CN113680370A - Preparation method and application of single-atom catalyst for synthesizing 1, 2-dimethyl cyclohexanedicarboxylate from dimethyl phthalate - Google Patents
Preparation method and application of single-atom catalyst for synthesizing 1, 2-dimethyl cyclohexanedicarboxylate from dimethyl phthalate Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 83
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 title claims abstract description 64
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229960001826 dimethylphthalate Drugs 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 35
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 18
- 239000001257 hydrogen Substances 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 14
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 10
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000000919 ceramic Substances 0.000 claims description 9
- 238000005984 hydrogenation reaction Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 229910052763 palladium Inorganic materials 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 7
- 150000002500 ions Chemical class 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229910052707 ruthenium Inorganic materials 0.000 claims description 7
- 239000012279 sodium borohydride Substances 0.000 claims description 7
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 7
- 239000011780 sodium chloride Substances 0.000 claims description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000010453 quartz Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims 1
- 238000004817 gas chromatography Methods 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 4
- 238000012546 transfer Methods 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract 1
- 239000004014 plasticizer Substances 0.000 description 8
- 125000004429 atom Chemical group 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000004873 anchoring Methods 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 239000000796 flavoring agent Substances 0.000 description 2
- 235000019634 flavors Nutrition 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000008029 phthalate plasticizer Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 206010019695 Hepatic neoplasm Diseases 0.000 description 1
- 235000010254 Jasminum officinale Nutrition 0.000 description 1
- 240000005385 Jasminum sambac Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 231100000025 genetic toxicology Toxicity 0.000 description 1
- 230000001738 genotoxic effect Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 208000014018 liver neoplasm Diseases 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 210000002824 peroxisome Anatomy 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000027 toxicology Toxicity 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
- B01J21/185—Carbon nanotubes
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
- B01J29/042—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing iron group metals, noble metals or copper
- B01J29/044—Iron group metals or copper
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/303—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by hydrogenation of unsaturated carbon-to-carbon bonds
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Abstract
The invention belongs to the field of catalyst preparation, and particularly relates to a preparation method and application of a 1, 2-dimethyl cyclohexanedicarboxylate monatomic catalyst for synthesizing dimethyl phthalate. The preparation method is simple, the M/nitrogen-doped carbon nanotube monatomic catalyst has the advantages of large specific surface area, high mechanical strength, small mass transfer limit, more uniform dispersion of metal active components on the surface of a carrier and the like, has high atom utilization rate and longer service life, and is used for the reaction of synthesizing the 1, 2-cyclohexane dimethyl phthalate by hydrogenating dimethyl phthalate, and the reaction activity of the catalyst and the selectivity of the 1, 2-cyclohexane dimethyl phthalate are obviously improved.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a preparation method and application of a single-atom catalyst for synthesizing 1, 2-dimethyl cyclohexanedicarboxylate from dimethyl phthalate.
Background
Plasticizers are substances added to polymer systems that significantly increase the plasticity of the polymer system. Plasticizers are generally non-volatile, high boiling point liquid organic compounds, with only a few being low melting point compounds. The largest amount of the plasticizer is phthalate plasticizer, which accounts for more than 90 percent of the amount of the plasticizer. Researches prove that the phthalate plasticizer can initiate peroxisome proliferation to further induce liver tumors. When a phthalate-based plasticized article comes into contact with a lipophilic liquid, migration and leaching tend to occur in the plastic article, and thus the use of the phthalate-based plasticizer in plastic articles for medical instruments, foods, toys for children, and the like has been recently restricted or prohibited.
