RU2187491C1 - Method of synthesis of ethyl alcohol and acetic acid (variants) - Google Patents
Method of synthesis of ethyl alcohol and acetic acid (variants) Download PDFInfo
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- RU2187491C1 RU2187491C1 RU2001108321A RU2001108321A RU2187491C1 RU 2187491 C1 RU2187491 C1 RU 2187491C1 RU 2001108321 A RU2001108321 A RU 2001108321A RU 2001108321 A RU2001108321 A RU 2001108321A RU 2187491 C1 RU2187491 C1 RU 2187491C1
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- RU
- Russia
- Prior art keywords
- acetic acid
- ethyl alcohol
- acetylene
- ammonia
- synthesis
- Prior art date
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 title claims abstract description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 18
- 235000019441 ethanol Nutrition 0.000 title claims abstract description 17
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 230000015572 biosynthetic process Effects 0.000 title abstract description 7
- 238000003786 synthesis reaction Methods 0.000 title abstract 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 15
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 10
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- CBNXGQUIJRGZRX-UHFFFAOYSA-N 5-[4-fluoro-3-(trifluoromethyl)phenyl]furan-2-carbaldehyde Chemical compound C1=C(C(F)(F)F)C(F)=CC=C1C1=CC=C(C=O)O1 CBNXGQUIJRGZRX-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000005997 Calcium carbide Substances 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 5
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 4
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 3
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- 239000000908 ammonium hydroxide Substances 0.000 abstract 1
- 238000004880 explosion Methods 0.000 abstract 1
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine group Chemical group NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002731 mercury compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Изобретение относится к получению этилового спирта и уксусной кислоты или их смеси и может быть использовано во многих отраслях народного хозяйства. The invention relates to the production of ethyl alcohol and acetic acid or a mixture thereof and can be used in many sectors of the economy.
Существует значительное количество способов приготовления этилового спирта и уксусной кислоты. В частности известны способы окислением этилена с получением уксусной кислоты в смеси с уксусным альдегидом (US 1943385) или взаимодействием этилена и кислорода с получением уксусной кислоты, минуя стадию образования уксусного альдегида (RU 2131409). Известен также способ получения уксусной кислоты из ацетилена и кислорода в присутствии ртутных соединений и необходимых для реакции количеств воды с добавлением, при необходимости, других катализаторов (SU 8015). There are a significant number of methods for the preparation of ethyl alcohol and acetic acid. In particular, methods are known for the oxidation of ethylene to produce acetic acid in a mixture with acetic aldehyde (US 1943385) or the interaction of ethylene and oxygen to produce acetic acid, bypassing the stage of formation of acetic aldehyde (RU 2131409). There is also known a method of producing acetic acid from acetylene and oxygen in the presence of mercury compounds and the amount of water necessary for the reaction with the addition, if necessary, of other catalysts (SU 8015).
Известен также способ получения уксусной кислоты или этилового спирта с использованием ацетилена, получаемого из карбида кальция, который является одним из ближайших аналогов (см. стр. 427, 444, Г.Реми, Курс неорганической химии, том 1, Издательство "Мир", Москва, 1972 г.). There is also a method of producing acetic acid or ethyl alcohol using acetylene obtained from calcium carbide, which is one of the closest analogues (see p. 427, 444, G. Remi, Inorganic Chemistry Course, Volume 1, Mir Publishing House, Moscow , 1972).
Согласно этому аналогу полученный из карбида кальция ацетилен расщепляется в генераторе в присутствии ртути при 70-80oС. В итоге образуется ацетальдегид, который затем перерабатывается в уксусную кислоту (кислород + перманганат калия) или в этиловой спирт (каталитически водородом).According to this analogue, acetylene obtained from calcium carbide is broken down in the generator in the presence of mercury at 70-80 o C. As a result, acetaldehyde is formed, which is then processed into acetic acid (oxygen + potassium permanganate) or into ethanol (catalytically with hydrogen).
