CN110560046A - Platinum/titanium dioxide catalyst for dehydrogenation of dodecahydroethylcarbazole and preparation method thereof - Google Patents
Platinum/titanium dioxide catalyst for dehydrogenation of dodecahydroethylcarbazole and preparation method thereof Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 120
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 115
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 58
- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- 229910003446 platinum oxide Inorganic materials 0.000 title claims abstract description 27
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 118
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 30
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims abstract description 14
- 239000001509 sodium citrate Substances 0.000 claims abstract description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 9
- 239000010936 titanium Substances 0.000 claims abstract description 9
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 31
- 239000011259 mixed solution Substances 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 17
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 14
- 229910052700 potassium Inorganic materials 0.000 claims description 14
- 239000011591 potassium Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- 239000004568 cement Substances 0.000 claims description 5
- 238000011068 loading method Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 229910001414 potassium ion Inorganic materials 0.000 claims description 2
- HOQAPVYOGBLGOC-UHFFFAOYSA-N 1-ethyl-9h-carbazole Chemical compound C12=CC=CC=C2NC2=C1C=CC=C2CC HOQAPVYOGBLGOC-UHFFFAOYSA-N 0.000 abstract description 10
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 239000002245 particle Substances 0.000 abstract description 7
- 229910000510 noble metal Inorganic materials 0.000 abstract description 6
- 239000002270 dispersing agent Substances 0.000 abstract description 4
- 239000004094 surface-active agent Substances 0.000 abstract description 4
- 239000002923 metal particle Substances 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 2
- 239000000843 powder Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract 1
- 239000012467 final product Substances 0.000 abstract 1
- 238000009827 uniform distribution Methods 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 25
- 239000001257 hydrogen Substances 0.000 description 25
- 229910052739 hydrogen Inorganic materials 0.000 description 25
- 238000003860 storage Methods 0.000 description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 4
- 239000011232 storage material Substances 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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
- B01J23/42—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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
the invention discloses a platinum/titanium dioxide catalyst for dehydrogenation of dodecahydroethyl carbazole and a preparation method thereof, wherein the catalyst comprises the components of platinum, titanium and oxygen, and the mass percentages of the platinum, the titanium and the oxygen in the catalyst are respectively 0.5-5.0%, 56.9-59.7% and 38.1-39.8%; the preparation method comprises the following two steps: pretreating carrier titanium dioxide, and synthesizing a platinum/titanium dioxide catalyst; in ethylene glycol, sodium citrate is used as a reducing agent to prepare a supported platinum/titanium dioxide catalyst, and the obtained catalyst powder has small particle size and uniform distribution; the problems of large metal particles and uneven distribution can be effectively solved under the condition of not adding any surfactant and dispersant; the catalyst of the invention can keep the reaction activity and simultaneously reduce the dosage of noble metal platinum, the selectivity of the final product of the dehydrogenation reaction, namely ethyl carbazole, is improved to more than 97 percent, and the total dehydrogenation amount is improved to 5.75 percent by weight.
Description
Technical Field
The invention belongs to the technical field of organic liquid hydride hydrogen storage, and particularly relates to a platinum/titanium dioxide catalyst for dehydrogenating dodecahydroethyl carbazole and a preparation method thereof.
Background
in recent years, the problems of energy crisis and environmental deterioration are always puzzling all over the world, and experts and scholars continuously try to find a more efficient and environment-friendly energy source so as to reduce or even replace the status of the traditional fossil fuel in national production and life. Hydrogen energy is one of the most likely energy sources to be widely used, and has attracted attention in many fields due to its advantages such as large storage capacity, high calorific value, and environmental friendliness. In the field of fuel cells in particular, researchers have been trying to apply hydrogen fuel cells to mobile transportation devices to reduce the emission of toxic and harmful gases. However, the development of hydrogen energy in commercial application is not smooth due to the difficulties in hydrogen storage technology at present. For example: the safety of the pressurized gaseous hydrogen storage technology is low, and the transportation is inconvenient; the metal alloy hydrogen storage technology has non-ideal hydrogen storage capacity and low hydrogen absorption and desorption rate; the low-temperature liquefied hydrogen storage technology has large energy consumption and high cost.