The 1, 2-cyclohexane dimethyl phthalate is an environment-friendly plasticizer, has better performance than phthalate, can greatly improve the flexibility of high polymers, has outstanding toxicological characteristics, does not present toxicity or genotoxicity, and can be naturally degraded in the environment, so the 1, 2-cyclohexane dimethyl phthalate can be used as a substitute of phthalate plasticizers. In addition, the 1, 2-cyclohexane dimethyl phthalate can also be used as an additive of perfume, has fruity flavor and jasmine flavor, has no toxicity or stimulation to skin, and can be prepared into various cosmetics. The 1, 2-cyclohexane dimethyl phthalate can be obtained by directly carrying out catalytic hydrogenation on dimethyl phthalate through a benzene ring, and the method is simple and can fully utilize the existing plasticizer production device. Most of traditional hydrogenation catalysts are metal catalysts, the phenomenon that catalytic activity is reduced due to the fact that active components are easy to agglomerate and lose exists more or less in hydrogenation reaction, the cost of the metal catalysts is relatively high, and the general atom utilization rate of the existing catalysts is low. At present, no document exists for preparing a hydrogenation catalyst with high atom utilization rate for synthesizing 1, 2-dimethyl cyclohexanedicarboxylate.
Disclosure of Invention
The invention provides a preparation method of a monatomic catalyst for synthesizing 1, 2-cyclohexane dimethyl phthalate through dimethyl phthalate hydrogenation. Aiming at the defects of easy agglomeration and loss of metal active components, low atom utilization rate and the like of the existing hydrogenation catalyst in the background technology, the invention prepares the Pd or Ni or Ru/nitrogen-doped carbon nanotube single-atom catalyst by using a dipping method by using a nitrogen-doped carbon nanotube as a carrier.
The preparation method comprises the following steps:
(1) preparation of nitrogen-doped carbon nanotube carrier
Using Fe/SBA-15 molecular sieve as a catalyst, using organic amine as a nitrogen source and a carbon source, placing a small porcelain boat filled with a certain amount of Fe/SBA-15 molecular sieve catalyst in a tube furnace, introducing nitrogen gas, heating for half an hour, then introducing a mixture of argon gas and organic amine, keeping for a period of time to obtain black powder, soaking the black powder in hydrofluoric acid for several hours to remove the catalyst, finally washing with deionized water to be neutral, and drying at 70 +/-10 ℃ to obtain the pure nitrogen-doped carbon nano-tubes.
Wherein the organic amine is one of diethylamine, triethylamine and ethylenediamine; the dosage of the molecular sieve catalyst is 0.5-1 g; the nitrogen flow is 60-80 ml/min; the temperature of the tubular furnace is 800 +/-50 ℃; keeping the time for 2-3 hours after the organic amine is introduced; the concentration of the used hydrofluoric acid is 2 +/-0.5 mol/L, and the soaking time is 3-5 hours.
Wherein the preparation method of the used Fe/SBA-15 molecular sieve catalyst comprises the following steps:
adding a certain amount of P123 into deionized water, dropwise adding 1mol/L HCl, stirring for 3 hours at 40 ℃, then gradually adding tetraethoxysilane and 1mol/L HCl, continuously stirring and aging for 24 hours at 40 ℃, pouring into a polytetrafluoroethylene-lined reaction kettle, sealing and crystallizing for 24 hours at 100 ℃, finally performing suction filtration and drying, and calcining for 3 hours at 550 ℃ to obtain the SBA-15 molecular sieve. Dispersing the SBA-15 molecular sieve into ethanol, dropwise adding a ferric nitrate solution, stirring and aging at 40 ℃ for 24 hours, and finally performing suction filtration and drying to obtain the Fe/SBA-15 molecular sieve catalyst.
(2) Preparation of monatomic catalyst
Dispersing the nitrogen-doped carbon nanotubes prepared in the step (1) in a dispersing wayMagnetically stirring in ion water at room temperature in ultrasonic bath for 1 hr to obtain suspension, adding soluble salt of Pd or Ni or Ru and NaCl water solution, stirring in ultrasonic bath at room temperature for 1 hr, and adding newly prepared NaBH4The aqueous solution was added to the slurry and stirred. Then filtering and separating, washing with deionized water, drying overnight to obtain the Pd or Ni or Ru/nitrogen-doped carbon nanotube monoatomic catalyst.
Preferably, the soluble salt is one of palladium chloride, nickel chloride and ruthenium chloride.
Preferably, the solid-to-liquid ratio of the nitrogen-doped carbon nanotubes to the deionized water is 1:100 +/-20; the dosage of the soluble salt of the metal M is calculated according to the mass of the metal M accounting for 3-7% of the carrier; the concentration of the NaCl solution is 0.01 mol/L; NaBH4The concentration of the solution is 0.5 +/-0.1 mol/L.
