CN110732325B - 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 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- NCPHGZWGGANCAY-UHFFFAOYSA-N methane;ruthenium Chemical compound C.[Ru] NCPHGZWGGANCAY-UHFFFAOYSA-N 0.000 title claims abstract description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 127
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 45
- 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 36
- 238000000034 method Methods 0.000 claims abstract description 35
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 20
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 19
- 238000011068 loading method Methods 0.000 claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims description 64
- 239000002105 nanoparticle Substances 0.000 claims description 51
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- 238000005406 washing Methods 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 18
- 229910017604 nitric acid Inorganic materials 0.000 claims description 18
- 238000002791 soaking Methods 0.000 claims description 16
- 239000003960 organic solvent Substances 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 239000000706 filtrate Substances 0.000 claims description 13
- 239000012298 atmosphere Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical group CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 11
- 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
- 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 9
- 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
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 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
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- -1 cyclohexanetricarboxylic anhydride Chemical class 0.000 abstract description 16
- 239000002904 solvent Substances 0.000 abstract description 10
- 239000002245 particle Substances 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 150000008065 acid anhydrides Chemical class 0.000 abstract description 2
- 239000003381 stabilizer Substances 0.000 abstract description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 14
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 description 12
- 229910001220 stainless steel Inorganic materials 0.000 description 12
- 239000010935 stainless steel Substances 0.000 description 12
- 239000012299 nitrogen atmosphere Substances 0.000 description 9
- 238000009210 therapy by ultrasound Methods 0.000 description 8
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical class OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
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- 238000002835 absorbance Methods 0.000 description 3
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- 239000000499 gel Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
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- 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
- 239000002923 metal particle Substances 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- RPNNPZHFJPXFQS-UHFFFAOYSA-N methane;rhodium Chemical compound C.[Rh] RPNNPZHFJPXFQS-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 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
- 229920001721 polyimide Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
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- 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
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- 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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Abstract
The invention discloses a ruthenium-carbon catalyst, a preparation method thereof and application thereof in synthesizing 1,2,4-cyclohexane tricarbamic acid anhydride, wherein the ruthenium-carbon catalyst takes metal ruthenium as an active component and active carbon as a carrier, and the mass loading capacity of the ruthenium is 0.5-2.5%. The preparation method of the single metal loaded ruthenium-carbon catalyst is novel; the catalyst 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 process does not need a stabilizer, namely the reaction can be completed under the condition of high-pressure hydrogen; the reaction process is green and environment-friendly and has no pollution. Can be at a lower temperature of 100-150 ℃ and a lower pressure of 4.0MPa H 2 The 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
(I) technical field
The invention belongs to the technical field of catalysts, and particularly relates to a single-metal-loaded ruthenium-carbon catalyst, preparation thereof and application thereof in preparation of 1,2,4-cyclohexane tricarboxylic acid anhydride by catalyzing hydrogenation of trimellitic anhydride.
(II) background of the invention
Ruthenium carbon catalysts have high catalytic activity and are widely used as catalysts for hydrogenation reactions. Therefore, the method has important theoretical significance and industrial application prospect in the development and research of the ruthenium-carbon catalyst. The preparation method of the common ruthenium catalyst mainly comprises the following steps: impregnation, ion exchange, coprecipitation, and the like. The impregnation method has certain defects, and factors influencing the impregnation method comprise the impregnation method, the strength of adsorption, chemical changes generated during heating and drying, and the like. The influence factors are difficult to control, so that the metal distribution is difficult to control according to the preset distribution, and the metal loading capacity may be low. The ion exchange method is to load active components on the carrier by ion exchange by utilizing the ion which exists on the surface of the carrier and can be exchanged, and then to prepare the loaded metal catalyst by washing, reducing and the like. The ruthenium loading of the ion exchange method mainly depends on the number of groups exchangeable on the surface of the activated carbon, and the ruthenium loading is higher when the number of exchangeable groups is larger; however, the activated carbon surface tends to lack exchangeable ions, so that the process is generally suitable only for the preparation of low-loading Ru/C catalysts. The coprecipitation method is to add a precipitant into a solution containing metal salts to generate insoluble salts, metal oxides or gels through double decomposition reaction, and then to precipitate the insoluble salts, metal oxides or gels from the solution. The precipitation process of the precipitation method is very complicated, the generated precipitated crystals are easy to agglomerate, so that the final metal particles are uneven in size distribution, and meanwhile, impurities are easy to be occluded and other impurities are introduced by the precipitation method. In the meantime, the finding of a Ru/C catalyst with simple preparation process, high catalytic activity and good stability is a popular subject at present due to some defects of the existing methods.
