Near-Infrared Spectroscopy Analysis of the Phytic Acid Content in Fuzzy Cottonseed Based on Machine Learning Algorithms.

Cottonseed is rich in oil and protein. However, its antinutritional factor content, of phytic acid (PA), has limited its utilization. Near-infrared (NIR) spectroscopy, combined with chemometrics, is an efficient and eco-friendly analytical technique for crop quality analysis. Despite its potential, there are currently no established NIR models for measuring the PA content in fuzzy cottonseeds. In this research, a total of 456 samples of fuzzy cottonseed were used as the experimental materials. Spectral pre-treatments, including first derivative (1D) and standard normal variable transformation (SNV), were applied, and the linear partial least squares (PLS), nonlinear support vector machine (SVM), and random forest (RF) methods were utilized to develop accurate calibration models for predicting the content of PA in fuzzy cottonseed. The results showed that the spectral pre-treatment significantly improved the prediction performance of the models, with the RF model exhibiting the best prediction performance. The RF model had a coefficient of determination in prediction (R2p) of 0.9114, and its residual predictive deviation (RPD) was 3.9828, which indicates its high accuracy in measuring the PA content in fuzzy cottonseed. Additionally, this method avoids the costly and time-consuming delinting and crushing of cottonseeds, making it an economical and environmentally friendly alternative.

Characteristics of the Blockage from Air Nozzle Guide Duct in Circulating the Fluidized-Bed Coal Gasifier and Its Formation Mechanism.

Blockage is often generated in the air nozzle guide duct in a circulating fluidized-bed coal gasifier (CFBG), especially with Zhundong sub-bituminous coal (ZSBC) as the raw material. A typical example is found in one CFBG sample from Xinjiang Yihua Chemical Industry Co, Ltd. The serious blockage can be observed obviously. As so far, it is not clear for the characteristics and generation mechanism of the blockage. For analysis, the blockage can be classified into two parts, wall-layer blockage (WLB) and center-layer blockage (CLB). To inhibit its formation, it is of significance to analyze the composition, surface morphology, and formation mechanism of the two blockages. In our experiments, WLB and CLB were tested by XRF, XRD, FTIR, SEM-EDS, and SEM-mapping methods. Results showed that WLB presents high content of Fe, Cr, and Ni, and Fe mainly existed in the form of metal oxides. CLB is dominated by Si (43.04%), derived from silica and alkali and alkaline-earth metals silicates, and the migration of Fe, Cr, and Ni elements from the duct material was observed. Compared with WLB, from FTIR analysis, CLB contains more inorganic minerals, and the absorption peak of inorganic minerals is mainly attributed to asymmetric Si-O-Si. Many fine particles are attached to the surface of the WLB, while the surface of the CLB is smooth, and there is noticeable raised texture, which is presumed to be the result of particle melting and agglomerating as the bottom ash enters the duct in the gasification process. For the formation of the blockage, this paper speculates that it is mainly due to the difference in flow resistance near the air nozzle outlet, resulting in the formation of a flow dead zone at the bottom of the gasifier, which leads to large amounts of ash overcoming the outlet resistance and leaking into the air nozzle, and next, the ash corrodes in the tube, resulting in wall deposition and ultimately blocking the air guide duct. Two methods can be tried to avoid or inhibit the formation of blockage in the duct, including optimizing air nozzle with more wear-resistant and heat-resistant materials and adjusting the distance between air nozzles to avoid mutual interference from ash particles.

Effect of Solvent Treatment on the Composition and Structure of Santanghu Long Flame Coal and Its Rapid Pyrolysis Products.

