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Catalysts · 2021 ·Vol. 11 ·期 12 ·1464 · IF 4.146

Synthesis of Brominated Alkanes via Heterogeneous Catalytic Distillation over Al2O3/SO42−/ZrO2

Su Yang,Xiaoxuan Guo,Xiaomei Pan,Liuyu Gu,Xueping Liu,Lijing Gao,Guomin Xiao

Concentrated sulfuric acid is generally used as a catalyst for producing brominated alkanes in traditional methods, but is highly corrosive and difficult to separate. This work reports the preparation of bromopropane from n-propanol based on a reactive distillation strategy combined with alumina-modified sulfated zirconia (Al2O3/SO42−/ZrO2) as a heterogenous catalyst. As expected, under the optimum reaction conditions (110 °C), the yield of bromopropane was 96.18% without side reactions due to the reactive distillation strategy. Meanwhile, the microscopic morphology and performance of Al2O3/SO42−/ZrO2were evaluated by X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), Brunner–Emmet–Teller (BET), Fourier transform infrared spectroscopy (FT–IR), and other characterization methods. The results confirmed that the morphology of zirconia sulfate is effectively regulated by the modification method of alumina, and more edges and angles provide more catalytic acid sites for the reaction. Furthermore, Al2O3/SO42−/ZrO2exhibited high stability and remarkable reusability due to the strong chemical bond Zr–Al–Zr. This work provides a practical method for the preparation of bromopropane and can be further extended to the preparation of other bromoalkanes.Keywords:sulfated zirconia;modification of alumina;bromopropane;catalytic distillation

CAS / MDL: 7699-43-6
研究领域: 化学工程 · 催化 · 有机化学
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Surfaces and Interfaces · 2021 · IF 4.837

Platinum-alumina modified SO42−-ZrO2/Al2O3 based bifunctional catalyst for significantly improved n-butane isomerization performance

Ikram Ullah,T.A. Taha,Asma M. Alenad,Ikram Uddin,Asif Hayat,Ashiq Hayat,Muhammad Sohail,Ahmad Irfan,Javid Khan,Arkom Palamanit

In this study, sulfated zirconia with loading of platinum (Pt) and platinum alumina (PA-Al 2 O 3 ) promoted sulfated zirconia (SZ) catalysts were synthesized by hydro-thermal route. The samples were characterized by XRD, BET, FT-IR, NH 3 -TPD, and TGA. The catalytic efficiency of all the synthesized catalysts was tested on the isomerization of n -butane. The results indicated that the conversion of n -butane (71.04%), selectivity to i -butane (98.96%), and yield of i -butane (70.30%) is significantly high for PA/SZ sample than that of Pt modified SZ and bare SZ. The results of this study suggest that the SZ modified by Pt/Al 2 O 3 (PA) provided better catalytic performance and higher stability (within 25 h of TOS), when compared with SZ, and Pt-modified SZ.

研究领域: 化学工程 · 催化科学
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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES · 2025 · IF 8.5

Memory effect based on layered double hydroxides for uniform modification of collagen by zirconium sulfate

Jianzhong Ma,Jiamin Zhao,Zhijie Cheng,Na Yang

Tanning agents are chemical substances that cause structural changes in collagen. Zirconium tanning agent is a promising alternative to chromium tanning agent, but the problem of uneven tanning due to its rapid binding to collagen limits its practical application in leather manufacturing. In this study, a combined tanning strategy based on layered double hydroxides (LDHs) and zirconium sulfate was proposed, aiming to promote the uniform distribution of conventional zirconium tanning agents in collagen fibers and to improve the physicochemical properties of tanned leather through the memory effect of LDHs. The nanostructure of LDHs was modulated by calcination treatment to increase their specific surface area, Al 3+ defects and oxygen vacancies. The results showed that by adding layered double oxides (LDO), the uptake of zirconium sulfate by collagen was increased and the uniform distribution of zirconium sulfate in collagen fibers was promoted, which improved the thermal stability and physico-mechanical properties of the leather. In addition, LDO binds to collagen via hydrogen, ionic and coordination bonds, whereas Zr(SO 4 ) 2 binds to collagen mainly via coordination bonds. This study provides a new strategy for the effective application of zirconium tanning agents in the clean production of leather.