1,2,4-cyclohexanetricarboxylic anhydride (hydrogenated trimellitic anhydride) is an alicyclic anhydride, and can be generally applied to high-performance coatings, polyester resins and glass fibers, 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 fields of automobiles, transportation, industrial maintenance, aerospace, buildings, equipment and instruments, common metal and gel coat coatings and the like. In recent years, the process for preparing 1,2,4-cyclohexanetricarboxylic anhydride by directly hydrogenating trimellitic anhydride (TMA) as a raw material has been rapidly developed. Chinese patent document CM428324A discloses a method for preparing hydrogenated aromatic polycarboxylic anhydride, and specifically discloses a method for preparing hydrogenated trimellitic acid from trimellitic anhydride, namely, trimellitic anhydride is used as a raw material, water is used as a single solvent, and hydrogenation reaction is carried out under the action of a rhodium-carbon catalyst with a large feeding amount (the weight of the catalyst is 66.67% of that of trimellitic acid). The hydrogenated trimellitic anhydride obtained by the method has low purity, large catalyst consumption and overhigh cost. Patent CN101891721B discloses a preparation method of electronic grade hydrogenated trimellitic anhydride, which is a process technology for preparing hydrogenated trimellitic anhydride by directly hydrogenating trimellitic anhydride as a raw material, tetrahydrofuran, ethanol, methanol and the like as solvents and palladium carbon or platinum carbon as a catalyst. The single metal supported ruthenium carbon catalyst has good hydrogenation performance and is widely used as a catalyst for hydrogenation reaction. Therefore, the method has important theoretical significance and industrial application prospect in the development and research of the single-metal supported ruthenium-carbon catalyst.
Disclosure of the invention
The invention aims to provide a single metal loaded ruthenium-carbon catalyst and a preparation method thereof, which are applied to the reaction of preparing 1,2,4-cyclohexane tricarboxylic 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-cyclohexane tricarboxylic anhydride by catalytic hydrogenation of the existing trimellitic anhydride.
The invention provides a single-metal-loaded ruthenium-carbon catalyst for synthesizing 1,2,4-cyclohexanetricarboxylic anhydride, which takes metal ruthenium as an active component and active carbon as a carrier, wherein the mass loading amount of ruthenium is 0.5-2.5%, and is preferably 1.0wt%.
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 atmosphere 2 Calcining 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 3 mol/L), and the volume consumption of the nitric acid aqueous solution is 6-10 ml/g (preferably 6 ml/g) by weight of the activated carbon;
b. preparation of Ru nanoparticles
Adding RuCl 3 ·3H 2 Dissolving O in an organic solvent, dispersing for 10-60 min by ultrasonic (preferably 25 KHz) 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 6 h) 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 1.6584 x 10 -3 mol/L～8.4624×10 -3 mol/L, preferably 3.3333mol/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 Shi Laike bottle, stirring and adsorbing for 6-24 h (preferably 30 ℃,600 r/min and 24 h) under the protection of nitrogen atmosphere and under the conditions of 0-60 ℃ and 300-800 r/min, 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 nanoparticle solution is 0.005-0.025.
The invention also provides an application of the ruthenium carbon catalyst in the synthesis of 1,2,4-cyclohexane tricarbamic acid anhydride, wherein the application comprises the following steps:
(1) Taking the mass ratio of 20:1, dissolving 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 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 due to 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 added is 4.0mL/g based on the weight of 1,2,4-cyclohexanetricarboxylic acid.
The preparation method of the nitric acid solution comprises the following steps: commercial concentrated nitric acid with the mass fraction of 68% and water are mixed together according to the volume ratio of 1.
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 of the invention has the H of 4.0MPa at the lower temperature of 100-150 ℃ and the lower pressure of 4.0MPa 2 The 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 the Ru/C catalyst obtained in example 3 at 1wt%.
