14 research outputs found
ΠΠ·ΡΡΠ΅Π½ΠΈΠ΅ ΡΠΎΠΏΡΡΠΆΠ΅Π½Π½ΠΎΠ³ΠΎ ΠΊΠ°ΡΠ°Π»ΠΈΡΠΈΡΠ΅ΡΠΊΠΎΠ³ΠΎ Π΄Π΅Π³ΠΈΠ΄ΡΠΈΡΠΎΠ²Π°Π½ΠΈΡ ΠΌΠ΅ΡΠ°Π½ΠΎΠ»Π° Π² ΡΠΎΡΠΌΠ°Π»ΡΠ΄Π΅Π³ΠΈΠ΄ Π² ΠΏΡΠΈΡΡΡΡΡΠ²ΠΈΠΈ ΠΏΠ΅ΡΠ΅ΠΊΠΈΡΠΈ Π²ΠΎΠ΄ΠΎΡΠΎΠ΄Π°
From the studies of the kinetics of methanol conjugate dehydration process, a kinetic model has been proposed and kinetic parameters calculated. It was discovered that when other substances like ethane, ethylene were used as initiators the catalyst surface coked rapidly. On the K-1 model in the presence of hydrogen peroxide (1% in water solution of the initial methanol) the temperature of the dehydration process reduces by 50-60ΒΊΠ‘ at 50% formaldehyde yield and allows for the reaction to be carried out at a temperature of 820-830ΒΊΠ‘Π ΡΠ΅Π°ΠΊΡΠΈΠΈ ΠΏΡΡΠΌΠΎΠ³ΠΎ Π΄Π΅Π³ΠΈΠ΄ΡΠΈΡΠΎΠ²Π°Π½ΠΈΡ ΠΌΠ΅ΡΠ°Π½ΠΎΠ»Π° ΠΎΠ±Π½Π°ΡΡΠΆΠ΅Π½ ΡΡΡΠ΅ΠΊΡ ΠΈΠ½ΠΈΡΠΈΠΈΡΠΎΠ²Π°Π½ΠΈΡ ΠΎΡΠ½ΠΎΠ²Π½ΠΎΠ³ΠΎ ΠΏΡΠΎΡΠ΅ΡΡΠ° ΠΏΠΎΠ»ΡΡΠ΅Π½ΠΈΡ ΡΠΎΡΠΌΠ°Π»ΡΠ΄Π΅Π³ΠΈΠ΄Π° ΠΏΠ΅ΡΠ΅ΠΊΠΈΡΡΡ Π²ΠΎΠ΄ΠΎΡΠΎΠ΄Π°. ΠΡΠ΅Π΄Π»ΠΎΠΆΠ΅Π½Π° Π³ΠΈΠΏΠΎΡΠ΅Π·Π° ΠΌΠ΅Ρ
Π°Π½ΠΈΠ·ΠΌΠ° ΡΠ΅Π°ΠΊΡΠΈΠΈ, ΠΏΡΠ΅Π΄ΠΏΠΎΠ»Π°Π³Π°ΡΡΠ°Ρ ΡΠΎΠΏΡΡΠΆΠ΅Π½ΠΈΠ΅ Π΄Π΅Π³ΠΈΠ΄ΡΠΈΡΠΎΠ²Π°Π½ΠΈΡ ΠΌΠ΅ΡΠ°Π½ΠΎΠ»Π° Ρ ΡΠ°Π·Π»ΠΎΠΆΠ΅Π½ΠΈΠ΅ΠΌ ΠΏΠ΅ΡΠ΅ΠΊΠΈΡΠΈ Π²ΠΎΠ΄ΠΎΡΠΎΠ΄Π°, ΡΠΎΠΏΡΠΎΠ²ΠΎΠΆΠ΄Π°Π΅ΠΌΠΎΠ³ΠΎ ΠΎΠ±ΡΠ°Π·ΠΎΠ²Π°Π½ΠΈΠ΅ΠΌ ΡΠ°Π΄ΠΈΠΊΠ°Π»ΠΎΠ² HO2β.ΠΠ·ΡΡΠ΅Π½Ρ ΠΊΠΈΠ½Π΅ΡΠΈΡΠ΅ΡΠΊΠΈΠ΅ Π·Π°ΠΊΠΎΠ½ΠΎΠΌΠ΅ΡΠ½ΠΎΡΡΠΈ ΠΏΡΠΎΡΠ΅ΡΡΠ° ΡΠΎΠΏΡΡΠΆΠ΅Π½Π½ΠΎΠ³ΠΎ Π΄Π΅Π³ΠΈΠ΄ΡΠΈΡΠΎΠ²Π°Π½ΠΈΡ ΠΌΠ΅ΡΠ°Π½ΠΎΠ»Π°, Π½Π° ΠΎΡΠ½ΠΎΠ²Π°Π½ΠΈΠΈ ΠΊΠΎΡΠΎΡΡΡ