When researchers research hydrocarbon organic substances and dehydrogenation reactions, the researchers find that hydrogen energy can be stored and utilized through reversible reaction of liquid organic hydride and hydrogen. The technology has the advantages of large hydrogen storage capacity, high hydrogen energy utilization rate, safety, stability, environmental friendliness, recyclable hydrogen storage material, capability of being transported for a long distance through the existing fossil fuel basic transportation equipment, and great reduction of commercial application cost.
Among the numerous reported organic liquid hydrogen storage materials, ethyl carbazole was the first proposed liquid organic hydrogen storage material that could achieve a hydrodeoxygenation cycle below 200 ℃. The theoretical hydrogen storage density is 5.79 wt%, and the purity of the released hydrogen can reach 99.9%, so that the hydrogen storage device not only meets the technical hydrogen storage indexes proposed by the U.S. department of energy, but also is environment-friendly.
Some literature reports indicate that the platinum and palladium catalysts can realize dehydrogenation reaction of dodecahydroethyl carbazole within the temperature range of 180-270 ℃. But different supported noble metal catalysts, such as: palladium/alumina, platinum/alumina, palladium/activated carbon, etc., all have low dehydrogenation efficiency (only about 60% of hydrogen can be released) at lower temperature, and the noble metal dosage is large. In order to better realize the commercial application of the organic liquid hydrogen storage material, the design and synthesis of a low-load metal catalyst capable of improving the dehydrogenation reaction rate of the dodecahydroethylcarbazole at a lower temperature are necessary.
Titanium dioxide is an N-type semiconductor, and is researched more in the field of photocatalysis for a long time due to the special photoelectric characteristic, but is not applied to dehydrogenation reaction of dodecahydroethylcarbazole.
the key to the current progress of the technology is how to design and develop a low-load metal catalyst capable of improving the dehydrogenation selectivity and the dehydrogenation rate of the dodecahydroethylcarbazole at a lower temperature, thereby effectively improving the energy conversion rate of the hydrogen fuel cell.
disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a platinum/titanium dioxide catalyst for dehydrogenation of dodecahydroethylcarbazole and a preparation method thereof, the catalyst provided by the invention can maintain excellent performance while reducing the loading of noble metal, so that the reaction time is greatly shortened, and the selectivity of the catalyst on final products of the dehydrogenation reaction, namely ethylcarbazole, is greatly improved; the synthesis process is simple and convenient, has low cost, and meets the conditions required by large-scale production.
In order to achieve the purpose, the invention adopts the following technical scheme:
The catalyst comprises the components of platinum, titanium and oxygen, wherein the mass percentages of the platinum, the titanium and the oxygen in the catalyst are respectively 0.5-5.0%, 56.9-59.7% and 38.1-39.8%.
the preparation method of the platinum/titanium dioxide catalyst for dehydrogenating dodecahydroethyl carbazole comprises the following steps:
Step one, pretreatment of carrier titanium dioxide, comprising the following specific steps:
1) adding titanium dioxide and ethylene glycol into a container, and placing the container on a magnetic stirrer to stir for 15-30 min, so that the titanium dioxide is uniformly dispersed in the ethylene glycol, wherein the titanium dioxide and the ethylene glycol correspond to 20ml of ethylene glycol according to the relation of the amount of each 1.0g of titanium dioxide;
2) heating the mixture of titanium dioxide and glycol to 110-130 ℃ while stirring, keeping the temperature for 10-20 min, stopping heating, and cooling to room temperature;
3) filtering the cooled mixture, washing the mixture by using deionized water and absolute ethyl alcohol until no ethylene glycol residue exists, and drying the mixture in a drying oven at the temperature of 60-80 ℃ for 6-12 hours; grinding after completely drying, and weighing required amount for later use;
Step two, synthesizing the platinum/titanium dioxide catalyst, which comprises the following specific steps:
1) Adding potassium chloroplatinate and ethylene glycol into a container, and placing the container on a magnetic stirrer to stir for 3-6 hours to fully disperse the potassium chloroplatinate in the ethylene glycol; weighing the pretreated titanium dioxide obtained in the first step, adding the titanium dioxide into the mixture of the ethylene glycol and the potassium chloroplatinate, and continuously stirring for 0.5-1.0 h to fully disperse the titanium dioxide; adding potassium chloroplatinate with corresponding mass according to the mass fraction of 0.5-5.0% of the platinum load, and adding ethylene glycol according to 20ml of ethylene glycol corresponding to each 1.0g of titanium dioxide);
2) adding a reducing agent sodium citrate according to the mass of 8-10 times of that of the potassium chloroplatinate, adding the reducing agent sodium citrate into the mixture, heating to 110-130 ℃, stirring for 20-30 min, stopping heating after the color of the mixed solution is changed from milky white to cement gray, and cooling to room temperature;
3) And filtering the mixed solution cooled to room temperature, washing the mixed solution by using deionized water and absolute ethyl alcohol until no ethylene glycol, sodium citrate, potassium ions and chloride ions remain, drying the mixed solution in a drying oven at the temperature of 60-80 ℃ for 6-12 h, and grinding the dried product to obtain the platinum/titanium dioxide catalyst for dehydrogenation of dodecahydroethylcarbazole.