(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 catalyst
a. Pretreating the active carbon to obtain carrier active 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 commercial concentrated nitric acid with the mass fraction of 68 percent and water according to the volume ratio of 1 2 Calcining for 4 hours at 600 ℃ under the atmosphere protection to obtain 4.5g of carrier active carbon;
b. preparation of Ru nanoparticles
Take 5.0005 × 10 -4 mol RuCl 3 ·3H 2 Dissolving O in 150ml propylene carbonate, and performing ultrasonic treatment at 25KHz frequency for 60min to obtain solution with concentration of 3.3333 × 10 -3 And (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 nanoparticle solution. The size of the ruthenium nanometer 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 Shi Laike 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 and the acetone for 3 times in sequence, drying to obtain 2.45g of a ruthenium-carbon (Ru/C) catalyst with the loading of 1wt%, 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 the mass ratio of 20: 10g of trimellitic anhydride (TMA) 1 and 0.5g of Ru/C catalyst prepared in the step C are placed in 150mL of water, uniformly dispersed and transferred to a stainless steel autoclave with a polytetrafluoroethylene lining, the mixture is replaced by hydrogen for 5 times, then hydrogenation reaction of trimellitic anhydride is carried out under the conditions of 130 ℃ and 4.0MPa of hydrogen pressure, when the hydrogen pressure is not changed, the reaction kettle is cooled to room temperature by circulating water, discharging and filtering are carried out, a ruthenium-carbon catalyst is separated from a filter cake, the catalyst can be recycled and used for next catalytic hydrogenation reaction after being dried in the air overnight, the filtrate is subjected to reduced pressure distillation to recover water to obtain hydrogenated trimellitic acid, the absorbance value of a product is measured at 289nm by an ultraviolet spectrophotometry method, and the mass yield and the conversion rate are obtained according to a standard curve of the hydrogenated trimellitic acid, and the results are shown in Table 1.
The preparation method of the hydrogenated trimellitic acid standard curve comprises the following steps: firstly, preparing a series of 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, and drawing a corresponding A-c curve according to the absorbance (A) and the concentration (c), wherein the curve equation is A =0.00802c-0.00133.
Example 2
Preparation of 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 N 2 Calcining for 4 hours at 600 ℃ under the atmosphere protection to obtain 4.5g of carrier active carbon;
b. preparation of Ru nanoparticles
Take 5.0005 × 10 -4 mol RuCl 3 ·3H 2 Dissolving O in 150ml propylene carbonate, and performing ultrasonic treatment at 25KHz frequency for 60min to obtain solution with concentration of 3.3333 × 10 -3 And (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 Shi Laike bottle, stirring and adsorbing for 24 hours at 30 ℃ and 600r/min under the protection of nitrogen atmosphere, then filtering, washing for 3 times by using alcohol and acetone in sequence, and drying to obtain 2.42g of Ru/C catalyst with the load of 1 wt%.
Catalytic hydrogenation reaction of (di) trimellitic anhydride
Step (two) was operated in the same manner as in step (two) of example 1, except that the catalyst was replaced with that prepared in step (one) of this example, and the results are shown in Table 1.
Example 3
Preparation of 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 filter cake with deionized water for 10-20 times until pH of filtrate is 7, and placing in a tube furnace in N 2 Calcining for 4 hours at 600 ℃ under the atmosphere protection to obtain 4.5g of carrier active carbon;
b. preparation of Ru nanoparticles
Take 5.0005 × 10 -4 mol RuCl 3 ·3H 2 Dissolving O in 150ml propylene carbonate, and performing ultrasonic treatment at 25KHz frequency for 60min to obtain solution with concentration of 3.3333 × 10 -3 And (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 (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 Shi Laike bottle, stirring and adsorbing for 24 hours at 30 ℃ and 600r/min under the protection of nitrogen atmosphere, then filtering, washing for 3 times by using alcohol and acetone in sequence, and drying to obtain 2.40g of Ru/C catalyst with the load 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 the one prepared in step (one) 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 N 2 Calcining for 4 hours at 600 ℃ under the atmosphere protection to obtain 4.5g of carrier active carbon;
b. preparation of Ru nanoparticles
Take 5.0005 × 10 -4 mol RuCl 3 ·3H 2 Dissolving O in 150ml propylene carbonate, and performing ultrasonic treatment at 25KHz frequency for 60min to obtain solution with concentration of 3.3333 × 10 -3 And (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 nanometer particle is 2.0 +/-0.27 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 Shi Laike bottle, stirring and adsorbing for 24 hours at 30 ℃ and 600r/min under the protection of nitrogen atmosphere, then filtering, washing for 3 times by using alcohol and acetone in sequence, and drying to obtain 2.38g of Ru/C catalyst with the load of 1 wt%.
