CN110732325A - ruthenium-carbon catalyst, and preparation method and application thereof - Google Patents
ruthenium-carbon catalyst, and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 71
- NCPHGZWGGANCAY-UHFFFAOYSA-N methane;ruthenium Chemical compound C.[Ru] NCPHGZWGGANCAY-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 152
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000011068 loading method Methods 0.000 claims abstract description 21
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 9
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 3
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 67
- 239000002105 nanoparticle Substances 0.000 claims description 53
- 238000001914 filtration Methods 0.000 claims description 23
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- 238000003756 stirring Methods 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 20
- 229910017604 nitric acid Inorganic materials 0.000 claims description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 238000002791 soaking Methods 0.000 claims description 16
- 239000000706 filtrate Substances 0.000 claims description 15
- 239000003960 organic solvent Substances 0.000 claims description 14
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 11
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical group CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 11
- 229910019891 RuCl3 Inorganic materials 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 10
- WTNDADANUZETTI-UHFFFAOYSA-N cyclohexane-1,2,4-tricarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)C(C(O)=O)C1 WTNDADANUZETTI-UHFFFAOYSA-N 0.000 claims description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 9
- FWHUTKPMCKSUCV-UHFFFAOYSA-N 1,3-dioxo-3a,4,5,6,7,7a-hexahydro-2-benzofuran-5-carboxylic acid Chemical compound C1C(C(=O)O)CCC2C(=O)OC(=O)C12 FWHUTKPMCKSUCV-UHFFFAOYSA-N 0.000 claims description 8
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
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- 238000001179 sorption measurement Methods 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims 2
- NPAXBRSUVYCZGM-UHFFFAOYSA-N carbonic acid;propane-1,2-diol Chemical compound OC(O)=O.CC(O)CO NPAXBRSUVYCZGM-UHFFFAOYSA-N 0.000 claims 1
- -1 cyclohexanetricarboxylic anhydride Chemical class 0.000 abstract description 15
- 239000002904 solvent Substances 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- 150000008064 anhydrides Chemical class 0.000 abstract description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 14
- 229910001220 stainless steel Inorganic materials 0.000 description 12
- 239000010935 stainless steel Substances 0.000 description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 description 11
- 238000009210 therapy by ultrasound Methods 0.000 description 8
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 125000005590 trimellitic acid group Chemical class 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
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- 239000008346 aqueous phase Substances 0.000 description 1
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- 239000003795 chemical substances by application Substances 0.000 description 1
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- 239000003822 epoxy resin Substances 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
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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
- 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
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
- C07D307/89—Benzo [c] furans; Hydrogenated benzo [c] furans with two oxygen atoms directly attached in positions 1 and 3
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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- Y02P20/584—Recycling of catalysts
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Abstract
The invention discloses ruthenium-carbon catalysts, a preparation method thereof and application thereof in synthesis of 1,2, 4-cyclohexane tricarbamic anhydride, wherein the ruthenium-carbon catalysts take metal ruthenium as an active component and active carbon as a carrier, and the mass loading amount of the ruthenium is 0.5-2.5%Low pressure 4.0MPa H2The hydrogenation of trimellitic anhydride is realized in the lower water phase, the preparation of cyclohexanetricarboxylic anhydride is completed, the cost is low, the conversion rate is as high as 97.5%, the selectivity is as high as 97.6%, the process is simple, and the used solvent is water, so that the method conforms to the principle of green chemistry.
Description
() technical field
The invention belongs to the technical field of catalysts, and particularly relates to single-metal-loaded ruthenium-carbon catalysts, preparation thereof, and application thereof in preparation of 1,2, 4-cyclohexanetricarboxylic anhydride by catalyzing hydrogenation of trimellitic anhydride.
(II) background of the invention
The ruthenium carbon catalyst has high catalytic activity and is widely used as a catalyst for hydrogenation reaction by , so that development and research on the ruthenium carbon catalyst have important theoretical significance and industrial application prospects, the common preparation method of the ruthenium catalyst mainly comprises an impregnation method, an ion exchange method, a coprecipitation method and the like, the impregnation method has -determined defects, and factors influencing the impregnation method comprise the impregnation method, the adsorption strength, chemical changes generated during heating and drying and the like.
1,2, 4-cyclohexane tricarboxylic anhydride (hydrogenated trimellitic anhydride) is alicyclic acid anhydrides, which can be generally applied to high-performance coatings, polyester resins and glass fibers, and can also be used as a curing agent for high-power blue-light LED epoxy resin packaging materials, and can be used as a raw material of functional polyimide with transparency and solvent solubility, the product can be used in the aspects of automobiles, transportation, industrial maintenance, aerospace, buildings, equipment and instruments, common metal and gel coating, and the like.