According to the preparation method of the platinum/titanium dioxide catalyst for dehydrogenation of dodecahydroethylcarbazole, the amounts of potassium chloroplatinate, titanium dioxide, ethylene glycol and sodium citrate can be increased or decreased in equal proportion.
Compared with the prior art, the invention has the following advantages:
1. the preparation method has the advantages of simple and convenient preparation steps, mild preparation conditions and low preparation cost, and is suitable for large-scale production.
2. the platinum/titanium dioxide catalyst prepared by a water immersion method and hydrogen high-temperature reduction is usually adopted, and the particle size of platinum particles is larger. The catalyst prepared in the ethylene glycol can ensure that the platinum is dispersed more fully, so that the distribution of active sites is more uniform. According to the invention, sodium citrate is used as a reducing agent, and the sodium citrate shows mild reducibility within the temperature range of 110-130 ℃, so that the platinum metal is prevented from being agglomerated due to too high reduction speed to generate larger particles.
3. In the traditional liquid phase reduction method of the platinum/titanium dioxide catalyst, sodium borohydride solution or hydrazine hydrate is commonly used as a reducing agent, and a certain amount of dispersing agent or surfactant is added. The reducing agent has strong reducibility, so that noble metal particles are easy to agglomerate and grow up and are not beneficial to dispersion, and the prepared catalyst has larger particle size. According to the invention, in an ethylene glycol system, sodium citrate is used as a reducing agent to prepare the platinum/titanium dioxide catalyst, and the obtained catalyst can also keep small particle size and is uniformly distributed under the condition of not adding any dispersing agent or surfactant. The invention overcomes the defects of large metal particle size and uneven dispersion of the traditional method under the condition of not adding a dispersant and a surfactant.
4. according to the method, the titanium dioxide powder is pretreated by using the ethylene glycol at the temperature of 110-130 ℃, so that impurities adsorbed on the surface of the titanium dioxide can be cleaned, and the influence of the impurities on the adsorption process of the active metal platinum can be reduced.
5. The platinum/titanium dioxide catalyst prepared by the method has excellent performance, not only greatly shortens the reaction time, but also greatly reduces the dosage of noble metal platinum while maintaining the excellent reaction performance, and finally the selectivity of the dehydrogenation product ethyl carbazole is greatly improved to more than 97 percent, and the dehydrogenation amount reaches more than 5.75 percent by weight.
drawings
FIG. 1 is an X-ray diffraction photograph of a platinum/titanium dioxide catalyst prepared according to the present invention.
FIG. 2 is a peak fitting of the platinum element in the X-ray photoelectron spectrum of the platinum/titanium dioxide catalyst prepared in the present invention.
FIG. 3 shows the macro-morphology of the platinum/titanium dioxide catalyst prepared by the present invention at 50nm, 10nm and 5nm scales in a high-resolution transmission electron microscope photograph.
FIG. 4 is a 20nm scale high angle annular dark field image of a platinum/titanium dioxide catalyst made in accordance with the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments.
