Supervisor(s): China Association for Science and Technology Sponsor(s): Chemical Industry and Engineering Society of China; Chemical Industry Press ISSN：0438-1157 CN：11-1946/TQ
CIESC Journal is supervised by China Association for Science and Technology and sponsored by Chemical Industry and Engineering Society of China, and Chemical Industry Press. The predecessor of the journal is Journal of China Chemical Industry Association launched in 1923 and Chemical Engineering launched in 1934. The journal aims at reflecting the major achievements of fundamental research and application in chemical and engineering and other related fields, as well as new technologies and methods. Its scope covers thermodynamics, separation engineering, process system engineering, bio-engineering and chemical engineering, energy and environmental engineering, material chemical engineering and nanotechnology, and modern chemical technology.
The journal is included in CA, JST, Pж(AJ), EI, CSCD.
A series of acidic deep eutectic solvents (DESs) EMIES/
nC
9H
10O
2 (
n = 0.25, 0.5, 1, 2, 4) were synthesized by simply heating the mixture of 1-ethyl-3-methylimidazolium ethylsulfate (EMIES) and 3-phenylpropionic acid (C
9H
10O
2). The structure of EMIES/
nC
9H
10O
2 was determined by FTIR,
1H NMR and TGA characterization. The extraction-oxidation desulfurization system was developed to remove sulfides from model oil using EMIES/
nC
9H
10O
2 as the extractant and catalyst, H
2O
2 as the oxidant. The influences of raw material ratio, reaction temperature, O/S ratio, amount of DESs and different sulfides on the desulfurization performance were investigated. The experimental results demonstrated the optimal reaction conditions were molar ratio of EMIES to C
9H
10O
2 of 1:1, temperature of 50 °C, O/S ratio of 8, the amount of DESs of 1.5 g and 5 ml model oil. The removal rates of DBT, 4,6-DMDBT and BT reached 94.8%, 91.6% and 46.4%, respectively, under the optimal condition. The DESs could be reused for 6 times without significant decrease in activity. In addition, the desulfurization mechanism of the oxidation-extraction desulfurization system was discussed.
The HPLC, LC-MS, GC-MS and other analytical methods were used to qualitatively and quantitatively analyze the intermediates and final products of Ni/W
2C catalyzed glucose hydrotreating under different process conditions. Ni-W
2C was recently reported as a promising catalyst for the hydrogenolysis of cellulose or glucose to EG with the highest yield of 75%, yet this was achieved at the substrate concentration less than 1% because the concentrated substrate would lead to coking. This meant low productivity and high cost for commercial production, thus hindering this promising process from industry application. Therefore, insights into the reaction network to elucidate the coking mechanism and to optimize the process are needed. In this work, the mechanism study on the glucose conversion, especially with the concentrated glucose substrate, over 2% Ni-30% W
2C/AC was systematically carried out. The reaction parameters including temperature, initial glucose concentration and H
2 pressure were investigated and the results, in combination with the intermediate analysis by LC, LC-MS and GC-MS, show that three parallel reaction pathways including retro-aldol reaction, isomerization and hydrogenation are involved in the reaction. C
2 product (EG) is originated from glucose hydrogenolysis while the C
3 products (1,2-PG and glycerol) are originated from fructose hydrogenolysis, and the dehydration of fructose leads to 5-HMF and finally to coke in concentrated glucose conversion. Based on these understanding, on one hand, the ratio of C
3 products to C
2 is manipulated by tuning of isomerization of glucose into fructose with base additive, and on the other hand, coking is avoided by accelerating its competing reactions even at the glucose concentration of 10% (mass). More interestingly, it is indicated that glucose of low concentration favors retro-aldol reaction while the one of high concentration tends to hydrogenate.
A series of graphene oxide composite metal catalysts were prepared and evaluated for their activity in the direct synthesis of dimethyl carbonate (DMC) by gas-phase oxidative carbonylation of methanol. The results show that the catalyst PdCl
2-CuCl
2-KOAc/AC@GO-HCl has the best catalytic activity and stability. The space–time yield (STY) of DMC was between 800 and 900 g·(L cat)
−1·h
−1, and the catalytic activity was stable in 16 h without significant decrease. The methanol selectivity was maintained above 95%, and the CO selectivity was between 35% and 40%. Combined with the results of XRD and XPS analyses, it was found that the formation of the active species Cu
2Cl(OH)
3 improved the catalytic activity of the catalyst. However, both CuO and KCl could cause the deactivation of the catalyst.