Easily soluble organic components in Santanghu long flame coal (SLFC) from Hami (Xinjiang, China) were separated by CS2 and acetone mixed solvent (v/v = 1:1) under ultrasonic condition, and the extract residue was stratified by carbon tetrachloride to obtain the light raffinate component (SLFC-L). The effect of solvent treatment on the composition and structure of the coal and its rapid pyrolysis products was analyzed. Solvent treatment can reduce the moisture content in coal from 9.48% to 6.45% and increase the volatile matter from 26.59% to 28.78%, while the macromolecular structure of the coal changed slightly, demonstrating the stability of coal's complex organic structure. Compared with raw coal, the relative contents of oxygen-containing functional groups and aromatic groups in SLFC-L are higher, and the weight loss rates of both SLFC and SLFC-L reached the maximum at about 450 °C. In contrast, the loss rate of SLFC-L is more obvious, being 33.62% higher than that of SLFC. Pyrolysis products from SLFC at 450 °C by Py-GC/MS are mainly aliphatic hydrocarbons and oxygenated compounds, and the relative contents of aliphatic hydrocarbons decreased from 48.48% to 36.13%, while the contents of oxygenates increased from 39.07% to 44.95%. Overall, the composition and functional group in the coal sample were changed after solvent treatment, resulting in a difference in the composition and distribution of its pyrolysis products.

Effect of Kaolin on the Thermal Conversion Performance of Zhundong Sub-bituminous Coal.

In order to investigate how kaolin affects the structure and thermal conversion performance of Zhundong sub-bituminous coal (ZSBC), this study focused on analyzing the pyrolysis, combustion, and gasification of both ZSBC and a mixture of kaolin and Zhundong sub-bituminous coal (ZSBC-K) using the TG-DTG technique. The findings demonstrated that the addition of kaolin enhanced the pyrolysis and combustion performance of ZSBC-K. To explain the above phenomena, the composition and structure of char from ZSBC and ZSBC-K were characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), Raman spectroscopy (Raman), scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The results showed that the addition of kaolin decreased the degree of graphitization of char and increased the relative content of oxygen on the surface of the char. Moreover, the addition of kaolin increased the degree of disorder of the char and formed more char pores. The rich pores were conducive to the entry of the gasification agent into the coal char particles, which enhanced the gasification activity. Additionally, the coal char mixed with kaolin contains several oxygen-containing functional groups and defect sites that facilitate the cracking and gasification performance of the macromolecular network's aromatic ring structure.

Investigation on the Composition and Extraction Mechanism of the Soluble Species from Oily Sludge by Solvent Extraction.

Oily sludge (OS) was extracted with petroleum ether (PE), methanol, carbon disulfide (CDS), acetone, and isometric CDS/acetone mixture (IMCDSAM), respectively, to obtain soluble species (E1-E5) and extraction residues (R1-R5). The soluble species were analyzed by gas chromatography/mass spectrometry (GC/MS), and the extraction residues were characterized by Fourier transform infrared spectrometry (FTIR) and thermogravimetric analysis (TGA). Results showed that the extract yield of the soluble species from OS using CDS and IMCDSAM as the solvent was 61.0 and 67.3%, respectively. GC/MS results exhibited that the compounds detected in E1-E5 are mainly hydrocarbons and oxygen-containing compounds. E1-E5 are rich in alkanes, alkenes, ketones, alcohols, and other oxygen-containing compounds. Double-bond equivalence (DBE) and carbon numbers (CNs) of the compounds detected in E1, E2, and E4 are distributed in 0-4 (DBE) and 10-20 (CNs), respectively, while the DBE and CNs of the detected compounds in E3 and E5 are concentrated in 0-6 and 15-35, respectively. Thermogravimetry-differential thermogravimetry (TG-DTG) profiles presented that pyrolysis of OS occurred mainly in the temperature range of 150-750 °C, while pyrolysis of R1-R5 took place in the range of 350-750 °C. In the temperature range of 150-550 °C, the weight losses of OS and each extraction residue differ significantly, with OS having a much higher weight loss than the extraction residues. Meanwhile, the possible mechanism of oily sludge extraction was considered. Results revealed that selecting a low-polar or nonpolar solvent capable of selectively destroying hydrogen bonds and/or aromatic interactions is critical for improving the extract yield of OS.

Copyrolysis and Cocombustion Performance of Karamay Oily Sludge and Zhundong Subbituminous Coal.