Disclosure of the invention
The invention aims to provide single-metal-loaded ruthenium-carbon catalysts and a preparation method thereof, which are applied to the reaction of preparing 1,2, 4-cyclohexanetricarboxylic anhydride by hydrogenating trimellitic anhydride and solve the problems of high reaction pressure, high temperature, large catalyst consumption, high cost and low yield in the process of synthesizing 1,2, 4-cyclohexanetricarboxylic anhydride by catalytic hydrogenation of the prior trimellitic anhydride.
The invention provides single-metal-loaded ruthenium-carbon catalysts for synthesizing 1,2, 4-cyclohexanetricarboxylic anhydride, wherein the ruthenium-carbon catalysts take metal ruthenium as an active component and active carbon as a carrier, and the mass loading of the ruthenium is 0.5-2.5%, preferably 1.0 wt%.
The ruthenium-carbon catalyst is prepared by the following method:
a. pretreating the activated carbon to obtain carrier activated carbon
Soaking activated carbon in nitric acid solution under stirring at room temperature for 8-24 hr (preferably 12 hr), filtering, washing the filter cake with deionized water for 10-20 times until the pH of the filtrate is 7, and placing in a tubular furnace under N atmosphere2Calcining for 2-6 h (preferably for 4h at 600 ℃) at 400-800 ℃ under the atmosphere protection to obtain carrier active carbon; the concentration of the nitric acid solution is 1-3 mol/L (preferably 3mol/L), and the volume usage of the nitric acid aqueous solution is 6-10 ml/g, preferably 6ml/g, based on the weight of the activated carbon;
b. preparation of Ru nanoparticles
Adding RuCl3·3H2Dissolving O in an organic solvent, dispersing for 10-60 min by ultrasonic (preferably 25KHz) to obtain a ruthenium chloride solution, transferring the solution to a stainless steel autoclave with a polytetrafluoroethylene lining, and reducing for 3-12 h (preferably 40 ℃, 4MPa and 6h) at 40-100 ℃ and under the hydrogen pressure of 1-4.0 MPa to obtain a Ru nanoparticle solution; the organic solvent is ethanol, isopropanol, propylene carbonate, preferably propylene carbonate; preferably, the concentration of Ru in the Ru nanoparticle solution is 1.6584X 10-3mol/L～8.4624×10-3mol/L, preferably 3.3333 mol/L;
c. loading of Ru nanoparticles
Adding the carrier activated carbon prepared in the step a into the ruthenium nanoparticle solution prepared in the step b, putting the carrier activated carbon into a Schlenk bottle, stirring and adsorbing for 6-24 h (preferably 30 ℃, 600r/min and 24h) at the conditions of 0-60 ℃ and 300-800 r/min under the protection of nitrogen atmosphere, then filtering, washing a filter cake for 3 times by using alcohol and acetone in sequence, and drying to obtain a ruthenium-loaded ruthenium-carbon catalyst, namely a Ru/C catalyst; the volume dosage of the ruthenium nano particle solution is 30ml/g based on the weight of the carrier activated carbon; the weight ratio of ruthenium to carrier active carbon in the ruthenium nano particle solution is 0.005-0.025: 1.
The invention also provides an application of ruthenium carbon catalysts in the synthesis of 1,2, 4-cyclohexane tricarboxylic acid anhydride, wherein the application comprises the following steps:
(1) taking the mass ratio of 20: dissolving 1 trimellitic anhydride and Ru/C catalyst in deionized water, uniformly dispersing to obtain a mixed solution, transferring the mixed solution to a stainless steel autoclave with a polytetrafluoroethylene lining, carrying out hydrogenation reaction at 100-150 ℃ under the condition that the hydrogen pressure is 4.0MPa, filtering the reaction solution after the reaction is finished, recovering the catalyst from a filter cake, and distilling the filtrate under reduced pressure to obtain 1,2, 4-cyclohexanetricarboxylic acid; the volume dosage of the deionized water is 15ml/g calculated by the weight of trimellitic anhydride;
(2) dissolving the 1,2, 4-cyclohexane tricarboxylic acid obtained in the step (1) in an organic solvent, refluxing and dividing water for 6-8 h (preferably 6h, the preferable temperature is different because of different solvents) at 120-160 ℃, and dividing the liquid to obtain 1,2, 4-cyclohexane tricarboxylic acid anhydride; the organic solvent is toluene, xylene or trimethylbenzene; the volume of the organic solvent is 4.0mL/g based on the weight of the 1,2, 4-cyclohexanetricarboxylic acid.