ΠΏΡΠ΅Π΄Π»ΠΎΠΆΠ΅Π½Π° ΠΊΠΈΠ½Π΅ΡΠΈΡΠ΅ΡΠΊΠ°Ρ ΠΌΠΎΠ΄Π΅Π»Ρ ΡΠ΅Π°ΠΊΡΠΈΠΈ ΠΈ ΡΠ°ΡΡΡΠΈΡΠ°Π½Ρ ΠΊΠΈΠ½Π΅ΡΠΈΡΠ΅ΡΠΊΠΈΠ΅ ΠΏΠ°ΡΠ°ΠΌΠ΅ΡΡΡ. ΠΠ±Π½Π°ΡΡΠΆΠ΅Π½ΠΎ, ΡΡΠΎ ΠΏΡΠΈ ΠΈΡΠΏΠΎΠ»ΡΠ·ΠΎΠ²Π°Π½ΠΈΠΈ Π² ΠΊΠ°ΡΠ΅ΡΡΠ²Π΅ ΠΈΠ½Π΄ΡΠΊΡΠΎΡΠΎΠ² ΠΏΡΠΎΡΠ΅ΡΡΠ° Π΄ΡΡΠ³ΠΈΡ
Π²Π΅ΡΠ΅ΡΡΠ², ΡΠ°ΠΊΠΈΡ
ΠΊΠ°ΠΊ ΡΡΠ°Π½ ΠΈ ΡΡΠΈΠ»Π΅Π½, ΠΏΠΎΠ²Π΅ΡΡ
Π½ΠΎΡΡΡ ΠΊΠ°ΡΠ°Π»ΠΈΠ·Π°ΡΠΎΡΠ° ΡΠΈΠ»ΡΠ½ΠΎ ΠΊΠΎΠΊΡΡΠ΅ΡΡΡ. ΠΠΎΠΊΠ°Π·Π°Π½ΠΎ, ΡΡΠΎ Π½Π° ΠΌΠΎΠ΄Π΅Π»ΡΠ½ΠΎΠΌ ΠΎΠ±ΡΠ°Π·ΡΠ΅ ΠΊΠ°ΡΠ°Π»ΠΈΠ·Π°ΡΠΎΡΠ° Π-1 ΠΏΡΠΈ ΠΏΡΠΎΠ²Π΅Π΄Π΅Π½ΠΈΠΈ ΡΠ΅Π°ΠΊΡΠΈΠΈ ΠΏΡΠΈ 820-880ΠΎΠ‘ Π² ΠΏΡΠΈΡΡΡΡΡΠ²ΠΈΠΈ ΠΏΠ΅ΡΠ΅ΠΊΠΈΡΠΈ Π²ΠΎΠ΄ΠΎΡΠΎΠ΄Π° (1 ΠΌΠ°ΡΡ.%) Π΄ΠΎΡΡΠΈΠ³Π°Π΅ΡΡΡ ΠΏΡΠΎΠΈΠ·Π²ΠΎΠ΄ΠΈΡΠ΅Π»Ρ-Π½ΠΎΡΡΡ ΠΊΠΎΠ½ΡΠ°ΠΊΡΠ° ΠΏΠΎ ΡΠΎΡΠΌΠ°Π»ΡΠ΄Π΅Π³ΠΈΠ΄Ρ 5-8 Π³/(Π³ ΠΊΠ°Ρ. Ρ) ΠΏΡΠΈ ΡΠ΅Π»Π΅ΠΊΡΠΈΠ²Π½ΠΎΡΡΠΈ ΠΏΡΠΎΡΠ΅ΡΡΠ° Π΄ΠΎ 90-95%
Π’Π΅ΡΠΌΠΎΠ΄ΠΈΠ½Π°ΠΌΠΈΡΠ΅ΡΠΊΠΈΠΉ ΠΈ ΠΊΠΈΠ½Π΅ΡΠΈΡΠ΅ΡΠΊΠΈΠΉ Π°Π½Π°Π»ΠΈΠ· Ρ ΠΈΠΌΠΈΡΠ΅ΡΠΊΠΎΠ³ΠΎ ΡΠΎΠΏΡΡΠΆΠ΅Π½ΠΈΡ Ρ ΡΠ΅Π°ΠΊΡΠΈΠ΅ΠΉ Π΄Π΅Π³ΠΈΠ΄ΡΠΈΡΠΎΠ²Π°Π½ΠΈΡ ΠΌΠ΅ΡΠ°Π½ΠΎΠ»Π° Π² ΡΠΎΡΠΌΠ°Π»ΡΠ΄Π΅Π³ΠΈΠ΄
Theoretical analysis of the possibility of conjugating the reaction of formaldehyde formation via dehydrogenation of methanol with other initiating reactions is conducted; and advantages of using hydrogen peroxide vs. organic inductors are discussed. When hydrogen peroxide is used, the reaction reaches stationary condition almost immediately. It is demonstrated that the induction and the targeted reaction proceed with high selectivity towards formaldehyde.