Further, the application of the M/nitrogen-doped carbon nanotube monatomic catalyst is to apply the monatomic catalyst to the dimethyl phthalate hydrogenation synthesis of the 1, 2-dimethyl cyclohexanedicarboxylate.
The specific application method is as follows:
in a fixed bed quartz tube reactor, the monatomic catalyst is arranged in the middle of the reactor, an inert ceramic ring is filled in the upper part of the reactor, hydrogen is introduced, dimethyl phthalate diluted by ethanol is introduced after the reaction temperature is raised, the reaction is carried out, the generated product is collected, and the detection and analysis are carried out by using a gas chromatograph with a hydrogen flame ion detector.
Wherein the catalyst is M/nitrogen-doped carbon nanotube monatomic catalyst (M is Pd, Ni and Ru), and the dosage of the monatomic catalyst is 1.0-1.5 g; the hydrogen flow is 70-80 ml/min, and the pressure is 3-4 MPa; the reaction temperature is 160-200 ℃; the space velocity is 5 +/-1 h-1。
The invention has the beneficial effects that: the prepared M/nitrogen-doped carbon nanotube monatomic catalyst has the advantages of strong acid and alkali resistance, large specific surface area, high mechanical strength, small mass transfer limit, good thermal stability and the like, and is an excellent hydrogenation catalyst carrier, after the carbon nanotube is doped with nitrogen atoms, the carbon atoms near the nitrogen atoms are positively charged due to the fact that the extra lone pair electrons of the nitrogen atoms can bring negative charges to an sp2 hybridized carbon skeleton delocalized pi system, so that the electron transfer characteristic and the chemical reaction activity of the carbon nanotube are enhanced, metal active components can be dispersed on the surface of the carbon nanotube more uniformly, the anchoring effect of the nitrogen atoms can effectively prevent agglomeration, the active components are not easy to lose, and the service life of the catalyst is greatly prolonged. The nitrogen-doped carbon nanotube is used as a carrier, so that metals such as Pd, Ni, Ru and the like are loaded on the surface of the nitrogen-doped carbon nanotube in a single atom form, the utilization rate of metal atoms can be improved, the metal consumption of the catalyst can be reduced, the cost is reduced, the full exposure of active atoms and the increase of active sites can also greatly improve the catalytic activity and the catalytic efficiency of the catalyst. The catalyst is used in the reaction of synthesizing 1, 2-cyclohexane dimethyl phthalate by hydrogenating dimethyl phthalate, avoids the rapid inactivation of the catalyst, prolongs the service life of the catalyst, and greatly improves the conversion rate of raw materials and the selectivity of the 1, 2-cyclohexane dimethyl phthalate.
Detailed Description
The present invention is further described below with reference to examples, but is not limited thereto.
Example 1
(1) Preparation of nitrogen-doped carbon nanotube carrier
A small ceramic boat filled with a certain amount of 0.5g Fe/SBA-15 molecular sieve catalyst is placed in a tube furnace, nitrogen is introduced at the flow rate of 60ml/min, and the boat is heated to 800 ℃ and kept for half an hour. A mixture of argon and diethylamine was then bubbled at a rate of 20mL/min and held for an additional period of time to give a black powder. Keeping the mixture at 800 ℃ for 2h, then soaking the black powder in 2mol/L hydrofluoric acid solution for 5h to remove the catalyst, finally washing the black powder to be neutral by deionized water, and drying the black powder at 70 ℃ to obtain the pure nitrogen-doped carbon nano-tube.
(2) Preparation of monatomic catalyst
Dispersing the nitrogen-doped carbon nano-tube prepared in the step (1) in deionized water, wherein the solid-to-liquid ratio of the nitrogen-doped carbon nano-tube to the deionized water is 1:100, magnetically stirring for 1h in ultrasonic bath at room temperature, and adding aqueous solution of palladium chloride and 0.01mol/L sodium chloride into the obtained suspension, wherein the dosage of the palladium chloride is calculated according to the mass of palladium atomsCalculated as 5% of the mass of the carrier, is stirred for 1h in an ultrasonic bath at room temperature, and then the newly prepared 0.5mol/L NaBH is added4The aqueous solution was added to the slurry and stirred. Then filtering and separating, washing with deionized water, drying overnight to obtain the Pd/nitrogen-doped carbon nanotube monoatomic catalyst.