Karamay oily sludge (KOS), Zhundong subbituminous coal (ZSBC), and their equal mass mixture (M KOS/ZSBC) were selected as the research samples, and composition characteristics and pyrolysis performance of KOS, ZSBC, and its mixture were investigated by means of various analytical methods. Results showed that yields of fixed carbon and volatile matter from ZSBC are higher than those from KOS, and the content of moisture in ZSBC is also higher; most of the components in KOS are inorganic minerals, with the ash yield of 71.4%, and the fixed carbon yield of nearly 0. According to Fourier transform infrared spectrometer (FTIR) analysis, the types of functional groups in KOS and ZSBC are basically the same, while the contents of which are different. Thermogravimetry-differential thermogravimetry (TG-DTG) analysis indicated that the mass loss of ZSBC, KOS, and M KOS/ZSBC are 41.1%, 25.7%, and 32.8% with a heating temperature up to 990 °C, respectively. By analyzing the theoretical pyrolysis and combustion TG-DTG profiles of M KOS/ZSBC and the measured composition of the flue gas produced during the tested processes, it is found that the mixture of oily sludge and coal helps generate remarkable combustible gases with significantly reduced CO2, indicating that there is an effective "synergistic effect" between KOS and ZSBC. Based on the Coats-Redfern (CR) model, in the main pyrolysis temperature range, when the reaction order is selected as 1, the kinetic fitting effect of pyrolysis and combustion profiles for ZSBC is better, with the correlation coefficient R 2 > 0.98. While for KOS and M KOS/ZSBC, in N2 atmosphere, the fitting effect is satisfactory as the reaction order is set to 5, in air atmosphere, the better fitting effect is considered that reaction order is selected as 1.

Pyrolysis Kinetic Analysis of Sequential Extract Residues from Hefeng Subbituminous Coal Based on the Coats-Redfern Method.

Sequential extract residues (R i , i = 1, 2, 3, 4, and 5) were obtained from Hefeng acid-washing coal (HFAC) by petroleum ether, carbon disulfide, methanol, acetone, and isometric carbon disulfide/acetone mixture, sequentially. Pyrolysis behavior of the residues was determined using thermogravimetry analysis. The Coats-Redfern method with different reaction orders was used to analyze the pyrolysis kinetic of each sample, and the kinetic parameters, including correlation coefficient (R 2), activation energy (E), and pre-exponential factor (A), were calculated. Results showed that the weight loss of extract residues was higher than HFAC, and pyrolysis behavior varies greatly for residues, which is related to the unstable structure after extraction. From conversion-temperature (α-T) curves, the pyrolysis process was divided into three stages: low-temperature stage (150-350 °C), medium-temperature stage (350-550 °C), and high-temperature stage (550-950 °C). The medium-temperature stage made great contribution to the process of pyrolysis, which was dominated by depolymerization and decomposition reaction. The relationship between kinetic parameters and reaction order showed that the swelling effect is an important reason for the discrepancy of E for each sample in the process of pyrolysis.

Analysis of Pyrolysis Performance and Molecular Structure of Five Kinds of Low-Rank Coals in Xinjiang Based on the TG-DTG Method.

Taking five coal samples (FCSs) in Xinjiang as the research object, characterizations such as proximate analysis, ultimate analysis, Fourier transform infrared (FTIR), and thermogravimetry-differential thermal analysis (TG-DTG) were carried out. The Coats-Redfern model was used to simulate pyrolysis kinetics of FCSs under different reaction orders (ROs). The results showed that except for HSBC, the R 2 of the other four coal samples are all higher than 0.9, which showed a good correlation effect. FCSs present similar reaction activation energy in the same RO and temperature range. Results of FTIR showed that the hydroxyl groups of FCSs, in the range of 3100-3600 cm-1, were mainly self-associated hydroxyl hydrogen bonds and hydroxyl π bonds, and they occupied over 63%. Among them, the pyrolysis characteristic index (D) of XBC was 4.139 × 10-6, higher than those of other samples, and it showed good pyrolysis performance. Moreover, by reducing the temperature range appropriately, the fitting results showed a better correlation effect.

