RU2293075C2 - Method for oxidation of liquid hydrocarbons in barrier discharge - Google Patents
Method for oxidation of liquid hydrocarbons in barrier discharge Download PDFInfo
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- RU2293075C2 RU2293075C2 RU2004135440/04A RU2004135440A RU2293075C2 RU 2293075 C2 RU2293075 C2 RU 2293075C2 RU 2004135440/04 A RU2004135440/04 A RU 2004135440/04A RU 2004135440 A RU2004135440 A RU 2004135440A RU 2293075 C2 RU2293075 C2 RU 2293075C2
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- Russia
- Prior art keywords
- oxidation
- cyclohexane
- carried out
- barrier discharge
- liquid hydrocarbons
- Prior art date
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- 230000003647 oxidation Effects 0.000 title claims abstract description 22
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 22
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 17
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims abstract description 14
- 230000004888 barrier function Effects 0.000 title claims abstract description 10
- 239000007788 liquid Substances 0.000 title claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 239000000654 additive Substances 0.000 claims abstract description 5
- 229910052786 argon Inorganic materials 0.000 claims abstract description 5
- 239000001307 helium Substances 0.000 claims abstract description 5
- 229910052734 helium Inorganic materials 0.000 claims abstract description 5
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 5
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 4
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000007787 solid Substances 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 4
- 239000010457 zeolite Substances 0.000 claims abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract 2
- 229910052782 aluminium Inorganic materials 0.000 claims abstract 2
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract 2
- 239000011733 molybdenum Substances 0.000 claims abstract 2
- 229910052759 nickel Inorganic materials 0.000 claims abstract 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 1
- 229910052802 copper Inorganic materials 0.000 claims 1
- 239000010949 copper Substances 0.000 claims 1
- 238000005265 energy consumption Methods 0.000 abstract description 16
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 8
- 230000001590 oxidative effect Effects 0.000 abstract 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical class [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 abstract 1
- 230000000694 effects Effects 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 abstract 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 13
- 239000000047 product Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- 150000001728 carbonyl compounds Chemical class 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- -1 Hexane Hexanal Chemical compound 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- ARSRKIQSWHMOJO-UHFFFAOYSA-N cyclohexane cyclohexanone Chemical compound C1CCCCC1.C1(CCCCC1)=O.C1(CCCCC1)=O ARSRKIQSWHMOJO-UHFFFAOYSA-N 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- ZOCHHNOQQHDWHG-UHFFFAOYSA-N n-hexan-3-ol Natural products CCCC(O)CC ZOCHHNOQQHDWHG-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Изобретение относится к окислению жидких углеводородов в барьерном электрическом разряде в гидроксильные и карбонильные соединения без разрушения углеродного скелета исходной молекулы. Полученные продукты могут использоваться в качестве промежуточных продуктов для органического и нефтехимического синтеза.The invention relates to the oxidation of liquid hydrocarbons in a barrier electric discharge to hydroxyl and carbonyl compounds without destroying the carbon skeleton of the original molecule. The resulting products can be used as intermediates for organic and petrochemical synthesis.
Известен способ проведения плазмохимических реакций с использованием барьерного разряда (патент №2118912, опубл. 20.09.1998 г.), однако получить таким способом жидкие углеводороды не удается.A known method of conducting plasma-chemical reactions using a barrier discharge (patent No. 211 18912, publ. 09/20/1998), however, it is not possible to obtain liquid hydrocarbons in this way.
Наиболее близким к предлагаемому способу является процесс окисления углеводородов кислородом в проточном газоразрядном реакторе с барьерным разрядом (патент России №2127248, опубл. 10.03.99 г.). Окисление углеводородов приводит к образованию гидроксильных и карбонильных соединений с тем же числом атомов углерода, что и в исходном соединении.Closest to the proposed method is the process of oxidation of hydrocarbons by oxygen in a flow-through gas-discharge reactor with a barrier discharge (Russian patent No. 2127248, publ. 10.03.99,). The oxidation of hydrocarbons leads to the formation of hydroxyl and carbonyl compounds with the same number of carbon atoms as in the starting compound.
Основным недостатком данного способа является высокие энергетические затраты на превращение исходного углеводорода.The main disadvantage of this method is the high energy costs for the conversion of the original hydrocarbon.
Задача изобретения - снижение энергетических затрат на окисление исходного углеводорода в барьерном разряде.The objective of the invention is the reduction of energy costs for the oxidation of the initial hydrocarbon in the barrier discharge.