CAS / MDL: 7446-31-3
研究领域: 材料科学 · 生物化学 · 制革工业
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Journal of Cleaner Production · 2019 · IF 6.395

A clean and economical processing system to improve the fluffiness of down fibers based on alkalized Zr(SO4)2

Taotao Qiang,Qi Zhang,Liang Chen

Down fibers is the most popular filling material and widely applied in daily life products such as homes, apparel and sporting gear due to its features of being natural, soft and warm keeping. The fluffiness is quite important to reflect the excellent performance of down fibers. However, owing to the short feeding cycle of poultry, the high content of immature down fibers leads to low fluffiness, which affects the quality of down fibers. In our work, the down fibers with amount of maximum raw materials and the fluffiness of 450 cm 3 /30 g were taken as the research samples. Clean and efficient alkaline zirconium sulfate was used as fluffing agent of down fibers. The cost of using alkalized zirconium sulfate treatment is relatively cheap compared with the traditional fluffing agent glutaraldehyde. Different doses of alkalized zirconium sulfate were used to cross-link the natural down fibers to improve the fluffiness. The results showed that when the dosage of alkalized zirconium sulfate was 2% of the weight of fibers, the performance of down fibers were the best and the fluffiness increased by 25%. It has a good practical significance to improve the economic benefits of down manufacturers. Meanwhile, the down fibers treated with alkalized zirconium sulfate were characterized by Energy dispersive spectrometer (EDS), X-ray diffractometer (XRD), Differential scanning calorimetry (DSC) and the changes of free amino content. Furthermore, measurement of zirconium ion concentration in wastewater by ICP showed that alkaline zirconium sulfate has achieved high absorption efficiency. Moreover, ultra depth microscope observation showed that the down fibers treated with alkalized zirconium sulfate have a better dyeing performance compared to untreated fibers. Overall, this work contributed a new insight into the sustainable development of down industry, and it further confirmed that it is a good approach to use the alkalized zirconium sulfate as the fluffing agent to improve the performance of down fibers.

CAS / MDL: 7699-43-6
研究领域: 材料科学 · 纺织工程 · 环境科学
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RESEARCH ON CHEMICAL INTERMEDIATES · 2018 ·Vol. 45 ·期 3 ·1073-1086 · IF 1.674

Preparation, characterization and application of ordered mesoporous sulfated zirconia

Wang Yun Jie,Yuan Hong,Zhang Hong

A series of ordered mesoporous sulfated zirconia (OMSZ) with different calcination temperatures (400–650 °C) have been synthesized by a self-assembly method using zirconium n -propoxide as raw material, P123 (EO 20 PO 70 EO 20 ) as structure-directing agent and ammonium sulfate as sulfonating agent. The transmission electron microscopy results indicated that the OMSZ had the ordered mesoporous structure and the X-ray diffraction analysis further revealed that the OMSZ had hexagonal ordering structure. The N 2 –BET results showed that the OMSZ were mesoporous materials and, when the calcination temperature was 500 °C, the BET surface area could reach 183 m 2 /g. Temperature-programed desorption of NH 3 (NH 3 –TPD) analysis confirmed that the OMSZ possessed a superacid when the calcination temperature was higher than 450 °C. FTIR-pyridine adsorption results indicated that the OMSZ surfaces were mainly the Lewis acid sites. The catalytic activity of OMSZ was observed for transesterification of waste frying oil, and 92% of yield could be obtained after 6 h at 200 °C.

研究领域: 材料科学 · 催化化学
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CHINESE JOURNAL OF CHEMICAL ENGINEERING · 2020 · IF 2.627

Promoting di-isobutene selectivity over ZnO/ZrO2-SO4 in isobutene oligomerization

Jiyuan Li,Mifen Cui,Zhuxiu Zhang,Xian Chen,Qing Liu,Zhaoyang Fei,Jihai Tang,Xu Qiao

Isooctane attracts great interest in recent years because of its promising potential as friendly-environmental gasoline, which is obtained by dimerization of isobutene with a hydrogenation step. Herein, a solid acid catalyst sulfated zirconia modified by ZnO was prepared. The oligomerization of isobutene had been investigated over ZrO 2 -SO 4 and ZnO( X )/ZrO 2 -SO 4 catalyst in order to find efficient catalysts for the production of isobutene oligomers . The presence of ZnO obviously enhanced the dimerization of isobutene and ZnO( X )/ZrO 2 -SO 4 exhibited the highest di-isobutene yield of 60%. Kinetic studies showed the higher trimerization-to-dimerization activation energy ratios of ZnO( X )/ZrO 2 -SO 4 than those of ZrO 2 -SO 4 from 353 to 393 K. In addition, reaction rate of dimerization was higher than trimerization over ZnO( X )/ZrO 2 -SO 4 . The high L/B ratio manifested the capability to enhance the selectivity of C 8 in isobutene dimerization. Furthermore, ZnO( X )/ZrO 2 -SO 4 exhibited stable conversion for the dimerization of isobutene.

