The production of industrial chemicals with renewable biomass feedstock holds potential to aid the world in pursuing a carbon-neutral society.Trimellitic and trimesic acids are important commodity chemicals in industr...The production of industrial chemicals with renewable biomass feedstock holds potential to aid the world in pursuing a carbon-neutral society.Trimellitic and trimesic acids are important commodity chemicals in industry that are prepared by the oxidation of petroleum-derived trimethylbenzene.To reduce the dependence on the limited oil source,we develop a potential sustainable alternative towards trimellitic and trimesic acids using biomass-based 2-methyl-2,4-pentandiol(MPD),acrylate and crotonaldehyde as starting materials.The process for trimellitic acid includes dehydration/D-A reaction of MPD and acrylate,flow aromatization over Pd/C catalyst,hydrolysis and catalytic aerobic oxidation(60%overall yield).The challenging regioselectivity issue of D-A reaction is tackled by a matched combination of temperature and deep eutectic solvent ChCl/HCO_(2)H.Crotonaldehyde can also participate in the reaction,followed by Pd/C-catalyzed decarbonylation/dehydrogenation and oxidation to provide trimesic acid in 54%overall yield.Life cycle assessment implies that compared to conventional fossil process,our biomass-based routes present a potential in reducing carbon emissions.展开更多
The fluorescence of terbium （Ⅲ） was enhanced by about three orders of magnitude in the presence of trimellitic acid （benzene-1, 2, 4-tricarboxylic acid （TLA）） in aqueous solution at pH 6. The fluorescence inten...The fluorescence of terbium （Ⅲ） was enhanced by about three orders of magnitude in the presence of trimellitic acid （benzene-1, 2, 4-tricarboxylic acid （TLA）） in aqueous solution at pH 6. The fluorescence intensity could be greatly increased when the system of Tb^3＋-TLA was treated with La^3＋ （or Gd^3＋） and TritonX- 100. The addition of La^3＋ （or Gd^3＋） enhanees the fluorescence of the system by about two orders of magnitude due to cofluorescenee, and the TritonX-100 micellar medium plays an important role for stabilization of the system. Both the intermolecular energy transfer mode and intramolecular energy transfer mode are responsible for the mechanism of fluorescence enhancement. In the optimum condi- tions, the fluorescence intensity is a linear function of Tb3~ concentration in the range of 7.8 × 10^-9-3.6 × 10^4 mol/L for the system Tb^3＋-La^3＋-TLA and 1.0 × 10^-8-4.7 × 10^-5 mol/L for the system Tb^3＋-Gd^3＋-TLA, and the limits of detection are 4.6 × 10^-10 mol/L and 6.0 × 10^-10 mol/L, respectively.展开更多
To explore the feasibility of extracting aromatic acid products from oxidizing coal, two aromatic acids, trimellitic and [1,1′-biphenyl]-2,2′-dicarboxylic acid, were selected as the solutes, and the extraction equil...To explore the feasibility of extracting aromatic acid products from oxidizing coal, two aromatic acids, trimellitic and [1,1′-biphenyl]-2,2′-dicarboxylic acid, were selected as the solutes, and the extraction equilibrium of the acids were studied with 1-octanol, 50% tributyl phosphate （TBP） in kerosene, and 10% trialkylphosphine oxide （TRPO） in kerosene. The results showed that the degree of extraction of [1,1′-biphenyl]-2,2′-dicarboxylic acid was larger than that of trimellitic acid for all of the solvent, and the extraction capacity with TRPO is more effective than the one with TBP. The extraction behavior of aromatic polyacid is different from that of carboxylic acid, and the reactive extraction function of aromatic acids with TBP and TRPO is not as effective as that of carboxylic acid. 1-octanol could be used to remove [1,1′-biphenyl]-2,2′-dicarboxylic acid from the mixture of trimellitic acid and [1,1′-biphenyl]-2,2′-dicarboxylic acid. Because the weak hydrogen bond association exists between -OH in 1-octanol and -COOH in aromatic acid, the extractive selectivity of [ 1, 1′-biphenyl]-2,2′-dicarboxylic to trimellitic acid depends on the stoichiometric ratio.展开更多
基金supported by the National Key R&D Program of China(no.2022YFA1504902,2022YFB4201802)National Natural Science Foundation of China(no.21721004,21801239,22178335,22078318),DICP(Grant:DICP I201944)the Joint Fund of the Yulin University and the Dalian National Laboratory for Clean Energy(grant:YLU-DNL Fund 2021020).