The occurrence and thermal stability of mercury in six samples of three coal ranks in two coal fields were studied by the sequential chemical extraction method and temperature-programmed pyrolysis method. The results show that the mercury in coal can be divided into five fractions: exchangeable mercury (F1), carbonate + sulfate + oxide-bound mercury (F2), silicate + aluminosilicate-bound mercury (F3), sulfide-bound mercury (F4) and residual mercury (F5). Among them, F2, F4 and F5 account for over 90%, and especially F4 ranges from 45.2% to 82.1%. Mercury speciation is heavily related to coal rank in this study. The proportion of F4 is significantly increased with increasing degree of coalification, whilst both F2 and F5 are gradually decreased, which can be inferred that the mercury combined with carbonate, sulfate and organic matter transforms into the sulfide during the metamorphic process of coal. The thermal release characteristics of mercury in coal depend on its speciation. F1 has the weakest thermal stability which completely releases when the temperature is lower than 150 °C, but F3 is the strongest in thermal stability with the release temperature above 600 °C. The release temperature of the other mercury species is between F1 and F3. As a result, the order of release temperature is F1 < F5 < F2 < F4 < F3. Based on the above findings, it should be an effective method to transform mercury into much more sulfide with stable state for stabilizing mercury speciation in liquid and solid by-products of coal combustion and other related processes.
Combined extraction of alumina from coal gangue and red mud was studied. The effects of red mud on the alumina extraction from coal gangue and the consumption of Na
2CO
3 were investigated. The effect of the red mud on the activation process of coal gangue by Na
2CO
3 calcination was studied by TG-DSC and XRD. The results showed that the dissolution of alumina for the mixed coal gangue-red mud-Na
2CO
3 sample increased with the Na/Al molar ratio and the calcination temperature. The alumina dissolution of the mixed sample reached 91.7% when the Na/Al molar ratio was 1.2 and the calcination temperature was 850 °C at the Al/Si molar ratio of 1. The consumption of Na
2CO
3 decreased 77.9% under this condition in comparison with that of coal gangue activated directly by Na
2CO
3. The results of TG-DSC and XRD showed that the interactions among coal gangue, red mud and Na
2CO
3 were weak at temperatures lower than 700 °C and were strengthened at temperatures higher than 800 °C. The addition of red mud would make the phases in the mixed sample selectively transformed into nepheline and zeolite with a Na:Al:Si molar ratio of 1:1:1 owing to the adjustment of the Al/Si molar ratio of the sample.
Under the condition of simulating coal-fired hot flue gas as a heat source and medium, Zhundong lignite was used as raw material to carry out carbonization–activation (one-step method) to prepare powdered activated coke by a one-dimensional settling furnace, and the Hg
0 adsorption capacity of activated coke was investigated. Further, the effects of SO
2, H
2O, O
2, CO
2, H
2O + O
2, SO
2 + O
2, and H
2O + SO
2 + O
2 on Hg
0 removal efficiency were examined in flue gas. The results indicate that the coke has high adsorption performance in Hg
0 removal. The N
2 atmosphere was used for comparison. The O
2, SO
2 + O
2, and H
2O + SO
2 + O
2 are beneficial for Hg
0 removal, while the H
2O, CO
2, SO
2, and H
2O + O
2 have an inhibiting effect on Hg
0 removal. Furthermore, we determined Hg 4f XPS spectra, in order to explore the mechanisms of inhibition and promotion of Hg
0 adsorption by activated coke under different flue gas. H
2O can inhibit the Hg
0 adsorption of activated coke by covering the activated coke sites and blocking the pores; SO
2 can inhibit the adsorption through the competitive adsorption of SO
2 and HgO on the activated coke, and THE CO
2 adsorbed by activated-coke micropores can also inhibit the adsorption of Hg
0 by activated coke. In the atmosphere of O
2 and SO
2 + O
2, the Hg
0 is oxidized into HgO and HgSO
3, respectively, and the HgSO
3 is further oxidized into HgSO
4 by O
2. Besides, in the atmosphere of H
2O + SO
2 + O
2, Hg
0 is oxidized into HgO and HgSO
4.