The first embodiment is as follows:
In this example, 1.5g of titanium dioxide and 30ml of ethylene glycol were added to a platinum/titanium dioxide catalyst for dehydrogenating dodecahydroethylcarbazole, and the mixture was stirred for 20min on a magnetic stirrer. Then heating to 120 ℃ and keeping for 20min, stopping heating, and cooling to room temperature. And filtering the cooled mixture, washing the mixture by using deionized water and absolute ethyl alcohol until no ethylene glycol residue exists, and drying the mixture in an oven at the temperature of 60 ℃ for 6 hours. After completely dried, the mixture was ground, and 1.0g of the ground mixture was weighed out for use.
Pouring 20ml of ethylene glycol into a container, adding 0.0249g of potassium chloroplatinate, placing on a magnetic stirrer for stirring for 3 hours, then adding weighed 1.0g of pretreated titanium dioxide into the mixture of the ethylene glycol and the platinum, continuing stirring for 0.5 hour, then weighing 0.249g of sodium citrate into the mixture, heating to 120 ℃, stirring for 25 minutes, stopping heating after the color of the mixed solution is changed from milky white to cement gray, and cooling to room temperature.
And filtering the mixed solution cooled to room temperature, washing the mixed solution by using deionized water and absolute ethyl alcohol until no ethylene glycol residue exists, drying the mixed solution in a drying oven at 60 ℃ for 12 hours, and grinding the dried product to obtain the platinum/titanium dioxide catalyst with the platinum mass loading of 1.0% (the mass percentages of platinum, titanium and oxygen are respectively 1.0%, 59.3% and 39.7%).
The catalyst was evaluated for performance and the results are shown in table 1.
TABLE 1 catalyst Performance during dehydrogenation of dodecahydroethylcarbazole to ethylcarbazole
| Reaction time (h) | Ethyl carbazole selectivity (%) | Amount of dehydrogenation (wt%) |
| 0 | 0 | 0 |
| 0.25 | 0 | 0.79 |
| 0.5 | 0 | 1.73 |
| 0.75 | 1.15 | 2.62 |
| 1 | 2.29 | 3.15 |
| 1.5 | 26.77 | 4.33 |
| 2 | 63.59 | 5.09 |
| 3 | 82.13 | 5.45 |
| 4 | 88.73 | 5.57 |
| 5 | 93.05 | 5.66 |
| 6 | 96.56 | 5.72 |
| 7 | 97.97 | 5.75 |
The catalyst prepared in this example is characterized, and its X-ray diffraction photo is shown in fig. 1, and its X-ray photoelectron spectroscopy photo is shown in fig. 2, so that it can be seen that the main catalytic function of platinum in the catalyst is elemental platinum. The transmission electron micrograph and the high-angle annular dark field image are shown in fig. 3 and 4, and it can be seen that the platinum has a small particle size and is uniformly dispersed.
The catalyst obtained in this example was evaluated for its performance, and after 7 hours of reaction time, the ethyl carbazole selectivity was 97.94% and the amount of dehydrogenation was 5.75 wt%. And the performance evaluation is carried out by adopting a commercial palladium/alumina catalyst in the prior art, after the reaction is carried out for 7 hours, the selectivity of the ethyl carbazole is 44.8%, and the dehydrogenation amount is 2.91 wt%.
example two:
in this example, 1.0g of titanium dioxide and 20ml of ethylene glycol were added to a platinum/titanium dioxide catalyst for dehydrogenating dodecahydroethylcarbazole, and the mixture was stirred for 15min on a magnetic stirrer. Then heating to 120 ℃ and keeping for 10min, stopping heating, and cooling to room temperature. The mixture was then filtered, washed with deionized water and absolute ethanol until no ethylene glycol remained, and dried in an oven at 70 ℃ for 8 h. After completely dried, ground and weighed 0.4g for use.
pouring 8ml of ethylene glycol into a container, adding 0.0248g of potassium chloroplatinate, placing the mixture on a magnetic stirrer for stirring for 3 hours, then adding weighed 0.4g of pretreated titanium dioxide into the mixture of the ethylene glycol and the platinum, continuing stirring for 0.5 hour, weighing 0.248g of sodium citrate into the mixture, heating to 110 ℃, stirring for 30 minutes, stopping heating after the color of the mixed solution is changed from milky white to cement gray, and cooling to room temperature.
and filtering the mixed solution cooled to room temperature, washing the mixed solution by using deionized water and absolute ethyl alcohol until no ethylene glycol residue exists, drying the mixed solution in a drying oven at 110 ℃ for 6 hours, and grinding the dried product to obtain the platinum/titanium dioxide catalyst with the platinum mass loading of 2.5% (the mass percentages of platinum, titanium and oxygen are respectively 2.5%, 58.4% and 39.1%).
the performance of the catalyst was evaluated, and after 7 hours of reaction, the ethyl carbazole selectivity was 99.12% and the amount of dehydrogenation was 5.77 wt%.