Указанный способ позволяет получать в нужном количестве эти продукты. Однако он имеет ряд недостатков: применение раздельного оборудования, стойкого к агрессивным средам; использование в качестве катализатора ртути, очень вредной для здоровья человека; образование твердых отходов и шлама; большие потери ртути и перманганата; необходимость разделения ацетальдегида и уксусной кислоты (этилового спирта). The specified method allows you to get the right amount of these products. However, it has several disadvantages: the use of separate equipment that is resistant to aggressive environments; use as a catalyst of mercury, which is very harmful to human health; solid waste and sludge formation; large losses of mercury and permanganate; the need for the separation of acetaldehyde and acetic acid (ethyl alcohol).
Настоящее изобретение позволяет использовать в качестве реагентов перекись водорода и гидразин-гидрат в виде 30-40%-ных водных растворов. При контакте этих веществ друг с другом и с ацетиленом в реакторе происходит образование спирта или кислоты
1. С2Н2+H2O2+N2H4•H2O=C2H5OH+2H2O+N2
26+34+50=46+36+28
1кг+1,3+1,9=1,8кг+1,4+1,0
2. 2С2Н2+4H2O2+N2H4•H2O=2CH3COOH+5H2O+N2
52+136+50=120+90+28
1кг+2,6+0,97=2,37+1,7+0,5
Течение реакций неогне- и невзрывоопасно, так как процесс протекает в среде азота, освобождающегося при разложении гидразина перекисью. Он является как бы побочным продуктом и может быть использован для любых нужд производства, в том числе и для получения гидразина.The present invention allows the use of hydrogen peroxide and hydrazine hydrate as reagents in the form of 30-40% aqueous solutions. Upon contact of these substances with each other and with acetylene in the reactor, the formation of alcohol or acid
1. C 2 H 2 + H 2 O 2 + N 2 H 4 • H 2 O = C 2 H 5 OH + 2H 2 O + N 2
26 + 34 + 50 = 46 + 36 + 28
1kg + 1.3 + 1.9 = 1.8kg + 1.4 + 1.0
2.2C 2 H 2 + 4H 2 O 2 + N 2 H 4 • H 2 O = 2CH 3 COOH + 5H 2 O + N 2
52 + 136 + 50 = 120 + 90 + 28
1kg + 2.6 + 0.97 = 2.37 + 1.7 + 0.5
The course of the reactions is non-flammable and non-explosive, since the process proceeds in a nitrogen environment, which is released upon decomposition of hydrazine by peroxide. It is a kind of by-product and can be used for any production needs, including hydrazine.
Таким образом, предлагаемый способ позволяет при использовании одних и тех же реагентов и аппаратов получать из ацетилена этиловый спирт и уксусную кислоту, минуя стадию образования ацетальдегида и его переработку в указанные продукты. Тепла, выделяемого первой реакцией, вполне достаточно для испарения этилового спирта из реактора. В случае уксусной кислоты необходимо последующее отделение ее от воды. Thus, the proposed method allows using the same reagents and apparatuses to obtain ethyl alcohol and acetic acid from acetylene, bypassing the stage of formation of acetaldehyde and its processing into these products. The heat generated by the first reaction is quite sufficient for the evaporation of ethyl alcohol from the reactor. In the case of acetic acid, its subsequent separation from water is necessary.
Предлагаемый способ лишен всех недостатков, присущих ближайшему аналогу, и имеет существенные преимущества: прост в исполнении; не требует излишнего оборудования; в зависимости от спроса позволяет перестраиваться с этилового спирта на уксусную кислоту, не меняя оборудования; технология не связана с применением катализаторов, так как роль окислителя-восстановителя ацетилена выполняет перекись водорода и гидразин-гидрат, выпускаемые промышленностью в значительных количествах. The proposed method is devoid of all the disadvantages inherent in the closest analogue, and has significant advantages: simple to execute; does not require excessive equipment; depending on demand, it allows you to change from ethyl alcohol to acetic acid without changing equipment; the technology is not associated with the use of catalysts, since the role of acetylene oxidizing reducing agent is played by hydrogen peroxide and hydrazine hydrate, which are produced by the industry in significant quantities.