研究领域: 化学工程 · 催化 · 石油化学
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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH · 2020 · IF 3.573

A Novel Process for the Production of Triethylene Glycol Di-2-ethylhexoate by Reactive Distillation Using a Sulfated Zirconia Catalyst

Xingang Li,Qingyu Zhang,Hong Li,Xin Gao

To solve the problem of catalyst recovery, high investment, and high energy consumption in the traditional manufacturing process of triethylene glycol di-2-ethylhexoate (TGDE), sulfated zirconia (HND-32) and reactive distillation (RD) were used in this work. Kinetics experiments for the esterification of triethylene glycol and 2-ethylhexanoic acid catalyzed by sulfated zirconia were performed at 463.15–493.15 K. The pseudo-homogeneous model was used to obtain the kinetics equation. Then, the process analysis results of the RD column indicate that there is an optimal theoretical plate number of the stripping section to obtain the highest yield of TGDE. The yield of TGDE can be enhanced to 98.15%, and 98.5 wt % TGDE can be obtained in the bottom of the RD column when the feed molar ratio is the stoichiometric ratio.

研究领域: 化学工程 · 催化化学
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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES · 2025 · IF 8.5

Harnessing the reversible reaction principle: A novel Zr-based halide Perovskite tanning system for effective Zr4+ penetration in the leather collagen

Jianzhong Ma,Tongtong Ma,Qianqian Fan,Yiming Shen,Mi Liu,Wenbo Zhang

The development of green chromium-free tanning agents continues to be actively researched as a prominent topic in the leather industry. Zirconium tanning agents have good tanning performance, but their permeability is poor. Halide perovskites, composed of metal ions and organic ligands, are metal-tunable nanomaterials. In order to improve the permeability of zirconium. In this study, Cs 2 ZrCl 6 was synthesized using zirconium ions and combined with Zr(SO 4 ) 2 for collagen modification application. Based on the principle of reversible reactions, the introduction of Zr(SO 4 ) 2 effectively alleviated the rapid hydrolysis of Cs 2 ZrCl 6 , ensuring the preservation of its nanostructure and enabling continuous penetration during the tanning process. The EDS analysis confirmed the uniform distribution of zirconium in leather collagen tanned with Cs 2 ZrCl 6 /Zr(SO 4 ) 2 . Compared with Zr(SO 4 ) 2 tanned leather (73.1 °C), the shrinkage temperatures of Cs 2 ZrCl 6 /Zr(SO 4 ) 2 tanned leather collagen (83.7 °C) is better. Additionally, the BOD 5 /COD cr ratio of the tannery wastewater in this system is 0.65, indicating excellent biodegradability. The development of the Cs 2 ZrCl 6 /Zr(SO 4 ) 2 tanning system provides a new approach for creating chromium-free tanning agents.

CAS / MDL: 8049-47-6
研究领域: 材料科学 · 化学工程 · 环境科学 · 纳米技术
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JOURNAL OF APPLIED POLYMER SCIENCE · 2018 ·Vol. 135 ·期 42 ·46758 · IF 1.901

Simultaneous enhancement of proton conductivity and methanol resistance of sulfonated poly(phthalazinone ether sulfone ketone)/superacid sulfated zirconia composite membranes for direct methanol fuel cells

Dongxing Zhen,Gaohong He,Xinlong Xu,Xiaoming Yan,Naixu Du,Xue Gong,Tiantian Li,Yan Dai,Xuemei Wu

Sulfonated poly(phthalazinone ether sulfone ketone) (SPPESK) is a kind of novel non-fluorine polymer, whose high proton conductivity is dependent on high degree of sulfonation, which resulting in loss of dimensional stability. SPPESK/superacid sulfated zirconia (SZrO 2 ) composite proton exchange membranes are fabricated first. The composite membrane shows good dimensional stability, ascribing to the restriction effect of hydrogen bonding force on the mobility and relaxation of polymer chains. Introducing SZrO 2 simultaneously enhances the conductivity and anti-methanol permeation, owing to the connected ion domains, enlarged and aggregated ion clusters, excess proton conduction sites, and good blocking effect to methanol of SZrO 2 . For composite membrane containing 1.5 wt % SZrO 2 , the highest conductivity of 180 mS cm −1 is obtained at 80 °C. Compared with pristine SPPESK and Nafion 115, the methanol permeability is reduced by 54 and 77%, and the maximum power density of direct methanol fuel cell is enhanced by 133 and 25%. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135 , 46758.