The preparation method of the nitric acid solution comprises the steps of mixing with commercial concentrated nitric acid with the mass fraction of 68% and water according to the volume ratio of 1:6.41, and preparing the dilute nitric acid solution with the required concentration of 3 mol/L.
Compared with the prior art, the invention has the beneficial effects that:
the single-metal loaded ruthenium-carbon catalyst prepared by the method has high catalytic activity, can be recycled and reused and has good stability; the ruthenium particles have small particle size and are uniformly dispersed; the preparation method is novel, and the reaction can be completed under the condition of high-pressure hydrogen without a stabilizer in the preparation process; the reaction process is green and environment-friendly and has no pollution. The ruthenium-carbon catalyst provided by the invention has the H of 4.0MPa at a lower temperature of 100-150 ℃ and a lower pressure of 4.0MPa2The hydrogenation of trimellitic anhydride is realized in the lower water phase, the preparation of cyclohexanetricarboxylic anhydride is completed, the cost is low, the conversion rate is as high as 97.5%, the selectivity is as high as 97.6%, the process is simple, and the used solvent is water, so that the method conforms to the principle of green chemistry.
(IV) description of the drawings
FIG. 1 is a TEM image of a 1 wt% Ru/C catalyst prepared in example 3.
(V) detailed description of the preferred embodiments
The invention is further illustrated by the following specific examples.
The active carbon used in the invention is from an Allantin purchase platform, the particle size is 200 meshes, and the room temperature is 25-30 ℃.
Example 1
() preparation of the catalyst
a. Pretreating the activated carbon to obtain carrier activated carbon
5g of activated carbon is taken and immersed in 30ml of 3mol/L nitric acid solution (the nitric acid solution is prepared by mixing the commercial concentrated nitric acid with the mass fraction of 68 percent and water according to the volume ratio of 1:6.41 at to prepare dilute nitric acid solution with the required concentration of 3mol/L, the same as the above example) at the temperature of 30 ℃, stirred and immersed for 12h, filtered, and the filter cake is washed by deionized water for 10 to 20 times until the pH of the filtrate is 7, and then the mixture is put into a tubular furnace in an N-type furnace2Calcining for 4 hours at 600 ℃ under the atmosphere protection to obtain 4.5g of carrier active carbon;
b. preparation of Ru nanoparticles
Take 5.0005X 10-4mol RuCl3·3H2Dissolving O in 150ml propylene carbonate, and performing ultrasonic treatment at 25KHz frequency for 60min to obtain a solution with a concentration of 3.3333 × 10-3And (3) transferring the solution to a stainless steel autoclave with a polytetrafluoroethylene lining, and reducing for 6 hours at the temperature of 40 ℃ and under the hydrogen pressure of 4.0MPa to prepare 150ml of Ru nano particle solution. The size of the ruthenium nano-particles is 2.0 +/-0.25 nm.
c: loading of Ru nanoparticles
And (b) adding 2.5g of the activated carbon prepared in the step (a) into 75ml of the Ru nanoparticle solution prepared in the step (b), putting the activated carbon into a Schlenk bottle, stirring and adsorbing the activated carbon for 24 hours at the temperature of 30 ℃ and at the speed of 600r/min under the protection of nitrogen, filtering the solution, washing the solution for 3 times by using alcohol and acetone in sequence, drying the solution to obtain 2.45g of the ruthenium-carbon (Ru/C) catalyst with the loading of 1 wt%, and detecting the actual loading of the ruthenium-carbon (Ru/C) catalyst to be 0.98 +/-0.02 wt% by ICP-MS.
Catalytic hydrogenation reaction of (di) trimellitic anhydride
Taking 10g of trimellitic anhydride (TMA) with the mass ratio of 20:1 and 0.5g of Ru/C catalyst prepared in the step C into 150mL of water, uniformly dispersing, transferring to a stainless steel autoclave with a polytetrafluoroethylene lining, replacing for 5 times by hydrogen, then carrying out hydrogenation reaction on the trimellitic anhydride under the conditions of 130 ℃ and 4.0MPa of hydrogen pressure, cooling the reaction kettle to room temperature by circulating water when the hydrogen pressure is unchanged, discharging and filtering, separating out a ruthenium-carbon catalyst from a filter cake, drying the catalyst in the air at night, recovering the catalyst for catalytic hydrogenation reaction in next batches, distilling the filtrate under reduced pressure to recover water, obtaining hydrogenated trimellitic acid, measuring a product absorbance value at 289nm by an ultraviolet spectroscopy method, and obtaining the mass yield and the conversion rate according to a standard curve of the hydrogenated trimellitic acid, wherein the luminosity is shown in Table 1.