ΠΡΠΎΠ²Π΅Π΄Π΅Π½ ΡΠ΅ΠΎΡΠ΅ΡΠΈΡΠ΅ΡΠΊΠΈΠΉ Π°Π½Π°Π»ΠΈΠ· Π²ΠΎΠ·ΠΌΠΎΠΆΠ½ΠΎΡΡΠΈ ΡΠΎΠΏΡΡΠΆΠ΅Π½ΠΈΡ Ρ ΡΠ΅Π°ΠΊΡΠΈΠ΅ΠΉ ΠΎΠ±ΡΡΠ½ΠΎΠ³ΠΎ Π΄Π΅Π³ΠΈΠ΄ΡΠΈΡΠΎΠ²Π°Π½ΠΈΡ ΠΌΠ΅ΡΠ°Π½ΠΎΠ»Π° Π² ΡΠΎΡΠΌΠ°Π»ΡΠ΄Π΅Π³ΠΈΠ΄ ΡΠ°Π·Π»ΠΈΡΠ½ΡΡ
ΡΠ΅Π°ΠΊΡΠΈΠΉ, ΠΈΠ½ΠΈΡΠΈΠΈΡΡΡΡΠΈΡ
ΠΏΡΠΎΡΠ΅ΠΊΠ°Π½ΠΈΠ΅ ΡΠ΅Π»Π΅Π²ΠΎΠ³ΠΎ ΠΏΡΠΎΡΠ΅ΡΡΠ°. ΠΠΎΠΊΠ°Π·Π°Π½ΠΎ ΠΏΡΠ΅ΠΈΠΌΡΡΠ΅ΡΡΠ²ΠΎ ΠΏΠ΅ΡΠ΅ΠΊΠΈΡΠΈ Π²ΠΎΠ΄ΠΎΡΠΎΠ΄Π° ΠΏΠ΅ΡΠ΅Π΄ ΠΈΠ½Π΄ΡΠΊΡΠΎΡΠ°ΠΌΠΈ ΠΎΡΠ³Π°Π½ΠΈΡΠ΅ΡΠΊΠΎΠ³ΠΎ ΠΏΡΠΎΠΈΡΡ
ΠΎΠΆΠ΄Π΅Π½ΠΈΡ. ΠΡΠΈ ΠΏΡΠΈΠΌΠ΅Π½Π΅Π½ΠΈΠΈ ΠΏΠ΅ΡΠ΅ΠΊΠΈΡΠΈ Π²ΠΎΠ΄ΠΎΡΠΎΠ΄Π° ΡΡΠ°ΡΠΈΠΎΠ½Π°ΡΠ½ΡΠΉ ΡΠ΅ΠΆΠΈΠΌ ΡΠ΅Π°ΠΊΡΠΈΠΈ ΡΡΡΠ°Π½Π°Π²Π»ΠΈΠ²Π°Π΅ΡΡΡ ΠΏΡΠ°ΠΊΡΠΈΡΠ΅ΡΠΊΠΈ ΠΌΠ³Π½ΠΎΠ²Π΅Π½Π½ΠΎ. Π£ΡΡΠ°Π½ΠΎΠ²Π»Π΅Π½ΠΎ, ΡΡΠΎ ΠΈΠ½ΠΈΡΠΈΠΈΡΠΎΠ²Π°Π½Π½ΡΠΉ ΠΏΡΠΎΡΠ΅ΡΡ ΡΠ²ΠΎΠ΄ΠΈΡΡΡ ΠΊ ΠΎΠ΄Π½ΠΎΠ²ΡΠ΅ΠΌΠ΅Π½Π½ΠΎΠΌΡ ΠΏΡΠΎΡΠ΅ΠΊΠ°Π½ΠΈΡ ΠΈΠ½Π΄ΡΠΊΡΠΈΡΡΡΡΠ΅ΠΉ ΠΈ ΡΠ΅Π»Π΅Π²ΠΎΠΉ ΡΠ΅Π°ΠΊΡΠΈΠΉ Ρ Π²ΡΡΠΎΠΊΠΎΠΉ ΡΠ΅Π»Π΅ΠΊΡΠΈΠ²Π½ΠΎΡΡΡΡ ΠΏΠΎ ΡΠΎΡΠΌΠ°Π»ΡΠ΄Π΅Π³ΠΈΠ΄Ρ
ΠΠΠ’ΠΠΠΠ’ΠΠ§ΠΠ‘ΠΠΠ― ΠΠΠΠΠΠ Π‘ΠΠ― ΠΠΠΠΠ’ΠΠΠΠΠ Π ΠΠ ΠΠΠΠ’ΠΠ§ΠΠ‘ΠΠΠ Π£ΠΠΠΠΠΠΠΠ ΠΠΠ« Π ΠΠ ΠΠ‘Π£Π’Π‘Π’ΠΠΠ ΠΠΠ ΠΠΠ‘ΠΠΠ ΠΠΠΠΠ ΠΠΠ
