CN117123250A - Nitrogen-doped graphene oxide/porous carbon supported metal catalyst and preparation method and application thereof - Google Patents
Nitrogen-doped graphene oxide/porous carbon supported metal catalyst and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 53
- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 40
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 21
- 239000002184 metal Substances 0.000 title claims abstract description 21
- 239000010948 rhodium Substances 0.000 claims abstract description 32
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 28
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 25
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 22
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 22
- 239000000661 sodium alginate Substances 0.000 claims abstract description 22
- 239000011259 mixed solution Substances 0.000 claims abstract description 18
- 239000000243 solution Substances 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 239000006185 dispersion Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 238000007037 hydroformylation reaction Methods 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 8
- -1 nitrogen-containing compound Chemical class 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 2
- 239000003495 polar organic solvent Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 16
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000002474 experimental method Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 229920000620 organic polymer Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 3
- XZOYHFBNQHPJRQ-UHFFFAOYSA-N 7-methyloctanoic acid Chemical compound CC(C)CCCCCC(O)=O XZOYHFBNQHPJRQ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 238000007172 homogeneous catalysis Methods 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 2
- JRPPVSMCCSLJPL-UHFFFAOYSA-N 7-methyloctanal Chemical compound CC(C)CCCCCC=O JRPPVSMCCSLJPL-UHFFFAOYSA-N 0.000 description 2
- OGDVHTQGJVGROD-UHFFFAOYSA-N [Na].[Na].[Na].c1ccc(cc1)P(c1ccccc1)c1ccccc1 Chemical class [Na].[Na].[Na].c1ccc(cc1)P(c1ccccc1)c1ccccc1 OGDVHTQGJVGROD-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- SZFRZEBLZFTODC-UHFFFAOYSA-N 2,3,4-trimethylpent-2-ene Chemical compound CC(C)C(C)=C(C)C SZFRZEBLZFTODC-UHFFFAOYSA-N 0.000 description 1
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical compound CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 1
- ILPBINAXDRFYPL-UHFFFAOYSA-N 2-octene Chemical compound CCCCCC=CC ILPBINAXDRFYPL-UHFFFAOYSA-N 0.000 description 1
- WTPYRCJDOZVZON-UHFFFAOYSA-N 3,5,5-Trimethylhexanal Chemical compound O=CCC(C)CC(C)(C)C WTPYRCJDOZVZON-UHFFFAOYSA-N 0.000 description 1
- DFVOXRAAHOJJBN-UHFFFAOYSA-N 6-methylhept-1-ene Chemical compound CC(C)CCCC=C DFVOXRAAHOJJBN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000764238 Isis Species 0.000 description 1
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- OMWMZVHNHFMUQJ-UHFFFAOYSA-N sodium;triphenylphosphane Chemical class [Na].[Na].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 OMWMZVHNHFMUQJ-UHFFFAOYSA-N 0.000 description 1
- VYFPSYVVFFFYBF-UHFFFAOYSA-N sodium;triphenylphosphane Chemical class [Na].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 VYFPSYVVFFFYBF-UHFFFAOYSA-N 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
- C07C45/505—Asymmetric hydroformylation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a nitrogen-doped graphene oxide/porous carbon supported metal catalyst, and a preparation method and application thereof. The preparation method of the catalyst comprises the following steps: (a) Mixing nitrogen-doped graphene oxide/porous carbon with a solvent to obtain a mixed solution A; (b) Mixing the mixed solution A with sodium alginate solution to obtain mixed solution B; (c) The mixed solution B is mixed with a rhodium-containing compound, and washed and dried. The nitrogen-doped graphene oxide/porous carbon supported metal catalyst can be used for taking the preparation cost, the catalyst activity and the product selectivity into consideration. After the reaction is finished, the catalyst composition has good recovery effect, can be recycled, reduces the production cost and is beneficial to industrial production and application.
Description
Technical Field
The invention belongs to the technical field of hydroformylation, and particularly relates to a nitrogen-doped graphene oxide/porous carbon supported metal catalyst, and a preparation method and application thereof.