The preparation method of the hydrogenated trimellitic acid standard curve comprises the steps of firstly preparing series trimellitic anhydride standard solutions with the concentration of 0, 20, 40, 60, 80, 100, 120 and 140ug/mL (the solvent is methanol), measuring the absorbance of the trimellitic anhydride standard solutions at the wavelength of 289nm, drawing a corresponding A-c curve according to the absorbance (A) and the concentration (c), and obtaining the curve equation of A-0.00802 c-0.00133.
Example 2
() preparation of the catalyst
a. Pretreating the activated carbon to obtain carrier activated carbon
Soaking 5g of activated carbon in 30ml of 3mol/L nitric acid solution, stirring and soaking at 30 ℃ for 12h, filtering, washing a filter cake with deionized water for 10-20 times until the pH value of the filtrate is 7, and then placing the filter cake in a tubular furnace in N2Calcining for 4 hours at 600 ℃ under the atmosphere protection to obtain 4.5g of carrier active carbon;
b. preparation of Ru nanoparticles
Take 5.0005X 10-4mol RuCl3·3H2Dissolving O in 150ml propylene carbonate, and performing ultrasonic treatment at 25KHz frequency for 60min to obtain a solution with a concentration of 3.3333 × 10-3And (3) transferring the solution to a stainless steel autoclave with a polytetrafluoroethylene lining, and reducing for 6 hours at the temperature of 60 ℃ under the condition that the hydrogen pressure is 4.0MPa to prepare 150ml of Ru nano particle solution. The size of the ruthenium nano-particles is 2.0 +/-0.23 nm.
c: loading of Ru nanoparticles
And (C) adding 2.5g of the activated carbon prepared in the step (a) into 75ml of the Ru nanoparticle solution prepared in the step (b), putting the activated carbon into a Schlenk bottle, stirring and adsorbing the activated carbon for 24 hours at the temperature of 30 ℃ and at the speed of 600r/min under the protection of nitrogen atmosphere, filtering, washing the activated carbon for 3 times by using alcohol and acetone in sequence, and drying to obtain 2.42g of Ru/C catalyst with the loading capacity of 1 wt%.
Catalytic hydrogenation reaction of (di) trimellitic anhydride
Step (two) was conducted in the same manner as in step (two) of example 1, except that the catalyst was replaced with that prepared in step () of this example, and the results are shown in Table 1.
Example 3
() preparation of the catalyst
a. Pretreating the activated carbon to obtain carrier activated carbon
Soaking 5g of activated carbon in 30ml of 3mol/L nitric acid solution, stirring and soaking at 30 ℃ for 12h, filtering, washing a filter cake with deionized water for 10-20 times until the pH value of the filtrate is 7, and then placing the filter cake in a tubular furnace in N2Calcining for 4 hours at 600 ℃ under the atmosphere protection to obtain 4.5g of carrier active carbon;
b. preparation of Ru nanoparticles
Take 5.0005X 10-4mol RuCl3·3H2Dissolving O in 150ml propylene carbonate, and performing ultrasonic treatment at 25KHz frequency for 60min to obtain a solution with a concentration of 3.3333 × 10-3And (3) transferring the solution to a stainless steel autoclave with a polytetrafluoroethylene lining, and reducing for 6 hours at the temperature of 80 ℃ under the condition that the hydrogen pressure is 4.0MPa to prepare 150ml of Ru nano particle solution. The size of the ruthenium nano-particles is 2.0 +/-0.20 nm.
c: loading of Ru nanoparticles
And (b) adding 2.5g of the activated carbon prepared in the step (a) into 75ml of the Ru nanoparticle solution prepared in the step (b), putting the activated carbon into a Schlenk bottle, stirring and adsorbing the activated carbon for 24 hours at the temperature of 30 ℃ and at the speed of 600r/min under the protection of nitrogen atmosphere, filtering, washing the activated carbon for 3 times by using alcohol and acetone in sequence, and drying to obtain 2.40g of Ru/C catalyst with the loading capacity of 1 wt%.
