WO2004037802A1 - Rückführung des bei der oxidation von olefinen nicht umgesetzten olefins - Google Patents
Rückführung des bei der oxidation von olefinen nicht umgesetzten olefins Download PDFInfo
- Publication number
- WO2004037802A1 WO2004037802A1 PCT/EP2003/011736 EP0311736W WO2004037802A1 WO 2004037802 A1 WO2004037802 A1 WO 2004037802A1 EP 0311736 W EP0311736 W EP 0311736W WO 2004037802 A1 WO2004037802 A1 WO 2004037802A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- exhaust gas
- olefin
- gas stream
- propene
- epoxidation
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
Definitions
- the invention relates to a process for the continuous recycling of the olefin not converted in the epoxidation of olefins with hydroperoxides to oxiranes.
- the exhaust gas stream resulting from the epoxidation is compressed with cooling and separated in a pressure distillation into an olefin-containing bottoms stream and an exhaust gas stream which is largely free of hydrocarbons.
- the olefin is returned to the epoxidation process.
- the process for recycling the propene used in the production of propene oxide can be used particularly advantageously.
- the invention also relates to a device with which the method can be carried out.
- a method has thus been proposed in which a gas mixture consisting of the olefin and oxygen, which comes from the decomposition reaction of the hydrogen peroxide used as the hydroperoxide in the epoxidation, is separated off, and the olefin is absorbed from the gas mixture in a liquid absorbent.
- a sufficient amount of inert gas must be added to the oxygen to prevent the formation of flammable gas compositions.
- this process is used to recover propene from the reaction of propene with hydrogen peroxide to propene oxide.
- Methane is preferably used as the inert gas and a mixture comprising isopropanol and water is used as the liquid absorbent (EP-B 0719 768).
- the low solubility of the olefin in the water-containing isopropanol has an unfavorable effect. Therefore, relatively large amounts of solvent have to be used in order to be able to extract the olefin from the exhaust gas stream by absorption. Furthermore, it is uneconomical to add another gas, in particular methane, to the column used for absorption in addition to the exhaust gas stream.
- This object could be achieved according to the invention by compressing the exhaust gas stream formed during the epoxidation of an olefin with hydroperoxide to give the oxirane with cooling, isolating the olefin contained therein from the exhaust gas stream by distillation and returning it to the epoxidation process.
- the invention thus relates to a process for the continuous recycling of the olefin which has not been converted in the epoxidation of olefins with hydroperoxide to oxiranes and which is contained in the exhaust gas stream formed during the epoxidation, characterized in that it has the stages (i) to (iii) includes
- the process according to the invention it is not necessary to additionally feed an inert gas into the separation device in the step of separating the olefin in order to avoid explosive mixtures.
- the isolation of the olefin via an absorption system is not required.
- the process according to the invention allows the olefin to be separated from the exhaust gas stream in high yield with relatively little effort and with only one distillation. Since the process can be operated continuously, it can be used extremely advantageously for industrial use.
- the epoxidation of olefins with hydroperoxide can be carried out in one or more stages.
- Such methods, as well as a technical process, are described for example in WO 00/07965.
- distillation columns can be used to separate off the oxiranes formed during the oxidation.
- Exhaust gas streams are obtained at the top of the columns.
- these exhaust gas streams always contain unreacted olefin and a small amount of oxygen, which comes from the decomposition reaction of the hydroperoxide used.
- Inert gases, preferably nitrogen, are usually used to better regulate the distillation. Since these are also removed via the top of the columns, the exhaust gas streams also contain these gases. In the process according to the invention, it is therefore no longer necessary to feed an additional gas into the absorption system to avoid explosive mixtures.
- step (i) it is sufficient in step (i) to cool the exhaust gas stream to a temperature of preferably 0 to 70 ° C., more preferably 15 to 55 ° C., in particular 30 to 40 ° C.
- the usual equipment such as reciprocating, diaphragm, screw or rotary compressors can be used for compression.
- the compression is preferably not carried out in one stage, but in several stages with cooling between the individual compression stages. This procedure has the advantage of an easily controlled final compression temperature to the permissible value range.
- the compression of the exhaust gas stream is carried out in two stages.
- the exhaust gas stream is then preferably under a pressure of 2 to 30 bar, more preferably 10 to 25 bar, in particular 12 to 20 bar. Accordingly, an embodiment of the method according to the invention is also characterized in that in step (i) the exhaust gas stream is cooled to a temperature of 0 to 70 ° C and compressed to a pressure of 2 to 30 bar.
- the waste gas stream pretreated by cooling and compression is then fed to a distillation column, it being possible to use the customary columns.