Example three:
In this example, 0.8g of titanium dioxide and 16ml of ethylene glycol were added to a platinum/titanium dioxide catalyst for dehydrogenating dodecahydroethylcarbazole, and the mixture was stirred for 30min on a magnetic stirrer. Then heating to 130 deg.C for 12min, stopping heating, and cooling to room temperature. The mixture was then filtered, washed with deionized water and absolute ethanol until no ethylene glycol remained, and dried in an oven at 110 ℃ for 6 h. After completely dried, the mixture was ground and 0.5g was weighed out for use.
Pouring 10ml of ethylene glycol into a container, adding 0.0655g of potassium chloroplatinate, placing the mixture on a magnetic stirrer for stirring for 3 hours, then adding 0.5g of weighed pretreated titanium dioxide into the mixture of the ethylene glycol and the platinum, continuing stirring for 0.5 hour, then weighing 0.524g of sodium citrate into the mixture, heating to 130 ℃, stirring for 20 minutes, stopping heating after the color of the mixed solution is changed from milky white to cement gray, and cooling to room temperature.
and filtering the cooled mixed solution, washing the mixed solution by using deionized water and absolute ethyl alcohol until no ethylene glycol residue exists, drying the mixed solution in a drying oven at the temperature of 60 ℃ for 6 hours, and grinding the dried mixed solution to obtain the platinum/titanium dioxide catalyst with the platinum mass loading of 5.0% (the mass percentages of platinum, titanium and oxygen are respectively 5.0%, 56.9% and 38.1%).
The performance of the catalyst was evaluated, and after 7 hours of reaction, the ethyl carbazole selectivity was 97.62% and the dehydrogenation amount was 5.75 wt%.
Claims (2)
1. A platinum/titania catalyst for dehydrogenation of dodecahydroethylcarbazole, characterized by: the catalyst comprises the components of platinum, titanium and oxygen, wherein the mass percentages of the platinum, the titanium and the oxygen in the catalyst are respectively 0.5-5.0%, 56.9-59.7% and 38.1-39.8%.
2. The method of preparing a platinum/titania catalyst for dehydrododecahydroethylcarbazole according to claim 1, wherein: the method comprises the following steps:
Step one, pretreatment of carrier titanium dioxide, comprising the following specific steps:
1) Adding titanium dioxide and ethylene glycol into a container, and placing the container on a magnetic stirrer to stir for 15-30 min, so that the titanium dioxide is uniformly dispersed in the ethylene glycol, wherein the titanium dioxide and the ethylene glycol correspond to 20ml of ethylene glycol according to the relation of the amount of each 1.0g of titanium dioxide;
2) Heating the mixture of titanium dioxide and glycol to 110-130 ℃ while stirring, keeping the temperature for 10-20 min, stopping heating, and cooling to room temperature;
3) Filtering the cooled mixture, washing the mixture by using deionized water and absolute ethyl alcohol until no ethylene glycol residue exists, and drying the mixture in a drying oven at the temperature of 60-80 ℃ for 6-12 hours; grinding after completely drying, and weighing required amount for later use;
Step two, synthesizing the platinum/titanium dioxide catalyst, which comprises the following specific steps:
1) Adding potassium chloroplatinate and ethylene glycol into a container, and placing the container on a magnetic stirrer to stir for 3-6 hours to fully disperse the potassium chloroplatinate in the ethylene glycol; weighing the pretreated titanium dioxide obtained in the first step, adding the titanium dioxide into the mixture of the ethylene glycol and the potassium chloroplatinate, and continuously stirring for 0.5-1.0 h to fully disperse the titanium dioxide; adding potassium chloroplatinate with the corresponding mass according to the mass fraction of platinum loading of 0.5-5.0%, and adding ethylene glycol into 20ml of ethylene glycol corresponding to every 1.0g of titanium dioxide;