Catalytic hydrogenation reaction of (di) trimellitic anhydride
Step (two) was conducted in the same manner as in step (two) of example 1, except that the catalyst was replaced with that prepared in step () of this example, and the results are shown in Table 1.
Example 4
a. Pretreating the activated carbon to obtain carrier activated carbon
Soaking 5g of activated carbon in 30ml of 3mol/L nitric acid solution, stirring and soaking at 30 ℃ for 12h, filtering, washing a filter cake with deionized water for 10-20 times until the pH value of the filtrate is 7, and then placing the filter cake in a tubular furnace in N2Calcining for 4 hours at 600 ℃ under the atmosphere protection to obtain 4.5g of carrier active carbon;
b. preparation of Ru nanoparticles
Take 5.0005X 10-4mol RuCl3·3H2Dissolving O in 150ml propylene carbonate, and performing ultrasonic treatment at 25KHz frequency for 60min to obtain a solution with a concentration of 3.3333 × 10-3And (3) transferring the solution to a stainless steel autoclave with a polytetrafluoroethylene lining, and reducing for 6 hours at the temperature of 100 ℃ under the condition that the hydrogen pressure is 4.0MPa to prepare 150ml of Ru nano particle solution. The size of the ruthenium nano-particles is 2.0 +/-0.27 nm.
c: loading of Ru nanoparticles
And (b) adding 2.5g of the activated carbon prepared in the step (a) into 75ml of the Ru nanoparticle solution prepared in the step (b), putting the activated carbon into a Schlenk bottle, stirring and adsorbing the activated carbon for 24 hours at the temperature of 30 ℃ and at the speed of 600r/min under the protection of nitrogen atmosphere, filtering, washing the activated carbon for 3 times by using alcohol and acetone in sequence, and drying to obtain 2.38g of Ru/C catalyst with the loading capacity of 1 wt%.
Catalytic hydrogenation reaction of (di) trimellitic anhydride
Step (two) was conducted in the same manner as in step (two) of example 1, except that the catalyst was replaced with that prepared in step () of this example, and the results are shown in Table 1.
Example 5
a. Pretreating the activated carbon to obtain carrier activated carbon
Soaking 5g of activated carbon in 30ml of 3mol/L nitric acid solution, stirring and soaking at 30 ℃ for 12h, filtering, washing filter cake with deionized water for 10-20 times until pH of filtrate is 7Then in a tube furnace in N2Calcining for 4 hours at 600 ℃ under the atmosphere protection to obtain 4.5g of carrier active carbon;
b. preparation of Ru nanoparticles
Take 5.0005X 10-4mol RuCl3·3H2Dissolving O in 150ml propylene carbonate, and performing ultrasonic treatment at 25KHz frequency for 60min to obtain a solution with a concentration of 3.3333 × 10-3And (3) transferring the solution to a stainless steel autoclave with a polytetrafluoroethylene lining, and reducing for 3 hours at the temperature of 80 ℃ under the condition that the hydrogen pressure is 4.0MPa to prepare 150ml of Ru nano particle solution, wherein the size of the ruthenium nano particle is 2.0 +/-0.25 nm.
c: loading of Ru nanoparticles
And (b) adding 2.5g of the activated carbon prepared in the step (a) into 75ml of the Ru nanoparticle solution prepared in the step (b), putting the activated carbon into a Schlenk bottle, stirring and adsorbing the activated carbon for 24 hours at the temperature of 30 ℃ and at the speed of 600r/min under the protection of nitrogen atmosphere, filtering, washing the activated carbon for 3 times by using alcohol and acetone in sequence, and drying to obtain 2.37g of Ru/C catalyst with the loading capacity of 1 wt%.
Catalytic hydrogenation reaction of (di) trimellitic anhydride
Step (two) was conducted in the same manner as in step (two) of example 1, except that the catalyst was replaced with that prepared in step () of this example, and the results are shown in Table 1.