The initiating action of hydrogen peroxide on the catalytical transformation of ethanol into aromatic hydrocarbons was studied. It was shown that the total yield of aromatic hydrocarbons increases with increasing time of contact and temperature, when rapid coking of the surface of the zeolite-containing catalyst HZSM-5 occurs in the absence of hydrogen. The modifying action of hydrogen peroxide by the catalyst surface hydroxylation and initiation of the rate-limiting step of ethylene oligomerization with the participation of peroxide radicals HO2 β’ was hypothesized.ΠΡΡΠ»Π΅Π΄ΠΎΠ²Π°Π½ΠΎ ΠΈΠ½ΠΈΡΠΈΠΈΡΡΡΡΠ΅Π΅ Π²Π»ΠΈΡΠ½ΠΈΠ΅ ΠΏΠ΅ΡΠΎΠΊΡΠΈΠ΄Π° Π²ΠΎΠ΄ΠΎΡΠΎΠ΄Π° Π½Π° ΠΏΡΠΎΡΠ΅ΡΡ ΠΊΠ°ΡΠ°Π»ΠΈΡΠΈΡΠ΅ΡΠΊΠΎΠ³ΠΎ ΠΏΡΠ΅-Π²ΡΠ°ΡΠ΅Π½ΠΈΡ ΡΡΠ°Π½ΠΎΠ»Π° Π² Π°ΡΠΎΠΌΠ°ΡΠΈΡΠ΅ΡΠΊΠΈΠ΅ ΡΠ³Π»Π΅Π²ΠΎΠ΄ΠΎΡΠΎΠ΄Ρ. ΠΠΎΠΊΠ°Π·Π°Π½ΠΎ, ΡΡΠΎ ΡΡΠΌΠΌΠ°ΡΠ½ΡΠΉ Π²ΡΡ
ΠΎΠ΄ Π°ΡΠΎΠΌΠ°-ΡΠΈΡΠ΅ΡΠΊΠΈΡ
ΡΠ³Π»Π΅Π²ΠΎΠ΄ΠΎΡΠΎΠ΄ΠΎΠ² ΠΏΠΎΠ²ΡΡΠ°Π΅ΡΡΡ Ρ ΡΠ²Π΅Π»ΠΈΡΠ΅Π½ΠΈΠ΅ΠΌ Π²ΡΠ΅ΠΌΠ΅Π½ΠΈ ΠΊΠΎΠ½ΡΠ°ΠΊΡΠ° ΠΈ ΡΠ΅ΠΌΠΏΠ΅ΡΠ°ΡΡΡΡ Π² ΡΠ΅Ρ
ΡΡΠ»ΠΎΠ²ΠΈΡΡ
, ΠΊΠΎΠ³Π΄Π° Π² ΠΎΡΡΡΡΡΡΠ²ΠΈΠ΅ ΠΏΠ΅ΡΠΎΠΊΡΠΈΠ΄Π° Π²ΠΎΠ΄ΠΎΡΠΎΠ΄Π° ΠΏΡΠΎΠΈΡΡ
ΠΎΠ΄ΠΈΡ Π±ΡΡΡΡΠΎΠ΅ ΠΊΠΎΠΊΡΠΎΠ²Π°Π½ΠΈΠ΅ ΠΏΠΎΠ²Π΅ΡΡ
-Π½ΠΎΡΡΠΈ ΡΠ΅ΠΎΠ»ΠΈΡΡΠΎΠ΄Π΅ΡΠΆΠ°ΡΠ΅Π³ΠΎ ΠΊΠ°ΡΠ°Π»ΠΈΠ·Π°ΡΠΎΡΠ° HZSM-5. ΠΡΡΠΊΠ°Π·Π°Π½Π° Π³ΠΈΠΏΠΎΡΠ΅Π·Π° ΠΎ ΠΌΠΎΠ΄ΠΈΡΠΈΡΠΈΡΡΡΡΠ΅ΠΌ Π΄Π΅ΠΉΡΡΠ²ΠΈΠΈ ΠΏΠ΅ΡΠΎΠΊΡΠΈΠ΄Π° Π²ΠΎΠ΄ΠΎΡΠΎΠ΄Π° ΠΏΡΡΠ΅ΠΌ Π³ΠΈΠ΄ΡΠΎΠΊΡΠΈΠ»ΠΈΡΠΎΠ²Π°Π½ΠΈΡ ΠΏΠΎΠ²Π΅ΡΡ
Π½ΠΎΡΡΠΈ ΠΊΠ°ΡΠ°Π»ΠΈΠ·Π°ΡΠΎΡΠ° ΠΈ ΠΈΠ½ΠΈΡΠΈΠΈΡΠΎΠ²Π°Π½ΠΈΠΈ Π»ΠΈΠΌΠΈΡΠΈΡΡΡΡΠ΅ΠΉ ΡΡΠ°Π΄ΠΈΠΈ ΠΎΠ»ΠΈΠ³ΠΎΠΌΠ΅ΡΠΈΠ·Π°ΡΠΈΠΈ ΡΡΠΈΠ»Π΅Π½Π° Ρ ΡΡΠ°ΡΡΠΈΠ΅ΠΌ ΠΏΠ΅ΡΠΎΠΊΡΠΈΠ΄Π½ΡΡ