- Columns are, for example, rectification columns with preferably between 3 and 20, preferably 5 and 10 theoretical plates.
- the compressed exhaust gas stream is fed continuously into the column.
- the feed point can be in the middle column area of the column.
- pressure and temperature are now selected, for example in the ranges as described above, so that the mixture of substances to be separated is partially evaporated.
- the olefin, as the high-boiling component of the waste gas stream at the bottom of the column, and the low-boiling components, such as, for example, the inert gases contained in the waste gas stream or other volatile by-products formed in the reaction, can be distilled off at the top of the column.
- the gas portion of the exhaust gas stream that is obtained with the low boilers can be supplied to a combustion, for example.
- the olefin obtained in the bottom of the column is preferably obtained in a purity of at least 90%. It can generally be added to the epoxidation process with the hydroperoxide without further purification steps.
- the olefin can be returned to the epoxidation process to the extent that it is separated from the exhaust gas stream from the epoxidation. This means that a process that can be operated continuously is extremely economical.
- the process according to the invention can be carried out particularly advantageously for the separation of propene from an exhaust gas stream which originates from the oxidation of propene to propene oxide.
- the exhaust gas stream then also comprises inert gases, in particular nitrogen, and a small amount of oxygen.
- inert gases in particular nitrogen
- oxygen a small amount of oxygen.
- propane propene and propane being present in a volume ratio of approximately 97: 3 to 95: 5.
- the exhaust gas stream as olefin therefore comprises propene from the epoxidation of propene to propene oxide and propane.
- the exhaust gas stream is preferably cooled to a temperature of 30 ° C. to 40 ° C. and compressed to a pressure of 12 to 20 bar.
- a temperature of approximately 35 ° C. and a pressure of approximately 16 bar are very particularly preferred.
- Said compressed exhaust gas stream is then fed into a distillation column for separation in stage (ii), which preferably takes place almost at the top separation stage.
- stage (ii) preferably takes place almost at the top separation stage.
- the column is operated almost as a pure stripping column. The consequence of this is that the evaporating gas mixture is only relatively slightly enriched with the high-boiling components within the column.
- the hydrocarbon-containing fraction containing propene and propane is rapidly and readily separated off as the bottom product, while the inert gases contained in the exhaust gas stream or other volatile by-products formed during the epoxidation distill off as a low boiler fraction via the top of the column. At least 93% of the hydrocarbons can be separated from the exhaust gas stream.
- the low boiler fraction therefore only has low concentrations of hydrocarbons, which are preferably below 7% by weight, the total sum of the components contained in the low boiler fraction being 100% by weight.
- the stream of the components propene and propane obtained via the column bottom can then be separated into the components propene and propane in a C 3 splitter, as described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, Vol A22, page 214.
- the separation can take place in a column at a pressure of approximately 15 to 25 bar.
- the C-splitter can also be carried out in the form of thermally coupled columns for separation. These can then be operated, for example, at a pressure of approximately 15 or 25 bar.
- the propene is obtained overhead, the propane with the sump.
- the propene can now be returned to the epoxidation process with the hydroperoxide.
- Propane can be used as an energy source for steam generation.
- olefins which can be separated from exhaust gas streams which are formed in the epoxidation of said olefins with hydroperoxide to give the corresponding oxiranes:
- olefins which are gaseous under normal conditions or have a boiling point below 150 ° C. are preferably used in the process according to the invention. These are preferably olefins having 2 to 8 carbon atoms. Ethene, propene and butene are particularly preferably used. Propene is particularly preferably used.
- hydroperoxides known from the prior art which are suitable for the reaction of the olefin can be used as the hydroperoxide for the epoxidation.
- hydroperoxides are, for example, tert-butyl hydroperoxide or ethylbenzene hydroperoxide.
- Hydrogen peroxide can also be used as the hydroperoxide, for example as an aqueous solution.
- the exhaust gas streams can also originate from oxidation processes in which the reaction of the olefin with the hydroperoxide is catalyzed, for example by heterogeneous catalysts.
- propene is separated off from an exhaust gas stream which is obtained in the epoxidation of propene with hydrogen peroxide to propene oxide, the reaction being catalyzed heterogeneously.
- the invention also relates to a device for carrying out the method according to the invention, which is characterized in that it has at least one reactor for producing propene oxide, at least one apparatus for compressing the exhaust gas stream, at least one distillation column for separating said propene and propane from the exhaust gas stream and a C 3 splitter for separation of propene and propane included.
