydrogenation supported metal catalyst:
macroporous gamma-Al 2 O 3 Pretreatment of a carrier: measured Al (NO) 3 ) 3 ·9H 2 Preparing 0.5mol/L solution of O, slowly dripping 2.5mol/L ammonia water under the condition of 85 ℃ water bath, violently stirring while dripping until precipitate is obtained, aging the mixture at 70 ℃ for 24 hours, then carrying out suction filtration, washing a filter cake for 3 times by using a certain amount of ethanol, transferring the filter cake into a crucible, placing the crucible into a muffle furnace, and firing at 550 ℃ for 4 hours to obtain the gamma-Al 2 O 3 And (3) a carrier.
Step two, preparation of the immobilized catalyst: 30g of Pd (NO) 3 ) 2 Dissolving in 100ml of 0.2mol/LHCl solution, slowly dripping the solution on 550g of carrier, standing the impregnated material at room temperature for 12h, drying at 120 ℃ for 6h, cooling to room temperature to obtain loose powder, and roasting at 350-400 ℃ for 4h to obtain the catalyst with the metal mass content of 2.5%.
Comparative example 3
The comparative example is a preparation method of a selective catalytic hydrogenation supported metal catalyst:
macroporous gamma-Al 2 O 3 Pretreatment of a carrier: measured Al (NO) 3 ) 3 ·9H 2 Preparing 0.5mol/L solution of O, slowly dripping 2.5mol/L ammonia water under the condition of 85 ℃ water bath, violently stirring while dripping until precipitate is obtained, aging the mixture at 70 ℃ for 24 hours, then carrying out suction filtration, washing a filter cake for 3 times by using a certain amount of ethanol, transferring the filter cake into a crucible, placing the crucible into a muffle furnace, and firing at 550 ℃ for 4 hours to obtain the gamma-Al 2 O 3 And (3) a carrier.
Step two, preparation of the immobilized catalyst: 163g of NiCl 2 ·6H 2 Dissolving O in 200ml of deionized water, slowly dripping the dissolved O on 100g of carrier, standing the impregnated material at room temperature for 12h, drying the impregnated material at 120 ℃ for 6h, cooling the dried impregnated material to room temperature to obtain loose powder, and roasting the loose powder at 350-400 ℃ for 4h to obtain the catalyst with the metal mass content of 40%.
Test example
The test example is the evaluation of the catalyst performance
The hydrogenation reaction is carried out on a 30mL adiabatic mini-fixed bed reactor, and the catalytic hydrogenation reaction is carried out by adopting the catalysts of examples 2-5 and the catalysts of comparative example 1 and comparative example 2 respectively; the catalytic effect was evaluated.
The method comprises the following specific operations: the loading of the catalyst is 20mL, and the prepared catalyst is firstly reduced by low hydrogen (V (H) 2 )：V(N 2 ) =5:95,GHSV = 120L/(h.g)) is subjected to in-situ prereduction for 12h according to a certain temperature-rising program; and reducing to the temperature required by the reaction after the reduction is finished.
Controlling the hydrogen flow by a gas flow regulating valve, mixing the hydrogen flow with 2-isopropyl-5-methyl-2-hexenal (cocoa aldehyde), preheating the mixture to a set temperature by a heating furnace, and entering a hydrogenation reactor. And (4) carrying out gas-liquid separation on the hydrogenated product by a high-pressure separator and a low-pressure separator, then feeding the product into a product tank, and sampling every 12 hours for chromatographic analysis. In the whole reaction process, the reaction temperature is controlled to be 50-100 ℃, the system pressure is 2-6MPa, the volume ratio of hydrogen to oil is 500-1000, and the liquid hourly space velocity is 0.6-1.0h -1 The process for synthesizing 2-isopropyl-5-methylhexanal by selective hydrogenation of 2-ethylhexenal double bond is investigated.
1. The comparison of the catalytic effects of different palladium metal contents is shown in table 1; aldehyde double bond hydrogenation catalyst N 2 The BET and TPR-CO results are shown in Table 2.
TABLE 1 evaluation results of catalysts with different active component contents in catalysis of double bond hydrogenation of cocoa aldehyde
TABLE 2 catalyst N for double bond hydrogenation of cocoa-aldehyde 2 BET and TPR-CO results
As can be seen from tables 1 and 2, the hydrogenation catalytic effect is not greatly different with the metal content of the metal palladium, which is bounded by the palladium content of 0.5%, but the pore volume and the specific surface area of the catalyst are slightly reduced with the increase of the Pd loading, which is mainly caused by the partial blockage of the carrier pore channels by the active metal due to the increase of the metal loading, so that the optimal catalyst metal content is not higher than 0.8%, which is greatly reduced compared with the transition metal content of 10-30% commonly used in the market.
2. The catalyst performance of example 2, example 3 and comparative example 3 are shown in table 3.
Table 3 table of catalyst performances of example 2 and example 3
As can be seen from table 3, the effect of using palladium (Pd) as the metal in the catalyst is better, and the content of Pd and Pt used in the present invention is 0.5%, but the content of Ni used in comparative example 3 is 40% to achieve the conversion rate of the present invention, and thus it can be seen that the present invention greatly reduces the content of the metal in the catalyst.