В случае использования в качестве исходного реагента ацетальдегидаммиака (твердое вещество, растворимое в воде), который образуется при воздействии на карбид кальция или ацетилен аммиаком или нашатырным спиртом, реакции идут по схемам:
3CH3CH=NH+3,75O2=3CH3COOH+1,5H2O+1,5N2
129+120=180+27+42
1кг+0,92=1,39+0,21+0,32
3CH3CH=NH+2,25O2=1,5CH3COOH+1,5C2H5OH+1,5N2
129+72=90+69+42
1кг+0,56=0,7+0,54+0,32
В качестве катализатора служит перманганат калия. Процесс протекает при 75-80oС. Азот и спирт испаряются. Уксусная кислота по первой схеме получается в виде 87- процентного водного раствора, а по второй (после улетучивания спирта и азота) - концентрированной. Такой метод не связан с применением гидразин-гидрата и перекиси водорода. В остальном, в части технологического оформления, он не отличается от вышеописанного. В обоих случаях исходным сырьем является карбид кальция или газообразный ацетилен.In the case of using acetaldehyde ammonia (a solid soluble in water) as the initial reagent, which is formed when calcium carbide or acetylene is subjected to ammonia or ammonia, the reactions proceed according to the schemes:
3CH 3 CH = NH + 3.75O 2 = 3CH 3 COOH + 1.5H 2 O + 1.5N 2
129 + 120 = 180 + 27 + 42
1kg + 0.92 = 1.39 + 0.21 + 0.32
3CH 3 CH = NH + 2.25O 2 = 1.5CH 3 COOH + 1.5C 2 H 5 OH + 1.5N 2
129 + 72 = 90 + 69 + 42
1kg + 0.56 = 0.7 + 0.54 + 0.32
Potassium permanganate is used as a catalyst. The process proceeds at 75-80 o C. Nitrogen and alcohol evaporate. Acetic acid in the first scheme is obtained in the form of an 87% aqueous solution, and in the second (after volatilization of alcohol and nitrogen) - concentrated. This method is not associated with the use of hydrazine hydrate and hydrogen peroxide. The rest, in terms of technological design, it does not differ from the above. In both cases, the starting material is calcium carbide or gaseous acetylene.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| RU2001108321A RU2187491C1 (en) | 2001-03-27 | 2001-03-27 | Method of synthesis of ethyl alcohol and acetic acid (variants) |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| RU2001108321A RU2187491C1 (en) | 2001-03-27 | 2001-03-27 | Method of synthesis of ethyl alcohol and acetic acid (variants) |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| RU2187491C1 true RU2187491C1 (en) | 2002-08-20 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| RU2001108321A RU2187491C1 (en) | 2001-03-27 | 2001-03-27 | Method of synthesis of ethyl alcohol and acetic acid (variants) |
Country Status (1)
| Country | Link |
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| RU (1) | RU2187491C1 (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1943385A (en) * | 1934-01-16 | Process for production of oxidation products of acetylene | ||
| US3574730A (en) * | 1966-12-20 | 1971-04-13 | Bp Chem Int Ltd | Production of acetic acid |
| RU2131409C1 (en) * | 1993-04-06 | 1999-06-10 | Сева Денко К.К. | Method of preparing acetic acid (variants) |
-
2001
- 2001-03-27 RU RU2001108321A patent/RU2187491C1/en active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1943385A (en) * | 1934-01-16 | Process for production of oxidation products of acetylene | ||
| US3574730A (en) * | 1966-12-20 | 1971-04-13 | Bp Chem Int Ltd | Production of acetic acid |
| RU2131409C1 (en) * | 1993-04-06 | 1999-06-10 | Сева Денко К.К. | Method of preparing acetic acid (variants) |
Non-Patent Citations (1)
| Title |
|---|
| РЕМИ Г. Курс неорганической химии, т.I. - М.: Мир, 1972, с. 427, 444. * |
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