ΡΠ°Π΄ΠΈΠΊΠ°Π»ΠΎΠ² HO2β’
ΠΠ΅ΡΠΎΠ΄Ρ Π°Π½Π°Π»ΠΈΠ·Π° ΡΠΎΡΠΌΠ°Π»ΡΠ΄Π΅Π³ΠΈΠ΄Π°
The literature data on the methods of formaldehyde analysis are generalized. Chromatographic, colorimetric, titrimetric, polarographic, biochemical and spectral methods are discussed. A complex analytical solution of the material balance of the reaction of conjugated dehydrogenation of methanol to formaldehyde in the presence of hydrogen peroxide is proposed.ΠΠ±ΠΎΠ±ΡΠ΅Π½Ρ Π»ΠΈΡΠ΅ΡΠ°ΡΡΡΠ½ΡΠ΅ Π΄Π°Π½Π½ΡΠ΅ ΠΏΠΎ ΠΌΠ΅ΡΠΎΠ΄Π°ΠΌ Π°Π½Π°Π»ΠΈΠ·Π° ΡΠΎΡΠΌΠ°Π»ΡΠ΄Π΅Π³ΠΈΠ΄Π°. Π Π°ΡΡΠΌΠΎΡΡΠ΅Π½Ρ Ρ
ΡΠΎΠΌΠ°ΡΠΎΠ³ΡΠ°ΡΠΈΡΠ΅ΡΠΊΠΈΠ΅, ΠΊΠΎΠ»ΠΎΡΠΈΠΌΠ΅ΡΡΠΈΡΠ΅ΡΠΊΠΈΠΉ, ΡΠΈΡΡΠΎΠΌΠ΅ΡΡΠΈΡΠ΅ΡΠΊΠΈΠΉ, ΠΏΠΎΠ»ΡΡΠΎΠ³ΡΠ°ΡΠΈΡΠ΅ΡΠΊΠΈΠΉ, Π±ΠΈΠΎΡ
ΠΈΠΌΠΈΡΠ΅ΡΠΊΠΈΠΉ ΠΈ ΡΠΏΠ΅ΠΊΡΡΠ°Π»ΡΠ½ΡΠ΅ ΠΌΠ΅ΡΠΎΠ΄Ρ. ΠΡΠ΅Π΄Π»ΠΎΠΆΠ΅Π½ΠΎ ΠΊΠΎΠΌΠΏΠ»Π΅ΠΊΡΠ½ΠΎΠ΅ Π°Π½Π°Π»ΠΈΡΠΈΡΠ΅ΡΠΊΠΎΠ΅ ΡΠ΅ΡΠ΅Π½ΠΈΠ΅ ΠΌΠ°ΡΠ΅ΡΠΈΠ°Π»ΡΠ½ΠΎΠ³ΠΎ Π±Π°Π»Π°Π½ΡΠ° ΡΠ΅Π°ΠΊΡΠΈΠΈ ΡΠΎΠΏΡΡΠΆΠ΅Π½Π½ΠΎΠ³ΠΎ Π΄Π΅Π³ΠΈΠ΄ΡΠΈΡΠΎΠ²Π°Π½ΠΈΡ ΠΌΠ΅ΡΠ°Π½ΠΎΠ»Π° Π² ΡΠΎΡΠΌΠ°Π»ΡΠ΄Π΅Π³ΠΈΠ΄ Π² ΠΏΡΠΈΡΡΡΡΡΠ²ΠΈΠΈ ΠΏΠ΅ΡΠ΅ΠΊΠΈΡΠΈ Π²ΠΎΠ΄ΠΎΡΠΎΠ΄Π°
Thermodynamic and kinetic analysis of the chemical reaction of methanol dehydration to formaldehyde