3. The effect of temperature on the catalyst is shown in table 4.
TABLE 4 influence of temperature on the catalyst
As can be seen from Table 4, (1) the 40% Ni catalyst has high hydrogenation activity, and the hydrogenation activity is higher at the lower temperature of 63.6 ℃, 3.74MPa and the liquid hourly volume space velocity of 0.39h -1 Under the condition of (1), the conversion rate of the cocoa aldehyde is 99.01 percent, the product is mainly C10 alcohol, the yield of the C10 aldehyde is only 19.35 percent, the content of the C10 aldehyde is gradually increased along with the reduction of the reaction temperature, and the selectivity of the catalyst to the C10 aldehyde is not obvious; (2) The Pt catalyst shows higher C = O hydrogenation selectivity, the activity of the catalyst is lower than that of Pd and Ni, the conversion rate of the cocoa-formaldehyde is only 12.28% at 94.1 ℃, the conversion rate and the contents of enol and saturated alcohol in the product are gradually increased along with the increase of the reaction temperature, and the product is mainly composed of the enol and the saturated alcohol. When the reaction temperature reaches 164.4 ℃, 3.66MPa and 0.41h -1 Under the condition, the conversion rate of the cocoa aldehyde reaches 84.28 percent, and the contents of C10 aldehyde, C10 enol and C10 alcohol in the product are respectively 10.14 percent, 30.78 percent and 30.00 percent.
The palladium catalyst produced in China mainly comprises Pd/A for hydrogen peroxide produced by Riming chemical research institute 2 O 3 The catalyst and the palladium catalyst used for gas purification, the palladium-containing mass fraction produced by a large-scale first organic chemical plant is more than or equal to 59 percent, the palladium-containing mass fraction is Q1060.84, the palladium/carbon catalyst produced by a large-scale chemical and physical research institute, the palladium/carbon catalyst and the palladium chloride catalyst produced by Shanghai petrochemical industry and general factory, the platinum-palladium series DH type dehydrogenation catalyst, CH dehydrogenation catalyst and DO type high-efficiency deoxidizer produced by the Lanzhou chemical of the Chinese academy and the like, the lowest content of palladium metal in the catalysts is more than or equal to 5 percent and less than 5 percent, and the catalysts can hardly play a role in catalysis, but the selective catalytic hydrogenation supported metal catalyst of the invention has the contents of metal Pd and Pt which are not more than 0.8 percent, better Pd effect and higher catalytic conversion rate.
Although the invention has been described in detail above with reference to a general description and specific examples, it will be apparent to one skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (2)
1. The application of a selective catalytic hydrogenation supported metal catalyst in synthesis of 2-isopropyl-5-methylhexanal by hydrogenation of double bonds of cocoa aldehyde is characterized in that the preparation method of the catalyst comprises the following steps:
firstly, pretreating a carrier needing to be loaded with transition metal, and forming to obtain a carrier compound;
dipping the active precursor, and then dropwise adding the active precursor onto the carrier compound to form a dipped material; drying and roasting the impregnated material to obtain the selective catalytic hydrogenation supported metal catalyst;
the carrier is macroporous gamma-Al 2 O 3 A carrier;
the macroporous gamma-Al 2 O 3 The carrier is pretreated by adding Al (NO) 3 ) 3 ·9H 2 Dissolving O in water to obtain Al (NO) 3 ) 3 Heating the solution in water bath, and adding Al (NO) 3 ) 3 Slowly adding ammonia water into the solution while stirring vigorously to obtain precipitate, aging the precipitate, suction filtering, washing the filter cake with ethanol for several times, and burning to obtain macroporous gamma-Al 2 O 3 A carrier;
the active precursor is a soluble salt solution of Pd.