研究领域: 材料科学 · 能源科学
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SEPARATION AND PURIFICATION TECHNOLOGY · 2022 · IF 9.136

Alkylation for removing trace olefins from reforming aromatics over novel Al2O3@SO42-/ZrO2 catalysts derived from the ZrO2-coated γ-Al2O3 strategy

Sitan Wang,Xuan Meng,Naiwang Liu,Li Shi

Sulfated zirconia, as a promising catalyst in various acid-catalytic reactions, still suffer from unsatisfactory catalytic stability and regeneration performance due to severe leaching of sulfur species, while aluminum modification can effectively overcome these drawbacks. Unfortunately, the limited acceptability of aluminum content by co-precipitation and milling methods remains a critical issue. Herein, an effective strategy of coating sulfated zirconia on the surface of γ-Al 2 O 3 was developed to synthesize the novel Al 2 O 3 @SO 4 2- /ZrO 2 catalyst with high aluminum content. The synthesis variables were investigated and systematically optimized. The structural and acidic properties of Al 2 O 3 @SO 4 2- /ZrO 2 were determined by XRD, HR-TEM equipped with EDX, N 2 adsorption-desorption isotherms, EA, FT-IR, NH 3 -TPD and Py-FTIR. Results indicated that the unique structure constructed by sulfated zirconia coated on γ-Al 2 O 3 not only realized the stabilization of favorable tetragonal zirconia phase even at exceedingly high aluminum content but also promoted Brønsted acid sites. Accordingly, the optimal Al 2 O 3 @SO 4 2- /ZrO 2 - 50% performed outstanding catalytic activity and stability, given the olefins conversion of 98%-75% during the continuous reaction experiment. Owing to the alleviation of sulfur loss by Al-promoting effects, excellent regeneration performance, with olefins conversion only slightly declining after 4 consecutive reaction-regeneration cycles, was also obtained. The mechanistic pathway for the alkylation of olefins with aromatics over Al 2 O 3 @SO 4 2- /ZrO 2 was also investigated and proposed by GC–MS analysis.

研究领域: 催化 · 化学工程 · 材料科学
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MICROPOROUS AND MESOPOROUS MATERIALS · 2022 · IF 5.876

Enhancement of the strong Brønsted acidity and mesoporosity: Zr4+ promoted framework modification of Zeolite Y

Bo Meng,Shenyong Ren,Xinyue Zhang,Kang Chen,Wenkai Wei,Qiaoxia Guo,Baojian Shen

Brønsted acid of zeolite Y plays an important role in catalytic cracking reaction. However the proportion of strong Brønsted acid in conventional zeolite Y is small which limits the efficiency of transformation. This work described a way to achieve the goal of significant increasing the density of strong Brønsted acid via introducing Zr 4+ into the framework of zeolite Y. The density of strong Brønsted acidity increased from 0.085 (HY) to 0.208 mmol/g ([Zr,Al]-HY). Systematic characterization results showed that the introduction of Zr 4+ could produce more Si(1Al) but less Si(3Al) and Si(2Al) species in zeolite which was responsible for the high density of Brønsted acid. And abundant mesopores were also formed during the Zr 4+ implanting. For the catalytic cracking results of n-octane, the conversion on [Zr,Al]-HY was 1.67 times of that on conventional HY. The apparent activation energy of cracking n-octane on [Zr,Al]-HY was reduced to 73.3%, which indicated that the increase of strong Brønsted acid had significant effect on catalytic cracking. On the other hand, a large number of mesoporous structures of [Zr,Al]-HY provided a good foundation for the catalytic cracking of steric hindered 1.3.5-triisopropylbenzene (1,3,5-TIPB).

研究领域: 材料科学 · 催化化学
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