(3) The use of the monatomic catalyst is as follows:
in a fixed bed quartz tube reactor (inner diameter 12mm, length 500mm), 1.5g of catalyst is loaded in the middle of the reactor, the upper part of the reactor is filled with an inert ceramic ring, hydrogen is introduced, the hydrogen flow is 80ml/min, after the reaction temperature is raised to 180 ℃, dimethyl phthalate diluted by ethanol is introduced for reaction, and the space velocity is 5h-1And collecting the generated product, and detecting and analyzing by using a gas chromatograph with a hydrogen flame ion detector.
Example 2
In example 1, the amount of palladium chloride was changed to 3% by mass of palladium atom based on the mass of the carrier.
The other operations were the same as in example 1.
Example 3
In example 1, the amount of palladium chloride was changed to 7% by mass of the carrier based on the mass of palladium atoms.
The other operations were the same as in example 1.
Example 4
The step (2) is changed into the following steps: adding aqueous solution of nickel chloride and 0.01mol/L sodium chloride into the obtained suspension, wherein the amount of nickel chloride is calculated by taking the mass of palladium atoms as 5 percent of the mass of the carrier, stirring for 1h in a room temperature ultrasonic bath, and then adding newly prepared 0.5mol/L NaBH4The aqueous solution was added to the slurry and stirred. Then filtering and separating, washing with deionized water, drying overnight, and obtaining the Ni/nitrogen-doped carbon nanotube monoatomic catalyst.
The other operations were the same as in example 1.
Example 5
The step (2) is changed into the following steps: adding an aqueous solution of ruthenium chloride and 0.01mol/L sodium chloride to the obtained suspension, wherein the amount of ruthenium chloride is 5% of the mass of the carrier based on the mass of palladium atoms, and then adding the mixture at room temperatureStirring for 1h in an ultrasonic bath, and then adding the newly prepared 0.5mol/L NaBH4The aqueous solution was added to the slurry and stirred. Then filtering and separating, washing with deionized water, drying overnight, and obtaining the Ru/nitrogen-doped carbon nanotube monoatomic catalyst.
The other operations were the same as in example 1.
Comparative example 1
The preparation method of the Pd/carbon nano-tube monatomic catalyst by using the carbon nano-tube as a carrier comprises the following steps:
a small ceramic boat filled with a certain amount of 0.5g Fe/SBA-15 molecular sieve catalyst is placed in a tube furnace, nitrogen is introduced at the flow rate of 60ml/min, and the boat is heated to 800 ℃ and kept for half an hour. Then a mixture of argon and methane was passed through at a rate of 20mL/min and held for an additional period of time to give a black powder. Keeping the temperature at 800 ℃ for 2h, then soaking the black powder in 2mol/L hydrofluoric acid solution for 5h to remove the catalyst, finally washing the black powder to be neutral by deionized water, and drying the black powder at 70 ℃ to obtain the carbon nanotube.
The other operations were the same as in example 1.
Comparative example 2
The Pd/active carbon catalyst is prepared by taking active carbon as a carrier, and the preparation process comprises the following steps:
dispersing activated carbon in deionized water, wherein the solid-to-liquid ratio of the activated carbon to the deionized water is 1:100, magnetically stirring for 1h in a room-temperature ultrasonic bath, adding an aqueous solution of palladium chloride and 0.01mol/L sodium chloride into the obtained suspension, wherein the using amount of the palladium chloride is calculated by taking the mass of palladium atoms as 5 percent of the mass of a carrier, stirring for 1h in the room-temperature ultrasonic bath, and then, newly preparing 0.5mol/L NaBH4The aqueous solution was added to the slurry and stirred. Then filtering and separating, washing with deionized water, and drying overnight to obtain the Pd/active carbon catalyst.