Effect of the Nickel Source on the Structure, Performance, and Carbon Deposition of the Ni/Al2O3 Catalyst for CO2-CH4 Reforming.

Ni/Al2O3 catalysts were prepared with Ni(NO3)2·6H2O, NiSO4·6H2O, NiCl2·6H2O, and NiC4H6O4·4H2O as nickel sources by the solution combustion method. The catalysts were characterized by X-ray diffraction, H2 temperature-programmed hydrogenation, TG-DTG, TPH, and transmission electron microscopy methods, and the effect of the nickel source on performance of the Ni/Al2O3 catalyst was investigated via the CO2-CH4 reforming experiment. Results showed that Ni dispersion, Ni size, and the metal-support interaction between active component Ni and the support were influenced significantly by anion in nickel sources, resulting in that the performance of each catalyst was different. Highly dispersed Ni species, small Ni crystallite size, and strong metal-support interaction were presented in the Ni/Al2O3 catalysts with Ni(NO3)2·6H2O and NiSO4·6H2O as nickel sources. Evaluation results showed that the catalyst prepared with Ni(NO3)2·6H2O exhibited higher activity and stability, with CH4 and CO2 conversions of 31.21 and 48.97%. Carbon deposition analysis demonstrated that the catalyst prepared with NiSO4·6H2O contained more graphite carbon.

Functional Group Characteristics and Pyrolysis/Combustion Performance of Karamay OS Based on FT-IR and TG-DTG Analyses.

Proximate analysis, ultimate analysis, Fourier-transform infrared spectroscopy (FT-IR), and thermogravimetry-differential thermal analysis characterization were carried out on oily sludge (OS) samples OS1-OS5, from Karamay, Xinjiang, China. The Coast-Redfern model (CRm) was used to simulate the pyrolysis and combustion kinetics of oily samples. The results showed that the peak area percentage of benzene ring trisubstitution of OS5, in the range of 700-900 cm-1, is close to 75%, corresponding to its high volatile content. Based on the kinetic analysis by the CRm, it is found that the fitting degree of the five samples is better when the reaction order is selected as n = 2, with R 2 close to 1.00 and 2RT/E to 0. Among them, the S N and D W of OS5 are 17.8 × 10-10%2 min-2 °C-3 and 0.10899 × 10-5% min-1 °C-2, respectively, higher than those of other samples, indicating a good combustion performance.

Influence of Ni Precursors on the Structure, Performance, and Carbon Deposition of Ni-Al2O3 Catalysts for CO Methanation.

Three Ni-Al2O3 catalysts were prepared, in planetary ball-milling machine, by the mechanochemical method with Al(NO3)3·9H2O as the aluminum precursor, (NH4)2CO3 as the precipitant, and Ni(NO3)2·6H2O, NiCl2·6H2O, and Ni(CH3COO)2·4H2O as nickel precursors (the corresponding catalysts were labeled as Ni-NO, Ni-Cl, and Ni-Ac). The prepared catalysts were characterized by X-ray diffraction (XRD), temperature-programmed reduction (H2-TPR), and N2 adsorption-desorption technologies, and CO methanation performance evaluation was carried out for the catalysts. Results showed that the catalyst with Ni(NO3)2·6H2O as the precursor presented good Ni dispersibility and a small Ni grain size of 6.80 nm. CO conversion, CH4 selectivity, and yield of the catalyst were as high as 78.8, 87.9, and 69.8%, respectively. Carbon deposition analysis from temperature-programmed hydrogenation (TPH) characterization showed that the H2 consumption peak area of the three samples followed the order: Ni-NO (2886.66 au) < Ni-Cl (4389.97 au) < Ni-Ac (5721.65 au), indicating that the Ni-NO catalyst showed higher resistance to carbon deposition, which might be due to its small Ni grain size.