Технический результат достигается тем, что углеводороды окисляют в барботажном плазмохимическом реакторе с барьерным разрядом кислородом воздуха, смесями кислорода с гелием, аргоном, азотом без и в присутствии твердых добавок Al2О3, Ni2O3, MoO3, CuCl2, цеолитного катализатора (ZSM-5+1.2% Fe).The technical result is achieved in that the hydrocarbon is oxidized in a bubble plasmochemical reactor barrier discharge air oxygen, mixtures of oxygen with helium, argon, nitrogen without and in the presence of solid additives Al 2 O 3, Ni 2 O 3, MoO 3, CuCl 2, zeolite catalyst (ZSM-5 + 1.2% Fe).
В качестве исходных углеводородов используют н-гексан и циклогексан.The starting hydrocarbons used are n-hexane and cyclohexane.
Во всех примерах температура стенок реактора 10°С, давление - 1.2 атм, амплитуда импульсов напряжения 28 кВ, частота повторения 50 Гц. Удельная энергия разряда - 2.8·10-2 Вт·ч·л-1.In all examples, the temperature of the walls of the reactor is 10 ° C, the pressure is 1.2 atm, the amplitude of the voltage pulses is 28 kV, and the repetition frequency is 50 Hz. The specific energy of the discharge is 2.8 · 10 -2 W · h · l -1 .
Способ иллюстрируется следующими примерами.The method is illustrated by the following examples.
Пример 1. Окисление н-гексана и циклогексана проводят кислородом воздуха. Энергозатраты на превращение н-гексана и циклогексана составляют 21.9 и 8.2 кВт·ч·кг-1 соответственно. Энегрозатраты и данные по составу продуктов в таблице 1.Example 1. The oxidation of n-hexane and cyclohexane is carried out with atmospheric oxygen. The energy consumption for the conversion of n-hexane and cyclohexane is 21.9 and 8.2 kWh · kg -1, respectively. Energy costs and data on the composition of the products in table 1.
Пример 2. Окисление н-гексана и циклогексана проводят кислородом по прототипу. Энергозатраты на превращение н-гексана и циклогексана составляют 29.2 и 16.6 кВт·ч·кг-1 соответственно. Состав продуктов и энергозатраты на превращение исходного углеводорода приведены в таблице 1.Example 2. The oxidation of n-hexane and cyclohexane is carried out with oxygen according to the prototype. The energy consumption for the conversion of n-hexane and cyclohexane is 29.2 and 16.6 kW · h · kg -1, respectively. The composition of the products and the energy consumption for the conversion of the original hydrocarbon are shown in table 1.
Пример 3. Окисление циклогексана проводят смесью Не(20%)-O2(80%). Энергозатраты на превращение циклогексана составляют 4.0 кВт·ч·кг-1.Example 3. The oxidation of cyclohexane is carried out with a mixture of He (20%) - O 2 (80%). The energy consumption for the conversion of cyclohexane is 4.0 kWh · kg -1 .
Пример 4. Окисление циклогексана проводят смесью Ar(50%)-02(50%). Энергозатраты на превращение циклогексана составляют 4.7 кВт·ч·кг-1.Example 4. The oxidation of cyclohexane is carried out with a mixture of Ar (50%) - 02 (50%). The energy consumption for the conversion of cyclohexane is 4.7 kW · h · kg -1 .
Пример 5. Окисление циклогексана проводят смесью N2(80%)-O2(20%). Энергозатраты на превращение циклогексана составляют 8.0 кВт·ч·кг-1.Example 5. The oxidation of cyclohexane is carried out with a mixture of N 2 (80%) - O 2 (20%). The energy consumption for the conversion of cyclohexane is 8.0 kW · h · kg -1 .
Пример 6. Окисление циклогексана проводят смесью Не(20%)-O2(80%) в присутствии 0.7 мас.% MoO3. Энергозатраты на превращение циклогексана составляют 3.2 кВт·ч·кг-1.Example 6. The oxidation of cyclohexane is carried out with a mixture of He (20%) - O 2 (80%) in the presence of 0.7 wt.% MoO 3 . The energy consumption for the conversion of cyclohexane is 3.2 kW · h · kg -1 .
Далее во всех примерах масса твердой добавки составляет 0.7 мас.% от массы углеводорода.Further, in all examples, the mass of the solid additive is 0.7 wt.% By weight of the hydrocarbon.
Пример 7. Окисление циклогексана проводят смесью Не(20%)-O2(80%) в присутствии Ni2O3. Энергозатраты на превращение циклогексана составляют 3.1 кВт·ч·кг-1.Example 7. The oxidation of cyclohexane is carried out with a mixture of He (20%) - O 2 (80%) in the presence of Ni 2 O 3 . Energy consumption for the conversion of cyclohexane constitute 3.1 kW · hr · kg -1.