In a fixed bed quartz tube reactor (inner diameter 12mm, length 500mm), 1.5g Pd/active carbon catalyst is arranged in the middle of the reactor, an inert ceramic ring is filled at the upper part of the reactor, hydrogen is introduced, the hydrogen flow is 80ml/min, dimethyl phthalate diluted by ethanol is introduced after the reaction temperature is raised to 180 ℃, the reaction is carried out, and the space velocity is 5h-1And collecting the generated product, and detecting and analyzing by using a gas chromatograph with a hydrogen flame ion detector.
Comparative example 3
The nitrogen-doped carbon nanotube is directly used as a reaction catalyst.
In a fixed bed quartz tube reactor (with an inner diameter of 12mm and a length of 500mm), 1.5g of nitrogen-doped carbon nanotube is arranged in the middle of the reactor, an inert ceramic ring is filled at the upper part of the reactor, hydrogen is introduced, the hydrogen flow is 80ml/min, dimethyl phthalate diluted by ethanol is introduced after the reaction temperature is raised to 180 ℃, the reaction is carried out, and the space velocity is 5h-1And collecting the generated product, and detecting and analyzing by using a gas chromatograph with a hydrogen flame ion detector.
Comparative example 4
With Pd/Al2O3As a reaction catalyst, the preparation process of the catalyst is as follows:
taking 10g of Al2O3Dispersing in 50ml palladium chloride solution, the palladium chloride amount is calculated by the mass of palladium atom as 5% of the carrier mass, gradually dropping 10% ammonium bicarbonate solution under stirring to deposit palladium particles on the carrier surface, keeping pH at 9 during deposition, aging at 60 deg.C for 3 hr, drying at 80 deg.C for 12 hr after aging, calcining at 300 deg.C for 3 hr to obtain Pd/Al2O3A catalyst.
In a fixed bed quartz tube reactor (internal diameter 12mm, length 500mm), 1.5Pd/Al2O3The catalyst is arranged in the middle of the reactor, an inert ceramic ring is filled in the upper part of the reactor, hydrogen is introduced, the hydrogen flow is 40ml/min, the temperature is raised to 300 ℃ and kept for 2 hours to reduce the catalyst, and after the temperature is reduced to room temperature, nitrogen is introduced to passivate the catalyst for reaction. Introducing hydrogen gas before reaction at a flow rate of 80ml/min, heating to 180 deg.C, introducing dimethyl phthalate diluted with ethanol, and reacting at an airspeed of 5 hr-1And collecting the generated product, and detecting and analyzing by using a gas chromatograph with a hydrogen flame ion detector.
The performance of the catalysts obtained in the respective examples and comparative examples is shown in Table 1.
TABLE 1
The data of catalytic performances of the catalysts obtained in example 1 and comparative examples 1 to 4, which were reused 5 times, are shown in Table 2
TABLE 2
Compared with catalysts using active carbon or aluminum oxide and the like as carriers, the monatomic catalyst prepared by the invention has higher catalytic activity, and is used for synthesizing 1, 2-cyclohexane dimethyl phthalate by hydrogenating dimethyl phthalate, so that the selectivity of the product is greatly improved. And after the carbon nanotube carrier is doped with nitrogen, the metal active components are dispersed on the surface of the carbon nanotube more uniformly, the agglomeration phenomenon is effectively reduced due to the anchoring effect of nitrogen atoms, the active components are not easy to lose, the stability of the catalyst is further improved, the catalyst can be recycled for multiple times, and the service life of the catalyst is greatly prolonged. The catalyst prepared by the invention is an environment-friendly catalyst and has good industrial application prospect.
The present invention is not limited to the above-described embodiments, and any obvious improvements, substitutions or modifications can be made by those skilled in the art without departing from the spirit of the present invention.