Effects of Promoters on the Structure, Performance, and Carbon Deposition of Ni-Al2O3 Catalysts for CO2-CH4 Reforming.

Modified Ni-Al2O3 catalysts with Ca, Co, and Ce species as promoters were prepared by the combustion method, and the structure, morphology, reduction characteristic, and CO2-CH4 reforming of the catalysts were discussed by X-ray diffraction (XRD), H2-temperature-programmed reduction (H2-TPR), energy-dispersive X-ray (EDX) mapping, NH3-temperature-programmed desorption (NH3-TPD), N2 adsorption-desorption, thermogravimetric-differential thermal analysis (TG-DTG), and temperature-programmed hydrogenation (TPH) methods. The crystal size of Ni on Ca-Ni-Al2O3 was 16.97 nm, and the active component and additive were distributed well in the catalyst. Co-Ni-Al2O3 presented a surface area of 65.70 m2·g-1 and a pore diameter of 161.60 nm. Ce-Ni-Al2O3 showed relatively stable nickel-aluminum spinel (NiAl2O4), which could not be easily reduced to the active component Ni. Evaluation results demonstrated that the performance of the catalysts followed the order Co-Ni-Al2O3 > Ca-Ni-Al2O3 > Ni-Al2O3 > Ce-Ni-Al2O3. Carbon deposition analysis showed that the carbon resistance of Ca-Ni-Al2O3 was poor and graphitic carbon was generated on the catalyst. However, Ce-Ni-Al2O3 showed less carbon deposition, which might have resulted from the lower activity of the catalyst.

Effect of Swelling by Organic Solvent on Structure, Pyrolysis, and Methanol Extraction Performance of Hefeng Bituminous Coal.

N-methyl-2-pyrrolidone (NMP), pyridine (Py), tetrahydrofuran (THF), and tetralin (THN) were used to swell Hefeng acid-washed bituminous coal (HBCAC). The swelling effect on HBCAC by each solvent is different, among which NMP presented well swelling performance, with a swelling degree of 2.11. FTIR results showed that acid washing and swelling processes presented a marginal effect on HBC, and there was no damage to the macromolecule structure of the coal. TG-DTG profiles of the swollen coals illustrated that the total weight loss of each sample was lower than that of the acid-washing one, while the temperature of the maximum weight loss rate peak was almost unchanged, around 445 °C. Extract yield by methanol followed the order of HBCAC > HBC > HBCAC-NMP (swelled by NMP), showing that acid washing promoted the methanol extraction process, with a higher extract yield of 3.21%, which is twice that of HBC (1.66%).

Effect of Ca Promoter on the Structure, Performance, and Carbon Deposition of Ni-Al2O3 Catalyst for CO2-CH4 Reforming.

Ni-Al2O3 catalyst with different Ca abundance for CO2-CH4 reforming was prepared by the solution combustion method. By some mature characterization methods, such as XRD, H2-TPR, EDX mapping, TEM, TPH and TG-DTG technologies, and the reforming experiment, the effect of Ca content on the structure, reforming performance, and carbon deposition of Ni-Al2O3 catalyst was investigated. Results showed that the grain size of active component Ni on the 4 wt % Ca-modified catalyst (Ni-Ca-4) was small (13.67 nm), presenting good dispersion, and that Ni and Ca elements were well distributed on the support, which was more conducive to the CO2-CH4 reforming. Evaluation results showed that activity of Ni-Ca-4 was higher than the others, with CH4 and CO2 conversions of 52.0 and 96.7%, respectively, and H2/CO ratio close to unit. Carbon deposition proposed that the amount of carbon deposited on the surface of Ni-Ca-4 was lower (18%), and the type of carbon was attributed to amorphous carbon, indicating that 4 wt % Ca-promoted catalyst presented better anticarbon deposition performance.

Sequential thermal dissolution of two low-rank coals and characterization of their structures by high-performance liquid chromatography/time-of-flight mass spectrometry and gas chromatography/mass spectrometry.