Example 6
a. Pretreating the activated carbon to obtain carrier activated carbon
Soaking 5g of activated carbon in 30ml of 3mol/L nitric acid solution, stirring and soaking at 30 ℃ for 12h, filtering, washing a filter cake with deionized water for 10-20 times until the pH value of the filtrate is 7, and then placing the filter cake in a tubular furnace in N2Calcining for 4 hours at 600 ℃ under the atmosphere protection to obtain 4.5g of carrier active carbon;
b. preparation of Ru nanoparticles
Take 5.0005X 10-4mol RuCl3·3H2Dissolving O in 150ml propylene carbonate, and performing ultrasonic treatment at 25KHz frequency for 60min to obtain a solution with a concentration of 3.3333 × 10-3A solution of ruthenium chloride in mol/L, which is then transferred to a stainless steel autoclave lined with Teflon, with hydrogen at 80 ℃Reducing for 12h under the condition of 4.0MPa to prepare 150ml of Ru nano particle solution, wherein the size of the Ru nano particle is 2.0 +/-0.25 nm.
c: loading of Ru nanoparticles
And (b) adding 2.5g of the activated carbon prepared in the step (a) into 75ml of the Ru nanoparticle solution prepared in the step (b), putting the activated carbon into a Schlenk bottle, stirring and adsorbing the activated carbon for 24 hours at the temperature of 30 ℃ and at the speed of 600r/min under the protection of nitrogen atmosphere, filtering, washing the activated carbon for 3 times by using alcohol and acetone in sequence, and drying to obtain 2.41g of Ru/C catalyst with the loading capacity of 1 wt%.
Catalytic hydrogenation reaction of (di) trimellitic anhydride
Step (two) was conducted in the same manner as in step (two) of example 1, except that the catalyst was replaced with that prepared in step () of this example, and the results are shown in Table 1.
Example 7
a. Pretreating the activated carbon to obtain carrier activated carbon
Soaking 5g of activated carbon in 30ml of 3mol/L nitric acid solution, stirring and soaking at 30 ℃ for 12h, filtering, washing a filter cake with deionized water for 10-20 times until the pH value of the filtrate is 7, and then placing the filter cake in a tubular furnace in N2Calcining for 4 hours at 600 ℃ under the atmosphere protection to obtain 4.5g of carrier active carbon;
b. preparation of Ru nanoparticles
Take 2.4876X 10-4mol RuCl3·3H2Dissolving O in 150ml propylene carbonate, and performing ultrasonic treatment at 25KHz frequency for 60min to obtain a solution with a concentration of 1.6584 × 10-3And (3) transferring the solution to a stainless steel autoclave with a polytetrafluoroethylene lining, and reducing for 6 hours at the temperature of 80 ℃ under the condition that the hydrogen pressure is 4.0MPa to prepare 150ml of Ru nano particle solution, wherein the size of the ruthenium nano particle is 2.0 +/-0.28 nm.
c: loading of Ru nanoparticles
And (C) adding 2.5g of the activated carbon prepared in the step (a) into 75ml of the Ru nanoparticle solution prepared in the step (b), putting the activated carbon into a Schlenk bottle, stirring and adsorbing the activated carbon for 24 hours at the temperature of 30 ℃ and at the speed of 600r/min under the protection of nitrogen atmosphere, filtering, washing the activated carbon for 3 times by using alcohol and acetone in sequence, and drying to obtain 2.40g of Ru/C catalyst with the loading capacity of 0.5 wt%.
Catalytic hydrogenation reaction of (di) trimellitic anhydride
Step (two) was conducted in the same manner as in step (two) of example 1, except that the catalyst was replaced with that prepared in step () of this example, and the results are shown in Table 1.
Example 8
a. Pretreating the activated carbon to obtain carrier activated carbon
Soaking 5g of activated carbon in 30ml of 3mol/L nitric acid solution, stirring and soaking at 30 ℃ for 12h, filtering, washing a filter cake with deionized water for 10-20 times until the pH value of the filtrate is 7, and then placing the filter cake in a tubular furnace in N2Calcining for 4 hours at 600 ℃ under the atmosphere protection to obtain 4.5g of carrier active carbon;
b. preparation of Ru nanoparticles
Take 1.2694X 10-3RuCl3·3H2Dissolving O in 150ml propylene carbonate, and performing ultrasonic treatment at 25KHz frequency for 60min to obtain a solution with a concentration of 8.4624 × 10-3And (3) transferring the solution to a stainless steel autoclave with a polytetrafluoroethylene lining, and reducing for 6 hours at the temperature of 80 ℃ under the condition that the hydrogen pressure is 4.0MPa to prepare 150ml of Ru nano particle solution, wherein the size of the ruthenium nano particle is 2.0 +/-0.24 nm.
c: loading of Ru nanoparticles
And (C) adding 2.5g of the activated carbon prepared in the step (a) into 75ml of the Ru nanoparticle solution prepared in the step (b), putting the activated carbon into a Schlenk bottle, stirring and adsorbing the activated carbon for 24 hours at the temperature of 30 ℃ and at the speed of 600r/min under the protection of nitrogen atmosphere, filtering, washing the activated carbon for 3 times by using alcohol and acetone in sequence, and drying to obtain 2.39g of Ru/C catalyst with the loading capacity of 2.5 wt%.