文摘The production of industrial chemicals with renewable biomass feedstock holds potential to aid the world in pursuing a carbon-neutral society.Trimellitic and trimesic acids are important commodity chemicals in industry that are prepared by the oxidation of petroleum-derived trimethylbenzene.To reduce the dependence on the limited oil source,we develop a potential sustainable alternative towards trimellitic and trimesic acids using biomass-based 2-methyl-2,4-pentandiol(MPD),acrylate and crotonaldehyde as starting materials.The process for trimellitic acid includes dehydration/D-A reaction of MPD and acrylate,flow aromatization over Pd/C catalyst,hydrolysis and catalytic aerobic oxidation(60%overall yield).The challenging regioselectivity issue of D-A reaction is tackled by a matched combination of temperature and deep eutectic solvent ChCl/HCO_(2)H.Crotonaldehyde can also participate in the reaction,followed by Pd/C-catalyzed decarbonylation/dehydrogenation and oxidation to provide trimesic acid in 54%overall yield.Life cycle assessment implies that compared to conventional fossil process,our biomass-based routes present a potential in reducing carbon emissions.
基金This work was financially supported by the Science Foundation of Hunan Province, China (No. 01C030)
文摘The fluorescence of terbium （Ⅲ） was enhanced by about three orders of magnitude in the presence of trimellitic acid （benzene-1, 2, 4-tricarboxylic acid （TLA）） in aqueous solution at pH 6. The fluorescence intensity could be greatly increased when the system of Tb^3＋-TLA was treated with La^3＋ （or Gd^3＋） and TritonX- 100. The addition of La^3＋ （or Gd^3＋） enhanees the fluorescence of the system by about two orders of magnitude due to cofluorescenee, and the TritonX-100 micellar medium plays an important role for stabilization of the system. Both the intermolecular energy transfer mode and intramolecular energy transfer mode are responsible for the mechanism of fluorescence enhancement. In the optimum condi- tions, the fluorescence intensity is a linear function of Tb3~ concentration in the range of 7.8 × 10^-9-3.6 × 10^4 mol/L for the system Tb^3＋-La^3＋-TLA and 1.0 × 10^-8-4.7 × 10^-5 mol/L for the system Tb^3＋-Gd^3＋-TLA, and the limits of detection are 4.6 × 10^-10 mol/L and 6.0 × 10^-10 mol/L, respectively.
基金Supported by the Science and Technology Foundation of Beijing(GYYKW05070015)
文摘To explore the feasibility of extracting aromatic acid products from oxidizing coal, two aromatic acids, trimellitic and [1,1′-biphenyl]-2,2′-dicarboxylic acid, were selected as the solutes, and the extraction equilibrium of the acids were studied with 1-octanol, 50% tributyl phosphate （TBP） in kerosene, and 10% trialkylphosphine oxide （TRPO） in kerosene. The results showed that the degree of extraction of [1,1′-biphenyl]-2,2′-dicarboxylic acid was larger than that of trimellitic acid for all of the solvent, and the extraction capacity with TRPO is more effective than the one with TBP. The extraction behavior of aromatic polyacid is different from that of carboxylic acid, and the reactive extraction function of aromatic acids with TBP and TRPO is not as effective as that of carboxylic acid. 1-octanol could be used to remove [1,1′-biphenyl]-2,2′-dicarboxylic acid from the mixture of trimellitic acid and [1,1′-biphenyl]-2,2′-dicarboxylic acid. Because the weak hydrogen bond association exists between -OH in 1-octanol and -COOH in aromatic acid, the extractive selectivity of [ 1, 1′-biphenyl]-2,2′-dicarboxylic to trimellitic acid depends on the stoichiometric ratio.