Background
Industrial hydroformylation processes are largely divided into homogeneous catalysis and two-phase catalysis. Homogeneous catalysis has the advantages of high reaction rate, high activity and the like, but the product and the catalyst are required to be separated by adopting a distillation method. As the carbon chain grows, the boiling point of the higher aldehydes of the hydroformylation reaction product increases, requiring higher temperatures to separate the products. The rhodium catalyst with high activity is easy to deactivate at high temperature, so that the high-temperature distillation used in the homogeneous catalysis process can cause the loss of the noble metal catalyst, and the production cost is increased.
CN111470962a discloses a process for the preparation of isononanoic acid from mixed isomeric octenes. The method for preparing isononanoic acid by the hydroformylation and oxidation of mixed isomeric octenes. In the presence of a novel porous organic polymer supported rhodium (Rh) based catalyst, mixed isooctene is subjected to hydroformylation reaction to obtain isononanal, and then isononanal is subjected to oxidation reaction with oxygen-containing gas in an oxidation reactor at low temperature and low pressure under the condition of no catalyst to generate isononanoic acid. The hydroformylation reaction comprises the following specific processes: pumping liquid mixed isomeric octene into a reactor by using a high-pressure pump, and carrying out hydroformylation reaction on the liquid mixed isomeric octene and synthesis gas in the presence of a catalyst at a certain pressure and a certain temperature to obtain isononyl aldehyde; the mixed isomeric octene consists of 2, 4-trimethyl-1-pentene and 2, 4-trimethyl-2-pentene, and the synthetic gas is CO and H 2 A mixed gas is formed; the catalyst is a high-dispersion heterogeneous solid catalyst composed of a main active component and a carrier, wherein the main active component is Rh, and the carrier is a porous organic polymer, namely a Rh-based catalyst immobilized by the porous organic polymer; the porous organic polymer is a polymer which is formed by modifying and then polymerizing an organic ligand containing P and optional N or S functional elements through vinyl functional groups, and has a rich multistage pore structure and a large specific surface area; the mass fraction of the main active component is 0.01-20%, and the rest isIs a carrier.
Although the method improves the activity of the catalyst, the method cannot achieve the effects of lower production cost, higher catalyst activity and product selectivity.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a novel nitrogen-doped graphene oxide/porous carbon supported metal catalyst and a preparation method thereof, wherein the catalyst improves the reactivity and aldehyde selectivity of a hydroformylation reaction by carrying out nitrogen doping on graphene oxide/porous carbon and adding sodium alginate in the preparation process, and the preparation cost is lower. In addition, the catalyst has a good recovery effect after the hydroformylation reaction is finished as a heterogeneous catalyst, and the separated and recovered catalyst composition can be recycled.
The first aspect of the invention provides a preparation method of a nitrogen-doped graphene oxide/porous carbon supported metal catalyst, which comprises the following steps:
(a) Mixing nitrogen-doped graphene oxide/porous carbon with a solvent to obtain a mixed solution A;
(b) Mixing the mixed solution A with sodium alginate solution to obtain mixed solution B;
(c) The mixed solution B is mixed with a rhodium-containing compound, and washed and dried.
In the present invention, "graphene oxide/porous carbon" refers to graphene oxide or porous carbon.
According to some embodiments of the preparation method of the present invention, the preparation method of nitrogen-doped graphene oxide/porous carbon comprises: and mixing the graphene oxide/porous carbon dispersion liquid with a nitrogen-containing compound, stirring, performing hydrothermal reaction, cooling, cleaning, filtering and vacuum drying.
According to some embodiments of the preparation method of the present invention, the weight ratio of graphene oxide/porous carbon dispersion to nitrogen-containing compound is 1:10-1:300, preferably 1:50-1:300, such as but not limited to: 1:50-1:300, 1:50-1:200, 1:100-1:300, 1:100-1:200, 1:50-1:100.
According to some embodiments of the process of the invention, the nitrogen-containing compound is urea.
According to some embodiments of the preparation method of the present invention, the content of graphene oxide/porous carbon is 1.0 to 6.0mg per mL of the dispersion of graphene oxide/porous carbon. Namely: the concentration of graphene oxide/porous carbon in the graphene oxide/porous carbon dispersion liquid is 1.0-6.0mg/mL.