Catalytic hydrogenation reaction of (di) trimellitic anhydride
Step (two) was conducted in the same manner as in step (two) of example 1, except that the catalyst was replaced with that prepared in step () of this example, and the results are shown in Table 1.
TABLE 1 catalyst Properties
| Examples | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 |
| Conversion rate% | 87.3％ | 92.2％ | 97.5％ | 96.9％ | 87.1％ | 97.5％ | 74.7％ | 97.2％ |
| Yield% | 93.1％ | 95.4％ | 97.6％ | 96.0％ | 96.3％ | 96.5％ | 96.7％ | 96.9％ |
From the analysis results of the above examples, it is understood that the catalyst of example 3 has the best overall effect, and the conditions for the catalytic hydrogenation reaction of trimellitic anhydride were searched for according to the catalyst prepared in example 3, and the following concrete operations were carried out:
example 9
10g of trimellitic anhydride with the mass ratio of 20:1 and 0.5g of ruthenium-carbon catalyst prepared by the method in example 3 are taken to be put into 150mL of deionized water, the deionized water is uniformly dispersed and then transferred to a stainless steel autoclave with a polytetrafluoroethylene lining, the hydrogen is firstly replaced for 5 times, then the hydrogenation reaction of the trimellitic anhydride is carried out under the conditions that the hydrogen pressure is 100 ℃ and the hydrogen pressure is 4.0MPa, when the hydrogen pressure is not changed, the reaction kettle is cooled to the ambient temperature by circulating water, discharging and filtering are carried out, the ruthenium-carbon catalyst is separated from filter cakes, the catalyst can be recovered and used for the next batches of catalytic hydrogenation reaction after being aired in air for night, 9.5g of hydrogenated trimellitic acid is obtained after water is recovered by reduced pressure distillation of the filtrate, and the mass yield and the conversion rate are analyzed by the method in example 1.
Examples 10 to 13
The reaction temperature of the catalytic hydrogenation of example 9 was changed to that shown in Table 2, and the product yield and substrate conversion rate were shown in Table 2, except for the same operation.
TABLE 2 catalytic Properties
| Examples | 9 | 10 | 11 | 12 | 13 |
| Temperature of | 100℃ | 120℃ | 130℃ | 140℃ | 150℃ |
| Conversion rate% | 79.4％ | 90.8％ | 97.5％ | 97.4％ | 97.5％ |
EXAMPLE 14 dehydration to anhydride reaction
30g of 1,2, 4-cyclohexanetricarboxylic acid prepared by the method of example 9 was charged into a 250mL three-necked flask, and 120mL of an organic solvent (acetic anhydride in Table 3) was added at the same time, and the mixture was refluxed and dehydrated at different temperatures (120 ℃ C. in Table 3) for 6 to 8 hours, after completion of the reaction, the organic solvent was recovered by separation to obtain 1,2, 4-cyclohexanetricarboxylic anhydride, and the conversion rate was analyzed based on the quality of the aqueous phase obtained by separation and the acidity of the product, and the results are shown in Table 3.
Examples 15 to 16
The solvent and temperature in example 14 were changed as shown in Table 3, and the results are shown in Table 3, except that the process was performed in the same manner as in example 14.
TABLE 3 yield of 1,2, 4-cyclohexanetricarboxylic anhydride under different dehydration solvent operations
| Examples | 14 | 15 | 16 |
| Solvent(s) | Acetic anhydride | Xylene | Mesitylene |
| Temperature of | 120℃ | 130℃ | 140～160℃ |
| Time of day | 6h | 6h | 6h |
| Yield of 1,2, 4-cyclohexanetrianhydride% | 93.3％ | 97.2％ | 97.7％ |
Example 17 catalyst recycle
The ruthenium charcoal catalyst prepared in example 3 was used in the catalytic hydrogenation of trimellitic anhydride in example 9, and the catalyst recycling results are shown in table 4 below.
TABLE 4 catalyst recycle effectiveness
| Number of cycles | 1 | 2 | 3 | 4 | 5 | 6 |
| Conversion rate% | 97.2％ | 96.9％ | 96.7％ | 96.0％ | 95.2％ | 94.5％ |
It can be seen from table 4 that the catalyst prepared by the method of the present invention has high stability, can be recycled for many times under conditions, and is beneficial to saving resources and reducing cost.