Theoretical analysis of the possibility of conjugating the reaction of formaldehyde formation via dehydrogenation of methanol with other initiating reactions is conducted; and advantages of using hydrogen peroxide vs. organic inductors are discussed. When hydrogen peroxide is used, the reaction reaches stationary condition almost immediately. It is demonstrated that the induction and the targeted reaction proceed with high selectivity towards formaldehyde
Catalytic bioethanol conversion into aromatic hydrocarbons with hydrogen peroxide
The initiating action of hydrogen peroxide on the catalytical transformation of ethanol into aromatic hydrocarbons was studied. It was shown that the total yield of aromatic hydrocarbons increases with increasing time of contact and temperature, when rapid coking of the surface of the zeolite-containing catalyst HZSM-5 occurs in the absence of hydrogen. The modifying action of hydrogen peroxide by the catalyst surface hydroxylation and initiation of the rate-limiting step of ethylene oligomerization with the participation of peroxide radicals HO2 β’ was hypothesized
Methods of formaldehyde analysis
The literature data on the methods of formaldehyde analysis are generalized. Chromatographic, colorimetric, titrimetric, polarographic, biochemical and spectral methods are discussed. A complex analytical solution of the material balance of the reaction of conjugated dehydrogenation of methanol to formaldehyde in the presence of hydrogen peroxide is proposed