Claims (8)
1. A preparation method of a single-atom catalyst for synthesizing 1, 2-cyclohexane dimethyl phthalate by dimethyl phthalate is characterized by comprising the following steps: the preparation method comprises the following steps:
(1) preparation of nitrogen-doped carbon nanotube carrier
Placing a small ceramic boat filled with a certain amount of Fe/SBA-15 molecular sieve catalyst in a tubular furnace, introducing nitrogen, heating for half an hour, then introducing a mixture of argon and organic amine, keeping for a period of time to obtain black powder, then soaking the black powder in hydrofluoric acid for several hours to remove the catalyst, finally washing the black powder to be neutral by using deionized water, and drying the black powder at 70 +/-10 ℃ to obtain the pure nitrogen-doped carbon nanotube.
(2) Preparation of monatomic catalyst
Dispersing the nitrogen-doped carbon nano-tube prepared in the step (1) in deionized water, magnetically stirring for 1h in a room-temperature ultrasonic bath, adding soluble salt of Pd or Ni or Ru and aqueous solution of NaCl into the obtained suspension, stirring for 1h in the room-temperature ultrasonic bath, and then adding NaBH4Adding the water solution into the slurry, stirring, filtering, separating, washing with deionized water, and drying overnight to obtain the Pd or Ni or Ru/nitrogen-doped carbon nanotube monoatomic catalyst.
2. The method for preparing the monatomic catalyst according to claim 1, wherein the organic amine in the step (1) is one of diethylamine, triethylamine, and ethylenediamine; the dosage of the molecular sieve catalyst is 0.5-1 g; the nitrogen flow is 60-80 ml/min; the temperature of the tubular furnace is 800 +/-50 ℃; keeping the time for 2-3 hours after the organic amine is introduced; the concentration of the used hydrofluoric acid is 2 +/-0.5 mol/L, and the soaking time is 3-5 hours.
3. The method for preparing the monatomic catalyst according to claim 1, wherein the Fe/SBA-15 molecular sieve catalyst used in step (1) is prepared by the following method:
adding a certain amount of P123 into deionized water, dropwise adding 1mol/L HCl, stirring for 3 hours at 40 ℃, then gradually adding tetraethoxysilane and 1mol/L HCl, continuously stirring and aging for 24 hours at 40 ℃, pouring into a polytetrafluoroethylene-lined reaction kettle, sealing and crystallizing for 24 hours at 100 ℃, finally performing suction filtration and drying, and calcining for 3 hours at 550 ℃ to obtain the SBA-15 molecular sieve;
dispersing the SBA-15 molecular sieve into ethanol, dropwise adding a ferric nitrate solution, stirring and aging at 40 ℃ for 24 hours, and finally performing suction filtration and drying to obtain the Fe/SBA-15 molecular sieve catalyst.
4. The method for preparing a monatomic catalyst according to claim 1, wherein the soluble salt in the step (2) is one of palladium chloride, nickel chloride, and ruthenium chloride.
5. The method for preparing the monatomic catalyst according to claim 1, wherein the solid-to-liquid ratio of the nitrogen-doped carbon nanotubes to the deionized water in the step (2) is 1:100 ± 20; the dosage of the soluble salt of the metal M is calculated according to the mass of the metal M accounting for 3-7% of the carrier; the concentration of the NaCl solution is 0.01 mol/L; NaBH4The concentration of the solution is 0.5 +/-0.1 mol/L.
6. The application of the monatomic catalyst is characterized in that the monatomic catalyst is used for synthesizing 1, 2-cyclohexane dimethyl phthalate through hydrogenation of dimethyl phthalate.
7. A method for synthesizing 1, 2-cyclohexane dimethyl phthalate by using monatomic catalyst in dimethyl phthalate hydrogenation is characterized by comprising the steps of arranging the monatomic catalyst in a fixed bed quartz tube reactor, filling an inert ceramic ring at the upper part of the reactor, introducing hydrogen, raising the reaction temperature, introducing dimethyl phthalate diluted by ethanol, reacting, collecting a generated product, and detecting and analyzing by using a gas chromatography with a hydrogen flame ion detector.
8. The method of claim 7, wherein the amount of the monatomic catalyst is 1.0 to 1.5 g; the hydrogen flow is 70-80 ml/min, and the pressure is 3-4 MPa; the reaction temperature is 160-200 ℃; the space velocity is 5 +/-1 h-1。
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