2. Use according to claim 1, wherein the metal content of the catalyst is between 0.2 and 0.8%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210545559.7A CN114768799B (en) | 2022-05-19 | 2022-05-19 | Selective catalytic hydrogenation supported metal catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210545559.7A CN114768799B (en) | 2022-05-19 | 2022-05-19 | Selective catalytic hydrogenation supported metal catalyst and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114768799A CN114768799A (en) | 2022-07-22 |
| CN114768799B true CN114768799B (en) | 2022-11-29 |
Family
ID=82408448
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210545559.7A Active CN114768799B (en) | 2022-05-19 | 2022-05-19 | Selective catalytic hydrogenation supported metal catalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114768799B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5371299A (en) * | 1990-11-20 | 1994-12-06 | Himont Incorporated | Process for the preparation of diethers |
| CN102078810A (en) * | 2009-11-30 | 2011-06-01 | 葛昌华 | Oxide supported palladium hydrogenation catalyst and preparation method thereof |
| CN103157468A (en) * | 2013-03-14 | 2013-06-19 | 北京化工大学 | Low-content supported ruthenium-palladium bimetal hydrogenation catalyst and preparation method thereof |
| CN110551278A (en) * | 2019-08-26 | 2019-12-10 | 浙江绿科安化学有限公司 | Supported catalyst and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BRPI1003516B1 (en) * | 2010-07-29 | 2018-10-30 | Int Instituto Nac De Tecnologia | catalytic process of biomass hydrogenolysis, composition and use of biofuel obtained in aviation fuels |
-
2022
- 2022-05-19 CN CN202210545559.7A patent/CN114768799B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5371299A (en) * | 1990-11-20 | 1994-12-06 | Himont Incorporated | Process for the preparation of diethers |
| CN102078810A (en) * | 2009-11-30 | 2011-06-01 | 葛昌华 | Oxide supported palladium hydrogenation catalyst and preparation method thereof |
| CN103157468A (en) * | 2013-03-14 | 2013-06-19 | 北京化工大学 | Low-content supported ruthenium-palladium bimetal hydrogenation catalyst and preparation method thereof |
| CN110551278A (en) * | 2019-08-26 | 2019-12-10 | 浙江绿科安化学有限公司 | Supported catalyst and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| "载体对不饱和醛/酮中C=O选择性加氢催化剂性能的影响";崔静等;《工业催化》;20170531;第25卷(第5期);第58-60页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114768799A (en) | 2022-07-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107649124B (en) | Monoatomic dispersed noble metal catalyst and application thereof | |
| CN109261182B (en) | Preparation method of nitrogen-doped activated carbon-loaded Cu catalyst and application of nitrogen-doped activated carbon-loaded Cu catalyst in catalytic furfural hydrogenation | |
| CN108144653A (en) | A kind of oil hydrogenation catalyst preparation and catalyst and application | |
| CN108772087B (en) | Supported Pd catalyst for synthesizing benzaldehyde by oxidizing benzyl alcohol in solvent-free system and preparation method thereof | |
| CN109954507B (en) | Ni-Rh/αβ-MoXC composite catalyst, preparation and application | |
| CN108380208B (en) | Pd-Mg/C catalyst for preparing 2, 3-dichloropyridine by catalytic hydrogenation of 2,3, 6-trichloropyridine and preparation method thereof | |
| CN111905755A (en) | Catalyst for hydrogenation of 2,2,4, 4-tetramethyl-1, 3-cyclobutanedione and preparation method and application thereof | |
| CN113070078B (en) | Rare earth element-doped organic hydrogen storage medium hydrogenation monatomic catalyst and preparation method thereof | |
| CN112452340B (en) | Catalyst for preparing propylene by selective hydrogenation of propyne, preparation method and application thereof | |
| CN113501761A (en) | Method for continuously producing N, N-diethyl-1, 3-propane diamine by one-step method | |
| CN114768799B (en) | Selective catalytic hydrogenation supported metal catalyst and preparation method and application thereof | |
| CN109382100A (en) | A kind of selection plus hydrogen obtain compound catalyst and preparation method thereof between the zinc-containing metal of 1,4- butylene glycol | |
| CN105727972B (en) | A kind of method for preparing catalyst for synthesizing gas by reforming methane with co 2 | |
| CN108380219B (en) | Catalyst for preparing ethanol by ethyl acetate hydrogenation, and preparation method and application thereof | |
| CN101234352B (en) | Catalyst based on second metal of different group VIII of platinum and iridium used for opening ring compounds | |
| CN115739080A (en) | Preparation of Pt-based catalyst and application of Pt-based catalyst in preparation of chloroaniline by selective hydrogenation of chloronitrobenzene | |
| CN114054023B (en) | Preparation method and application of alloy monoatomic catalyst | |
| CN114082421A (en) | Hydrogenation catalyst, preparation method thereof and application thereof in hydrogenation of isooctylaldehyde | |
| CN112871159A (en) | Ru nano catalyst and preparation method and application thereof | |
| CN109894131B (en) | Dimethyl terephthalate (DMT) hydrogenation catalyst and preparation method thereof | |
| JPH02216A (en) | Chemical reaction method and proper catalyst for said reaction | |
| CN107876040B (en) | Catalyst for one-step synthesis of isobutyraldehyde from methanol and ethanol and preparation method thereof | |
| CN111013561A (en) | Preparation method of catalyst for liquid-phase hydrogenation of nitrobenzene to prepare aniline | |
| CN109772331B (en) | CoFe catalyst for preparing allyl alcohol by glycerol hydrogenation, and preparation method and application thereof | |
| CN114471608B (en) | Method for refining and purifying diethylene glycol through hydrofining |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder |
Address after: Cg05-223, building 8, yard 1, Zhongguancun East Road, Haidian District, Beijing 100086 Patentee after: Yanfeng Technology (Beijing) Co.,Ltd. Address before: Cg05-223, building 8, yard 1, Zhongguancun East Road, Haidian District, Beijing 100086 Patentee before: Yanfeng Technology (Beijing) Co.,Ltd. |
|
| CP01 | Change in the name or title of a patent holder | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A selective catalytic hydrogenation supported metal catalyst and its preparation method and application Granted publication date: 20221129 Pledgee: Zhongguancun Beijing technology financing Company limited by guarantee Pledgor: Yanfeng Technology (Beijing) Co.,Ltd. Registration number: Y2024990000041 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right |