Пример 8. Окисление циклогексана проводят смесью Не(20%)-O2(80%) в присутствии Al2О3. Энергозатраты на превращение циклогексана составляют 3.6 кВт·ч·кг-1.Example 8. The oxidation of cyclohexane is carried out with a mixture of He (20%) - O 2 (80%) in the presence of Al 2 O 3 . The energy consumption for the conversion of cyclohexane is 3.6 kW · h · kg -1 .
Пример 9. Окисление циклогексана проводят смесью Не(20%)-O2(80%) в присутствии CuCl2. Энергозатраты на превращение циклогексана составляют 3.2 кВт·ч·кг-1.Example 9. The oxidation of cyclohexane is carried out with a mixture of He (20%) - O 2 (80%) in the presence of CuCl 2 . The energy consumption for the conversion of cyclohexane is 3.2 kW · h · kg -1 .
Пример 10. Окисление циклогексана проводят смесью Не(20%)-O2(80%) в присутствии цеолитного катализатора ZSM-5+1.2% Fe. Энергозатраты на превращение циклогексана составляют 3.6 кВт·ч·кг-1.Example 10. The oxidation of cyclohexane is carried out with a mixture of He (20%) - O 2 (80%) in the presence of a zeolite catalyst ZSM-5 + 1.2% Fe. The energy consumption for the conversion of cyclohexane is 3.6 kW · h · kg -1 .
Состав продуктов реакции и селективность их образования в примерах 3-10, как в примере 1.The composition of the reaction products and the selectivity of their formation in examples 3-10, as in example 1.
Таким образом, предлагаемое изобретение позволяет окислять жидкие углеводороды в присутствии добавок или без них в барботажном плазмохимическом реакторе с барьерным разрядом кислородом воздуха, или смесями воздуха с инертными газами с малыми энергетическими затратами.Thus, the present invention allows the oxidation of liquid hydrocarbons in the presence of additives or without them in a bubble plasma-chemical reactor with a barrier discharge of atmospheric oxygen, or air mixtures with inert gases with low energy costs.
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| Application Number | Priority Date | Filing Date | Title |
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| RU2004135440/04A RU2293075C2 (en) | 2004-12-03 | 2004-12-03 | Method for oxidation of liquid hydrocarbons in barrier discharge |
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| RU2004135440/04A RU2293075C2 (en) | 2004-12-03 | 2004-12-03 | Method for oxidation of liquid hydrocarbons in barrier discharge |
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| RU2293075C2 true RU2293075C2 (en) | 2007-02-10 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7592493B2 (en) * | 2007-06-27 | 2009-09-22 | H R D Corporation | High shear process for cyclohexanol production |
| RU2694829C2 (en) * | 2016-09-06 | 2019-07-17 | Общество с ограниченной ответственностью ОКСО | Method for catalytic oxidation of n-hexane |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2127248C1 (en) * | 1997-08-05 | 1999-03-10 | Институт химии нефти СО РАН | Process for preparing cyclohexanol and cyclohexanone |
| WO1999011572A1 (en) * | 1997-09-01 | 1999-03-11 | Laxarco Holding Limited | Electrically assisted partial oxidation of light hydrocarbons by oxygen |
| US6730275B2 (en) * | 1997-09-05 | 2004-05-04 | Battelle Memorial Institute | Corona method and apparatus for altering carbon containing compounds |
-
2004
- 2004-12-03 RU RU2004135440/04A patent/RU2293075C2/en not_active IP Right Cessation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2127248C1 (en) * | 1997-08-05 | 1999-03-10 | Институт химии нефти СО РАН | Process for preparing cyclohexanol and cyclohexanone |
| WO1999011572A1 (en) * | 1997-09-01 | 1999-03-11 | Laxarco Holding Limited | Electrically assisted partial oxidation of light hydrocarbons by oxygen |
| US6730275B2 (en) * | 1997-09-05 | 2004-05-04 | Battelle Memorial Institute | Corona method and apparatus for altering carbon containing compounds |
Non-Patent Citations (2)
| Title |
|---|
| А.И.Долгинов, Техника высоких напряжений в электроэнергетике. М.: Энергия, 1968, стр.82-84. * |
| Н.И.Гельперин, Основные процессы и аппараты химической технологии. М.: Химия, 1981, т.1, стр.182, 183. * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7592493B2 (en) * | 2007-06-27 | 2009-09-22 | H R D Corporation | High shear process for cyclohexanol production |
| RU2694829C2 (en) * | 2016-09-06 | 2019-07-17 | Общество с ограниченной ответственностью ОКСО | Method for catalytic oxidation of n-hexane |
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