• Korean Chemical Engineering Research
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• v.44 no.4
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• pp.345-349
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• 2006

Conversion of DME (dimethyl ether) or methanol to light olefins (ethylene, propylene, butenes) over SAPO-34 were systematically studied, where it was observed that DME was dehydrated to light olefins and partially converted to by-products such as CO and $CO_2$ at various reaction temperatures on the time-on-stream. SAPO-34 catalyst during the DTO (dimetyl ether-to-olefins) reaction was significantly deactivated compared with MTO (methanol-toolefins) reaction. By addition of water to the reaction feed, the yield to light olefins was not only increased, but the life time of the catalyst was also prolonged by the suppression of the coke formation by steam.

• Applied Chemistry for Engineering
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• v.34 no.5
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• pp.548-555
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• 2023

SAPO-34 catalysts were modified with polyethylene glycol (PEG) and Pb to improve their catalytic lifetime and selectivity for light olefins in the conversion of dimethyl ether to olefins (DTO). Hierarchical SAPO-34 catalysts and PbAPSO-34 catalysts were synthesized according to changes in the molecular weight of PEG (M.W. = 1000, 2000, 4000) and the molar ratio of Pb/Al (Pb/Al = 0.0015, 0.0025, 0.0035), respectively. By introducing PEG into the SAPO-34 catalyst crystals, an enhanced volume of mesopores and reduced acidity were observed, resulting in improved catalytic performance. Pb was successfully substituted into the SAPO-34 catalyst frameworks, and an increased BET surface area and concentration of acid sites in the PbAPSO-34 catalysts were observed. In particular, the concentrations of the weak acid sites, which induce a mild reaction, were increased compared with the concentrations of strong acid sites. Then, the P2000-Pb(25)APSO-34 catalyst was prepared by simultaneously utilizing the synthesis conditions for the P2000 SAPO-34 and Pb(25)APSO-34 catalysts. The P2000-Pb(25)APSO-34 catalyst showed the best catalytic lifetime (183 min based on DME conversion > 90%), with an approximately 62% improvement compared to that of the unmodified catalyst (113 min).

• Applied Chemistry for Engineering
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• v.25 no.1
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• pp.34-40
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• 2014

Mesoporous SAPO-34 catalyst was successfully synthesized by the hydrothermal method using carbon nanotube (CNT) as a secondary template. The effects of CNT contents (0.5, 1.5, 2.5, and 4.5 mol%) on catalytic performances were investigated. The synthesized catalysts were characterized with XRD, SEM, nitrogen physisorption isotherm and $NH_3$-TPD. Among the synthesized catalysts, SAPO-34 catalyst prepared by the addition of 1.5 mol% CNT (1.5C-SAPO-34) observed not only the largest amounts of mesopore volume but also acid sites. However, the mesopore volume was relatively decreased by further increasing of CNT contents due to the formation of small crystalline. The catalytic lifetime and the selectivity of light olefins ($C_2{\sim}C_4$) were examined for the dimethyl ether to olefins reaction. As a result, the 1.5C-SAPO-34 catalyst showed an improvement of ca. 36% in a catalytic lifetime and a better selectivity to light olefins as compared with the general SAPO-34 catalyst.

• Bulletin of the Korean Chemical Society
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• v.7 no.5
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• pp.372-376
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• 1986

Substituted 3,4-dihydro-2H-pyrans ($1_{a-e}$) were prepared by (4 + 2) cycloaddition reaction of dimethyl dicyanofumarate with the corresponding electron-rich olefins. The compounds $1_{a-e}$ were ring-open polymerized by cationic initiators to obtain polymers of 1:1 alternating sequence. Polymerizations were carried out with boron trifluoride etherate in methylene chloride at $-78^{\circ}C$. All the polymers obtained were soluble in common solvents and were reprecipitated by pouring its chloroform solution into diethyl ether. All the compounds $1_{a-e}$ were not as reactive as the corresponding pyrans derived from ${\alpha}$ -cyanoacrylate.