Comparing the results, we can know that the 1 wt% Ru/C catalyst prepared by the method has the advantages of simple preparation process, high catalytic activity, good stability and the like, can realize the hydrogenation of trimellitic anhydride in a water phase at a lower temperature and a lower pressure to complete the preparation of 1,2, 4-cyclohexanetricarboxylic anhydride, and has the advantages of low cost, high yield, simple process and realization of industrialization.
Claims (10)
1, ruthenium on carbon catalyst, characterized in that the catalyst is prepared as follows:
a. pretreating the activated carbon to obtain carrier activated carbon
Taking activated carbon, immersing the activated carbon in a nitric acid solution, stirring and soaking for 8-24 h at room temperature, filtering, washing a filter cake with deionized water until the pH of the filtrate is 7, and then placing the filtrate in a tubular furnace in N2Calcining for 2-6 h at 400-800 ℃ under the protection of atmosphere to obtain carrier active carbon;
b. preparation of Ru nanoparticles
Adding RuCl3·3H2Dissolving O in an organic solvent, performing ultrasonic dispersion to obtain a ruthenium chloride solution, and reducing the ruthenium chloride solution for 3-12 h under the conditions of 40-100 ℃ and 1-4.0 MPa of hydrogen pressure to obtain a ruthenium nanoparticle solution; the organic solvent is ethanol, isopropanol or propylene glycol carbonate;
c. loading of Ru nanoparticles
And (c) adding the carrier activated carbon prepared in the step (a) into the ruthenium nanoparticle solution prepared in the step (b), stirring and adsorbing for 6-24 h under the protection of nitrogen atmosphere at the temperature of 0-60 ℃ and at the speed of 300-800 r/min, then filtering, washing a filter cake for 3 times by using alcohol and acetone in sequence, and drying to obtain the ruthenium-loaded ruthenium-carbon catalyst.
2. The ruthenium carbon catalyst according to claim 1, wherein the concentration of the nitric acid solution in step a is 1mol/L to 3mol/L, and the volume of the nitric acid solution is 6ml/g to 10ml/g based on the weight of the activated carbon.
3. The ruthenium carbon catalyst as claimed in claim 1, wherein the ultrasonic dispersion condition in step b is 25KHz ultrasonic for 10min to 60 min.
4. The ruthenium on carbon catalyst according to claim 1, wherein the organic solvent in step b is propylene carbonate.
5. The ruthenium on carbon catalyst of claim 1, wherein the ruthenium concentration in the ruthenium nanoparticle solution in step b is the same as the ruthenium concentration in the ruthenium on carbon catalystIs 1.6584X 10-3mol/L～8.4624×10-3mol/L。
6. The ruthenium carbon catalyst according to claim 1, wherein the stirring adsorption condition in step c is 30 ℃ and 600r/min stirring adsorption for 24 h.
7. The ruthenium carbon catalyst of claim 1, wherein in step c the weight ratio of ruthenium to supported activated carbon in the ruthenium nanoparticle solution is from 0.005 to 0.025: 1.
Use of the ruthenium on carbon catalyst of claim 1 in the synthesis of 1,2, 4-cyclohexanetricarboxylic anhydride.
9. The use according to claim 8, characterized in that said use is:
(1) dissolving trimellitic anhydride and a ruthenium-carbon catalyst in deionized water, uniformly dispersing to obtain a mixed solution, carrying out hydrogenation reaction on the mixed solution at 100-150 ℃ under the condition that the hydrogen pressure is 4.0MPa, filtering the reaction solution after the reaction is finished, recovering the catalyst from a filter cake, and distilling the filtrate under reduced pressure to obtain 1,2, 4-cyclohexanetricarboxylic acid;
(2) dissolving the 1,2, 4-cyclohexane tricarboxylic acid obtained in the step (1) in an organic solvent, carrying out reflux reaction at 120-160 ℃, and after the reaction is completed, separating liquid and recovering the organic solvent to obtain 1,2, 4-cyclohexane tricarboxylic acid anhydride; the organic solvent is toluene, xylene or trimethylbenzene; the addition amount of the organic solvent is 4.0mL/g based on the amount of 1,2, 4-cyclohexanetricarboxylic acid.
10. The method according to claim 9, wherein the mass ratio of the trimellitic anhydride to the ruthenium carbon catalyst in the step (1) is 20:1, and the volume usage of the deionized water is 15ml/g based on the weight of the trimellitic anhydride.
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