Catalytic hydrogenation reaction of (di) trimellitic anhydride
Step (two) was operated in the same manner as in step (two) of example 1, except that the catalyst was replaced with that prepared in step (one) 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 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 mannerIn a furnace at N 2 Calcining for 4 hours at 600 ℃ under the atmosphere protection to obtain 4.5g of carrier active carbon;
b. preparation of Ru nanoparticles
Take 5.0005 × 10 -4 mol RuCl 3 ·3H 2 Dissolving O in 150ml propylene carbonate, and performing ultrasonic treatment at 25KHz frequency for 60min to obtain solution with concentration of 3.3333 × 10 -3 And (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 (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 Shi Laike bottle, stirring and adsorbing for 24 hours at 30 ℃ at 600r/min under the protection of nitrogen atmosphere, filtering, washing for 3 times by using alcohol and acetone in sequence, and drying to obtain 2.37g of Ru/C catalyst with the load of 1 wt%.
Catalytic hydrogenation reaction of (di) trimellitic anhydride
Step (two) was operated in the same manner as in step (two) of example 1, except that the catalyst was replaced with that prepared in step (one) 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 filter cake with deionized water for 10-20 times until pH of filtrate is 7, and placing in a tube furnace in N 2 Calcining for 4 hours at 600 ℃ under the atmosphere protection to obtain 4.5g of carrier active carbon;
b. preparation of Ru nanoparticles
Take 5.0005 × 10 -4 mol RuCl 3 ·3H 2 Dissolving O in 150ml propylene carbonate, and performing ultrasonic treatment at 25KHz frequency for 60min to obtain solution with concentration of 3.3333 × 10 -3 A solution of ruthenium chloride in mol/L, which is then transferred to a stainless steel autoclave lined with polytetrafluoroethylene, at 80 ℃ in strips with a hydrogen pressure of 4.0MPaReducing for 12 hours under the condition of a workpiece to prepare 150ml of Ru nano particle solution, wherein the size of the Ru nano particles is 2.0 +/-0.25 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 Shi Laike bottle, stirring and adsorbing for 24 hours at 30 ℃ at 600r/min under the protection of nitrogen atmosphere, filtering, washing for 3 times by using alcohol and acetone in sequence, and drying to obtain 2.41g of Ru/C catalyst with the load of 1 wt%.
Catalytic hydrogenation reaction of (di) trimellitic anhydride
Step (two) was operated in the same manner as in step (two) of example 1, except that the catalyst was replaced with that prepared in step (one) 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 N 2 Calcining for 4 hours at 600 ℃ under the atmosphere protection to obtain 4.5g of carrier active carbon;
b. preparation of Ru nanoparticles
Take 2.4876 × 10 -4 mol RuCl 3 ·3H 2 Dissolving O in 150ml propylene carbonate, and performing ultrasonic treatment at 25KHz frequency for 60min to obtain solution with concentration of 1.6584 × 10 -3 And (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 Shi Laike bottle, stirring and adsorbing for 24 hours at 30 ℃ at 600r/min under the protection of nitrogen atmosphere, filtering, washing for 3 times by using alcohol and acetone in sequence, and drying to obtain 2.40g of Ru/C catalyst with the load of 0.5 wt%.
Catalytic hydrogenation reaction of (di) trimellitic anhydride
Step (two) was operated in the same manner as in step (two) of example 1, except that the catalyst was replaced with that prepared in step (one) 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 N 2 Calcining for 4 hours at 600 ℃ under the atmosphere protection to obtain 4.5g of carrier active carbon;
b. preparation of Ru nanoparticles
Take 1.2694 × 10 -3 RuCl 3 ·3H 2 Dissolving O in 150ml propylene carbonate, and performing ultrasonic treatment at 25KHz frequency for 60min to obtain solution with concentration of 8.4624 × 10 -3 And (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 Ru nano particles 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 Shi Laike bottle, stirring and adsorbing for 24 hours at 30 ℃ at 600r/min under the protection of nitrogen atmosphere, filtering, washing for 3 times by using alcohol and acetone in sequence, and drying to obtain 2.39g of Ru/C catalyst with the load of 2.5 wt%.
Catalytic hydrogenation reaction of (di) trimellitic anhydride
Step (two) was operated in the same manner as in step (two) of example 1, except that the catalyst was replaced with that prepared in step (one) of this example, and the results are shown in Table 1.