According to some embodiments of the methods of preparation of the present invention, the conditions of the hydrothermal reaction include: the temperature is 100-200deg.C, and the time is 6-36h.
According to some embodiments of the preparation method of the present invention, the solvent is added in an amount of 400-600mL per g of nitrogen-doped graphene oxide/porous carbon. Namely: the addition amount of the nitrogen doped graphene oxide/porous carbon is 1g/400-600mL of solvent.
According to some embodiments of the preparation method of the present invention, the solvent is selected from at least one of water, a polar organic solvent and a nonpolar organic solvent, preferably water.
According to some embodiments of the preparation method of the present invention, the content of sodium alginate is 0.005-0.01g per mL of sodium alginate solution. Namely: the concentration of sodium alginate in the sodium alginate solution is 0.005-0.01g/mL.
According to some embodiments of the preparation method of the present invention, the volume ratio of the mixed solution A to the sodium alginate solution is 300:50-100.
According to some embodiments of the preparation process of the present invention, the concentration of the rhodium-containing compound is 0.01 to 0.5mg/mL in terms of rhodium content.
According to some embodiments of the preparation process of the invention, the rhodium-containing compound is used in an amount such that: the content of rhodium in elemental form is 0.1 to 10% by weight, based on the weight of the metal catalyst.
According to some embodiments of the preparation process of the present invention, the rhodium-containing compound is represented by formula (I):
Rh(L 1 ) x (L 2 ) y (L 3 ) z formula (I)
Wherein L is 1 Selected from carbonyl, halogen, acetylacetone, diphenyl phosphine, cyclooctadiene, norbornene and triphenylphosphine; l (L) 2 And L 3 And are the same or different and are each independently selected from hydrogen, carbonyl, chlorine, acetylacetone, diphenyl phosphine, cyclooctadiene, norbornene and triphenylphosphine, x is an integer from 1 to 3, y and z are each independently selected from an integer from 0 to 4, and x+y+z is less than or equal to 5.
According to some embodiments of the preparation methods of the present invention, the rhodium-containing compound is selected from at least one of rhodium trichloride, rhodium acetylacetonate dicarbonyl, rhodium monochloro-carbonyl bis (trisulfonated triphenylphosphine trisodium salt), rhodium monochloro-carbonyl bis (disulfonated triphenylphosphine disodium salt), rhodium monochloro-carbonyl bis (monosulfonated triphenylphosphine monosodium salt) rhodium, and rhodium monohydrocarbonyl tris (trisulfonated triphenylphosphine trisodium salt).
According to some embodiments of the preparation methods of the present invention, a preparation method of a nitrogen-doped graphene oxide/porous carbon supported metal catalyst includes, but is not limited to: mixing nitrogen-doped graphene oxide/porous carbon and a solvent, and performing ultrasonic dispersion to obtain a mixed solution A; mixing the mixed solution A with sodium alginate solution to obtain mixed solution B; and adding a rhodium-containing compound into the mixed solution B, stirring overnight under the protection of nitrogen, and finally washing the solid, carrying out suction filtration and vacuum drying to obtain the uniformly dispersed rhodium-loaded nitrogen-doped graphene oxide/porous carbon catalyst.
The second aspect of the invention provides the nitrogen-doped graphene oxide/porous carbon supported metal catalyst prepared by the preparation method.
According to some embodiments of the catalyst of the present invention, the rhodium content is 0.1 to 10% by weight, calculated as element, based on the weight of the metal catalyst. In the present invention, the content of rhodium in the metal catalyst can be changed by adjusting the concentration of the leaching solution of rhodium, but it was found by measurement that the effect of the metal catalyst of the present invention is more excellent when the content of rhodium is in the range of 0.1 to 10% by weight in terms of element.
The third aspect provides the preparation method and the application of the nitrogen-doped graphene oxide/porous carbon supported metal catalyst in olefin hydroformylation.
The invention has the beneficial effects that:
the nitrogen-doped graphene oxide/porous carbon supported metal catalyst can be used for taking the preparation cost, the catalyst activity and the product selectivity into consideration. After the reaction is finished, the catalyst composition has good recovery effect, can be recycled, reduces the production cost and is beneficial to industrial production and application.