2) adding a reducing agent sodium citrate according to the mass of 8-10 times of that of the potassium chloroplatinate, adding the reducing agent sodium citrate into the mixture, heating to 110-130 ℃, stirring for 20-30 min, stopping heating after the color of the mixed solution is changed from milky white to cement gray, and cooling to room temperature;
3) And filtering the mixed solution cooled to room temperature, washing the mixed solution by using deionized water and absolute ethyl alcohol until no ethylene glycol, sodium citrate, potassium ions and chloride ions remain, drying the mixed solution in a drying oven at the temperature of 60-80 ℃ for 6-12 h, and grinding the dried product to obtain the platinum/titanium dioxide catalyst for dehydrogenation of dodecahydroethylcarbazole.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113522279A (en) * | 2021-07-16 | 2021-10-22 | 西安海望能源科技有限公司 | Gold palladium catalyst for hydrogen desorption of dodecahydroethylcarbazole and preparation method thereof |
| CN115260084A (en) * | 2022-07-26 | 2022-11-01 | 江苏诺盟氢能技术有限公司 | Rapid dehydrogenation method of liquid organic matter and special Venturi ejector |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102553579A (en) * | 2011-05-27 | 2012-07-11 | 中国科学院福建物质结构研究所 | Preparation method of high-dispersity supported nano metal catalyst |
| CN103232382A (en) * | 2013-04-19 | 2013-08-07 | 西安交通大学 | Hydrogenation method of ethylcarbazole and dehydrogenation method of product thereof |
| CN106964346A (en) * | 2017-03-16 | 2017-07-21 | 西安交通大学 | A kind of palladium/graphene catalyst for being used for ten dihydro ethyl carbazole dehydrogenations and preparation method thereof |
| CN107537560A (en) * | 2016-06-29 | 2018-01-05 | 中国石油化工股份有限公司 | Dehydrogenation, preparation method and its application method |
| JP2018144016A (en) * | 2017-03-09 | 2018-09-20 | 千代田化工建設株式会社 | Dehydrogenation catalyst and method for producing the same, and dehydrogenation treatment method using the same |
-
2019
- 2019-09-09 CN CN201910849446.4A patent/CN110560046B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102553579A (en) * | 2011-05-27 | 2012-07-11 | 中国科学院福建物质结构研究所 | Preparation method of high-dispersity supported nano metal catalyst |
| CN103232382A (en) * | 2013-04-19 | 2013-08-07 | 西安交通大学 | Hydrogenation method of ethylcarbazole and dehydrogenation method of product thereof |
| CN107537560A (en) * | 2016-06-29 | 2018-01-05 | 中国石油化工股份有限公司 | Dehydrogenation, preparation method and its application method |
| JP2018144016A (en) * | 2017-03-09 | 2018-09-20 | 千代田化工建設株式会社 | Dehydrogenation catalyst and method for producing the same, and dehydrogenation treatment method using the same |
| CN106964346A (en) * | 2017-03-16 | 2017-07-21 | 西安交通大学 | A kind of palladium/graphene catalyst for being used for ten dihydro ethyl carbazole dehydrogenations and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| ZHAO JIANG ET AL.: "A experimental study on the dehydrogenation performance of dodecahydro-N-ethylcarbazole on M/TiO2 catalysts", 《INTERNATIONAL JOURNAL OF HYDROGEN ENERGY》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113522279A (en) * | 2021-07-16 | 2021-10-22 | 西安海望能源科技有限公司 | Gold palladium catalyst for hydrogen desorption of dodecahydroethylcarbazole and preparation method thereof |
| CN115260084A (en) * | 2022-07-26 | 2022-11-01 | 江苏诺盟氢能技术有限公司 | Rapid dehydrogenation method of liquid organic matter and special Venturi ejector |
| CN115260084B (en) * | 2022-07-26 | 2024-03-29 | 江苏诺盟氢能技术有限公司 | Rapid dehydrogenation method for liquid organic matters and special venturi ejector |
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