TABLE 1 catalyst Performance
| 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
Taking the mass ratio of 20: 10g of trimellitic anhydride 1 and 0.5g of ruthenium-carbon catalyst prepared in example 3 are uniformly dispersed in 150mL of deionized water, then transferred to a stainless steel autoclave with a polytetrafluoroethylene lining, replaced by hydrogen for 5 times, and then subjected to hydrogenation reaction of trimellitic anhydride under the conditions of 100 ℃ and 4.0MPa of hydrogen pressure, when the hydrogen pressure is unchanged, 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 recycled and used for the next catalytic hydrogenation reaction after being aired in the air overnight, 9.5g of hydrogenated trimellitic acid is obtained after water is recovered by vacuum distillation of filtrate, and the mass yield and the conversion rate are analyzed by the method of example 1, and the results are shown in Table 2.
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 added to 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 ℃ in Table 3) for 6 to 8 hours, after the reaction was completed, the organic solvent was separated and recovered to obtain 1,2,4-cyclohexanetricarboxylic anhydride, and the conversion rate was analyzed based on the quality of the aqueous phase obtained by the 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 operation
| Examples | 14 | 15 | 16 |
| Solvent(s) | Acetic anhydride | Xylene | Mesitylene |
| Temperature of | 120℃ | 130℃ | 140～160℃ |
| Time | 6h | 6h | 6h |
| 1,2,4-Cyclohexanetrianhydride yield% | 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 |
| Percent conversion% | 97.2％ | 96.9％ | 96.7％ | 96.0％ | 95.2％ | 94.5％ |
As can be seen from Table 4, the catalyst prepared by the method of the present invention has high stability, can be recycled for many times under certain conditions, and is beneficial to resource saving and cost reduction. The decrease in conversion with increasing number of uses is due to the relative attrition of the catalyst.
Comparing the above results, we can know that the 1wt% 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, has low cost, high yield and simple process, and has the scene of realizing industrialization.
Claims (9)
1. The application of the ruthenium carbon catalyst in the synthesis of 1,2,4-cyclohexanetricarboxylic anhydride is characterized in that the ruthenium carbon catalyst is used in the reaction of preparing 1,2,4-cyclohexanetricarboxylic anhydride by hydrogenating trimellitic anhydride;
the ruthenium carbon catalyst takes metal ruthenium as an active component and active carbon as a carrier, and the mass loading capacity of the ruthenium is 0.5-2.5%;
the catalyst is prepared by the following method:
a. pretreating the activated carbon to obtain carrier activated carbon
Immersing activated carbon in a nitric acid solution, stirring and soaking for 8 to 24h at room temperature, filtering, washing a filter cake with deionized water until the pH of the filtrate is 7, and then placing the filter cake in a tubular furnace in N 2 Calcining at 400-800 ℃ for 2h-6h under the protection of atmosphere to obtain carrier active carbon;
b. preparation of Ru nanoparticles
RuCl is added 3 •3H 2 Dissolving O in an organic solvent, performing ultrasonic dispersion to obtain a ruthenium chloride solution, and reducing the ruthenium chloride solution for 3h to 12h under the conditions of 40-100 ℃ and 10-4.0 MPa of hydrogen pressure to prepare 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 6h to 24h under the protection of nitrogen at the temperature of 0-60 ℃ and at the speed of 300 r/min-800 r/min, 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 method of claim 1, wherein the concentration of the nitric acid solution in the step a is 1 mol/L-3 mol/L, and the volume of the nitric acid solution is 6 ml/g-10 ml/g based on the weight of the activated carbon.
3. The method of claim 1, wherein the ultrasonic dispersion conditions in step b are 25KHz ultrasonic ranging from 10min to 60min.
4. The use according to claim 1, wherein the organic solvent in step b is propylene carbonate.
5. The use according to claim 1, wherein in step b the ruthenium concentration in the ruthenium nanoparticle solution is 1.6584 x 10 -3 mol/L~8.4624×10 -3 mol/L。
6. The method of claim 1, wherein the stirring adsorption condition in step c is 30 ℃ and 600r/min stirring adsorption for 24h.
7. The use according to 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.
8. The use according to claim 7, 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 1,2,4-cyclohexane tricarboxylic acid obtained in the step (1) in an organic solvent, carrying out reflux reaction at 120-160 ℃, and after complete reaction, 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 amount of the organic solvent added was 4.0mL/g based on the amount of 1,2,4-cyclohexanetricarboxylic acid.
9. The method according to claim 8, wherein the mass ratio of the trimellitic anhydride to the ruthenium carbon catalyst in the step (1) is 20.
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