Detailed Description
In order that the invention may be more readily understood, the invention will be described in detail below with reference to the following examples, which are given by way of illustration only and are not limiting of the scope of application of the invention.
[ example 1 ]
Preparing graphene oxide dispersion liquid with the concentration of 4mg/mL (the content of graphene oxide is 4mg relative to the graphene oxide dispersion liquid per mL), adding urea in a state of intense stirring, wherein the weight ratio of the dispersion liquid to the urea is 1:200, intense stirring for 2 hours at room temperature, pouring the mixed liquid into a hydrothermal synthesis reaction kettle, and heating for 12 hours at 180 ℃. And then cooling to room temperature, cleaning, filtering and drying in vacuum overnight to obtain the nitrogen doped graphene oxide.
Weighing 0.6g of nitrogen doped graphene oxide, adding into 300mL of ultrapure water, vigorously sonicating for 2 hours, adding 80mL of sodium alginate solution (0.005 g/mL, sodium alginate content is 0.005g relative to each mL of sodium alginate solution), stirring for 30 minutes, and adding 0.032g of RhCl 3 ·3H 2 O, stirring overnight at room temperature under nitrogen blanket. Finally, cleaning the solid, carrying out suction filtration, and carrying out vacuum drying at 65 ℃ to obtain the target catalyst.
The content of rhodium in elemental form was 1.4% by weight based on the weight of the metal catalyst as determined by inductively coupled plasma mass spectrometry (ICP).
[ example 2 ]
The experimental method was the same as in example 1, wherein the weight ratio of graphene oxide dispersion to urea was changed to 1:100 when preparing nitrogen-doped graphene oxide, and the rest of the experimental conditions were unchanged.
[ example 3 ]
The experimental method was the same as in example 1, wherein the weight ratio of graphene oxide dispersion to urea was changed to 1:50 when preparing nitrogen-doped graphene oxide, and the rest of the experimental conditions were unchanged.
[ example 4 ]
The experimental method was the same as in example 1, wherein the weight ratio of graphene oxide dispersion to urea was changed to 1:10 when preparing nitrogen-doped graphene oxide, and the rest of the experimental conditions were unchanged.
[ example 5 ]
The experimental method was the same as in example 1, wherein the weight ratio of graphene oxide dispersion to urea was changed to 1:300 when preparing nitrogen-doped graphene oxide, and the rest of the experimental conditions were unchanged.
[ example 6 ]
The experimental procedure is the same as in example 2, wherein the concentration of the added sodium alginate solution is 0.006g/mL, and the rest of the experimental conditions are unchanged.
[ example 7 ]
The experimental procedure was the same as in example 2, wherein the concentration of the sodium alginate solution added was 0.008g/mL, and the remaining experimental conditions were unchanged.
[ example 8 ]
The experimental method is the same as in example 2, wherein the concentration of the added sodium alginate solution is 0.01g/mL, and the rest experimental conditions are unchanged.
[ example 9 ]
The experimental procedure is the same as in example 1, wherein the hydrothermal 180℃heating for 12 hours is changed to 120℃heating for 36 hours, and the rest of the experimental conditions are unchanged.
[ example 10 ]
The experimental procedure is the same as in example 1, wherein the hydrothermal 180℃heating for 12h is changed to 250℃heating for 12h, and the rest of the experimental conditions are unchanged.
[ example 11 ]
The experimental procedure is the same as in example 1, wherein graphene oxide is replaced with porous carbon, nitrogen doped porous carbon is used, and the rest of the experimental conditions are unchanged.
Comparative example 1
The experimental method is the same as in example 2, wherein the graphene oxide is not doped with nitrogen, and the rest of the experimental conditions are unchanged.
Comparative example 2
The experimental method is the same as in example 2, wherein sodium alginate is not added in the catalyst preparation process, and the rest experimental conditions are unchanged.
[ comparative example 3 ]
The experimental procedure is the same as in example 11, wherein the porous carbon is not doped with nitrogen and the rest of the experimental conditions are unchanged.