• Applied Chemistry for Engineering
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• v.26 no.2
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• pp.138-144
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• 2015

Effects of Co/Al and Si/Al molar ratios of cobalt incorporated SAPO-34 catalysts (CoAPSO-34) on their catalytic lifetime were investigated in dimethyl to olefin (DTO) reaction. The property of CoAPSO-34 catalysts was characterized using XRD, SEM, $^{29}Si$ MAS NMR, and $NH_3$-TPD techniques. First, the lifetime of CoAPSO-34 prepared by varying Co/Al molar ratios was improved than that of using the SAPO-34 catalyst, and the optimal Co/Al molar ratio was 0.0025. The total acid site amounts increased from 0.432 to 1.111 mmol/g with increasing Si/Al molar ratios from 0.05 to 0.20 while fixing a Co/Al molar ratio of 0.0025. However, the catalysts with too high acid site amounts were deactivated rapidly with blockages of the pores due to the fast accumulation of polycyclic aromatic hydrocarbons in the cage. Therefore, the CoAPSO-34 catalyst with a proper Si/Al molar ratio of 0.10 was the most superior in terms of the lifetime, which was improved by about 87% as compared with that of the SAPO-34 catalyst.

• Transactions of the Korean hydrogen and new energy society
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• v.22 no.2
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• pp.232-239
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• 2011

DME has received much attention because of its possible use as a fuel and a chemical feedstock. Chemical conversion of DME to olefin (DTO) over various SAPO-34 catalysts was carried out using a fixed bed reactor. Main products of the reaction were light olefins such as ethylene, propylene and butenes. The best reaction conditions for high life time of the catalyst and high selectivity of light olefins were a reaction temperature of $400^{\circ}C$ and a WHSV of $3.54h^{-1}$. In addition, it was found that the deactivation of a SAPO-34 catalyst can be significantly suppressed by the addition of $ZrO_2$ as a supporter.

• Applied Chemistry for Engineering
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• v.32 no.1
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• pp.20-27
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• 2021

Effects of the etching treatment of SAPO-34 catalyst were investigated to improve the catalytic lifetime in DTO reaction. The aqueous NH3 solution was a more appropriate treatment agent which could control the degree of etching progress, compared to that of using a strong acid (HCl) or alkali (NaOH) solution. Therefore, the effect on characteristics and lifetime of SAPO-34 catalyst was observed using the treatment concentration and time of aqueous NH3 solution as variables. As the treatment concentration or time of aqueous NH3 solution increased, the growth of erosion was proceeded from the center of SAPO-34 crystal plane, and the acid site concentration and strength gradually decreased. Meanwhile, it was found that external surface area and mesopore volume of SAPO-34 catalyst increased at appropriate treatment conditions. When the treatment concentration and time were 0.05 M and 3 h, respectively, the lifetime of the treated SAPO-34 catalyst was the longest, and was significantly enhanced by ca. 36% (based on DME conversion of > 90%) compared to that of using the untreated catalyst. The model for the etching progress of SAPO-34 catalyst in a mild treatment process using aqueous NH3 solution was also proposed.

• Applied Chemistry for Engineering
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• v.26 no.2
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• pp.217-223
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• 2015

Effects of the post-acid treatment of SAPO-34 sample by hydrochloric acid were investigated to enhance the catalytic performance in DTO reaction. Uniformly sized SAPO-34 samples with cubic-like morphology were prepared by hydrothermal method using TEAOH and DEA as the structure directing agents. It was modified in terms of the HCl concentration and treating time. As a result, the total surface area and micropore volume for the well modified samples increased and the total acid site was somewhat decreased along with the erosion of the external surface. Especially, the catalytic lifetime and light olefins selectivity for acid treated SAPO-0.2 M (3 h) samples were considerably enhanced compared with those of untreated SAPO-34 samples. It indicates that the deactivation by coke formation proceeds mainly at the pore entrance on the external surface. Therefore, the acid treatment was confirmed to be a simple method which can significantly improve the catalytic performance by modifying the external surface of SAPO-34 catalyst.

• Applied Chemistry for Engineering
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• v.32 no.3
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• pp.305-311
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• 2021

Effects of chitosan as a mesopore directing agent of SAPO-34 catalysts were investigated to improve the catalytic lifetime in DTO reaction. The synthesized catalysts were characterized by XRD, SEM, N₂ adsorption-desorption isotherm and NH₃-temperature programmed desorption (TPD). The modified SAPO-34 catalysts prepared by varying the added amount of chitosan showed the same cubic morphology and chabazite structure as the conventional SAPO-34 catalyst. As the added amount of chitosan increased to 3 wt%, the surface area, mesopore volume and concentration of weak acid sites of modified SAPO-34 catalysts increased. The modified SAPO-34 catalysts showed enhanced catalytic lifetime and high selectivity for light olefins in the DTO reaction. In particular, the SAPO-CHI 3 catalyst (3 wt%) exhibited the longest catalytic lifetime than that of the conventional SAPO-34. Therefore, it was confirmed that chitosan was a suitable material as a mesopore directing agent to delay deactivation of the SAPO-34 catalyst.