RATIONALE: Gas chromatography/mass spectrometry (GC/MS) and high-performance liquid chromatography/time-of-flight mass spectrometry (HPLC/TOF-MS) were used to separate and reveal the molecular characteristics of organic matter in low-rank coals. METHODS: Six soluble portions (SPs) were obtained by sequential thermal dissolution (TD) of two low-rank coals in the order of cyclohexane, acetone and methanol solvents at 300°C. Organic matter with different molecular characteristics were enriched in eachTD extract, which was further separated and analyzed by GC/MS and HPLC/TOF-MS using an electrospray ionization source in positive mode to obtain a comprehensive understanding of the structural composition of coals. RESULTS: Low polarity compounds like alkanes and arenes have a better solubility in cyclohexane. Phorone has the highest relative abundance in the acetone SPs, and the main compounds detected in the methanol SPs are alcohols and phenols. According to the data from HPLC/TOF-MS, most of the oxygen atoms are in the form of carbonyl and alkoxy groups. The nitrogen-containing compounds in SPs are mainly saturated aliphatic amines and pyridines. The sulfur-containing compounds mainly exist in the form of thioalkanes and thiophenes. CONCLUSIONS: Non-destructive methods were used to obtain soluble matter from coals, and different chromatographic and mass spectrometric techniques were used to separate and analyze the organic matter in coals. Detailed molecular structural information was obtained for the efficient and clean utilization of low-rank coals.

Effects of calcination temperatures on the structure-activity relationship of Ni-La/Al2O3 catalysts for syngas methanation.

A series of Ni-La/Al2O3 catalysts for the syngas methanation reaction were prepared by a mechanochemical method and characterized by thermogravimetric analysis (TG-DTA), X-ray fluorescence (XRF), X-ray diffraction (XRD), N2 adsorption-desorption, H2 temperature-programmed reduction (H2-TPR), and X-ray photoelectron spectroscopy (XPS). The calcination temperatures (350-700 °C) had significant impacts on the crystallite sizes and interactions between NiO and Al2O3. The catalyst calcined at 400 °C (cat-400) showed a 12.1% Ni dispersion degree and the maximum bound state of NiO (54%) through the Gaussian fitting of H2-TPR. Cat-400 also achieved the highest CO conversion, CH4 selectivity and yield. Cat-400 exhibited good stability and catalytic activity in a lifetime testing of 200 h. The deactivation of cat-400 was mainly caused by carbon deposition according to the data from XRD, TG-DTG and XPS.

Effects of a forming process on the properties and structure of RANEY®-Ni catalysts for the hydrogenation of 1,4-butenediol.

Three commercial Ni-Al alloys formed by a vacuum atomization method (NAV), atmospheric atomization method (NAA) and high-temperature melting method (NAH) were leached by 10 wt% NaOH solution to prepare three RANEY®-Ni catalysts (RNAV, RNAA and RNAH, correspondingly). The effects of a forming process on the structure of Ni-Al alloys and the corresponding RANEY®-Ni catalysts were investigated via XRD, XPS, SEM, TEM, NH3-TPD, N2 adsorption-desorption and EDX-mapping studies. Also, the as-prepared RANEY®-Ni catalysts were evaluated via the hydrogenation of 1,4-butenediol (BED) to produce 1,4-butanediol (BDO). The results showed that the specific surface areas and surface morphologies of the Ni-Al alloys present significant differences. Meanwhile, the RNAA sample presented a comparatively regular morphology, similar to a small piece of sugar cane. The weak and medium acid peak areas of the RNAA catalyst were lower than those of the other samples. RNAV showed higher weak and medium acid peak areas, demonstrating the higher number of acid centers on the surface of the catalyst. The surface of the RNAA catalyst obtained from NAA contained more active component-Ni, about 90 wt% on the surface, and the specific surface area of the sample was 75 times that of its precursor Ni-Al alloy powder (NAA). The evaluation results present that the RNAA catalyst shows better hydrogenation performance, with BED conversion of 100%, both BDO selectivity and yield of 46.11%.