[ comparative example 4 ]
The experimental method is the same as in example 11, wherein sodium alginate is not added in the catalyst preparation process, and the rest experimental conditions are unchanged.
[ test case ]
The catalysts of examples 1-11 and comparative examples 1-4 were tested separately for activity and selectivity using a laboratory autoclave evaluation apparatus. The reaction vessel was placed in a heating mantle at a volume of 50 mL. The measurement conditions of the catalyst activity and selectivity used are shown in table 1:
TABLE 1 determination conditions of catalyst Activity and Selectivity
| Reaction temperature | Reaction pressure | Composition of synthesis gas | Reaction time | Olefin feedstock | Solvent(s) |
| 100℃ | 4MPa | H 2 :CO＝1:1 | 10h | 2-octene | Toluene (toluene) |
The catalyst activity and selectivity are characterized by olefin conversion and aldehyde selectivity, which are calculated as follows:
the test results are shown in Table 2.
TABLE 2 effect of catalyst on hydroformylation of 2-octene
As can be seen from the comparative examples, nitrogen doping of graphene oxide and addition of sodium alginate during the catalyst preparation process are both beneficial to improving the reactivity and selectivity of the catalyst. And the preparation cost is lower in terms of the preparation cost.
What has been described above is merely a preferred example of the present invention. It should be noted that other equivalent modifications and improvements will occur to those skilled in the art, and are intended to be within the scope of the present invention, as a matter of common general knowledge in the art, in light of the technical teaching provided by the present invention.
Claims (11)
1. A preparation method of a nitrogen-doped graphene oxide/porous carbon supported metal catalyst comprises the following steps:
(a) Mixing nitrogen-doped graphene oxide/porous carbon with a solvent to obtain a mixed solution A;
(b) Mixing the mixed solution A with sodium alginate solution to obtain mixed solution B;
(c) The mixed solution B is mixed with a rhodium-containing compound, and washed and dried.
2. The preparation method according to claim 1, wherein the preparation method of the nitrogen-doped graphene oxide/porous carbon comprises: and mixing the graphene oxide/porous carbon dispersion liquid with a nitrogen-containing compound, stirring, performing hydrothermal reaction, cooling, cleaning, filtering and vacuum drying.
3. The method of preparation according to claim 2, characterized in that the weight ratio of graphene oxide/porous carbon dispersion to nitrogen-containing compound is 1:10-1:300, preferably 1:50-1:300.
4. A method of preparation according to claim 2 or 3, wherein the nitrogen-containing compound is urea.
5. The production method according to any one of claims 2 to 4, wherein the content of graphene oxide/porous carbon is 1.0 to 6.0mg per mL of the graphene oxide/porous carbon dispersion.
6. The method of any one of claims 2-5, wherein the hydrothermal reaction conditions include: the temperature is 100-200deg.C, and the time is 6-36h.
7. The production method according to any one of claims 1 to 6, wherein the solvent is added in an amount of 400 to 600mL per g of nitrogen-doped graphene oxide/porous carbon; and/or the number of the groups of groups,
the solvent is at least one selected from water, polar organic solvents and nonpolar organic solvents, preferably water.
8. The preparation method according to any one of claims 1 to 7, wherein the content of sodium alginate is 0.005 to 0.01g per mL of sodium alginate solution; and/or the number of the groups of groups,
the volume ratio of the mixed solution A to the sodium alginate solution is 300:50-100.
9. The production process according to any one of claims 1 to 8, wherein the concentration of the rhodium-containing compound is 0.01 to 0.5mg/mL in terms of rhodium content; and/or the number of the groups of groups,
the rhodium-containing compound is used in an amount such that: the content of rhodium in elemental form is 0.1 to 10% by weight, based on the weight of the metal catalyst.
10. A nitrogen-doped graphene oxide/porous carbon supported metal catalyst prepared according to the preparation method of any one of claims 1 to 9;
preferably, the rhodium content is 0.1 to 10% by weight, calculated as element, based on the weight of the metal catalyst.
11. The preparation method of any one of claims 1 to 9 and the use of the nitrogen doped graphene oxide/porous carbon supported metal catalyst of claim 10 in the hydroformylation of olefins.
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