- the flow diagram shown in the figure illustrates how propene can be recovered from the epoxidation (oxidation) of propene to propene oxide by the process according to the invention, the compression taking place in two stages with cooling in between.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Epoxy Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/532,096 US7408073B2 (en) | 2002-10-23 | 2003-10-23 | Returning an olefin which is not reacted during the oxidation of olefins |
MXPA05004183A MXPA05004183A (es) | 2002-10-23 | 2003-10-23 | Retorno de las olefinas que no reaccionan durante la oxidacion de olefinas. |
AU2003278127A AU2003278127A1 (en) | 2002-10-23 | 2003-10-23 | Returning an olefin which is not reacted during the oxidation of olefins |
CA002503449A CA2503449A1 (en) | 2002-10-23 | 2003-10-23 | Process for the continuous recirculation of the olefin which has not been reacted in the oxidation of olefins by hydroperoxides, by means of compression and pressure distillation |
DE50310044T DE50310044D1 (de) | 2002-10-23 | 2003-10-23 | Rückführung des bei der oxidation von olefinen nicht umgesetzten olefins |
EP03769439A EP1558596B1 (de) | 2002-10-23 | 2003-10-23 | Rückführung des bei der oxidation von olefinen nicht umgesetzten olefins |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10249378.2 | 2002-10-23 | ||
DE10249378A DE10249378A1 (de) | 2002-10-23 | 2002-10-23 | Verfahren zur kontinuierlichen Rückführung des bei der Oxidation von Olefinen mit Hydroperoxiden nicht umgesetzten Olefins mittels Verdichtung und Druckdestillation |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2004037802A1 true WO2004037802A1 (de) | 2004-05-06 |
Family
ID=32087126
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2003/011736 WO2004037802A1 (de) | 2002-10-23 | 2003-10-23 | Rückführung des bei der oxidation von olefinen nicht umgesetzten olefins |
Country Status (11)
Country | Link |
---|---|
US (1) | US7408073B2 (de) |
EP (1) | EP1558596B1 (de) |
CN (1) | CN1329384C (de) |
AT (1) | ATE399160T1 (de) |
AU (1) | AU2003278127A1 (de) |
CA (1) | CA2503449A1 (de) |
DE (2) | DE10249378A1 (de) |
MX (1) | MXPA05004183A (de) |
MY (1) | MY139768A (de) |
WO (1) | WO2004037802A1 (de) |
ZA (1) | ZA200503273B (de) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7863468B2 (en) | 2005-06-29 | 2011-01-04 | Basf Aktiengesellschaft | Process for producing propylene oxide |
WO2018015430A1 (en) | 2016-07-20 | 2018-01-25 | Basf Se | A process for preparing propylene oxide |
WO2018197234A1 (en) | 2017-04-24 | 2018-11-01 | Basf Se | Propene recovery by scrubbing with a solvent/water mixture |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2149569A1 (de) | 2008-08-01 | 2010-02-03 | Hexion Specialty Chemicals Research Belgium S.A. | Verfahren zur Herstellung eines 1,2-Epoxid |
EP2149570A1 (de) * | 2008-08-01 | 2010-02-03 | Hexion Specialty Chemicals Research Belgium S.A. | Verfahren zur Herstellung von Epichlorhydrin mit Wasserstoffperoxid und einem Mangankomplex |
EP3380448B1 (de) | 2015-11-25 | 2019-08-28 | Evonik Degussa GmbH | Verfahren zur herstellung von 1,2-propandiol aus propen und wasserstoffperoxid |
HUE054720T2 (hu) | 2015-11-26 | 2021-09-28 | Evonik Operations Gmbh | Eljárás és reaktor propén epoxidálására |
WO2017089074A1 (en) | 2015-11-26 | 2017-06-01 | Evonik Degussa Gmbh | Process for the epoxidation of an olefin |
TWI707847B (zh) * | 2015-11-26 | 2020-10-21 | 德商贏創運營有限公司 | 丙烯之環氧化方法 |
US10676450B2 (en) | 2016-01-19 | 2020-06-09 | Evonik Operations Gmbh | Process for the epoxidation of an olefin |
MY185641A (en) | 2016-03-21 | 2021-05-27 | Evonik Operations Gmbh | Process for the epoxidation of propene |
EP3246323A1 (de) | 2016-05-17 | 2017-11-22 | Evonik Degussa GmbH | Integrierter prozess zur herststellung von propenoxid aus propan |
EP3406603A1 (de) * | 2017-05-22 | 2018-11-28 | Evonik Degussa GmbH | Verfahren zur epoxidierung von propen |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0467538A1 (de) * | 1990-07-09 | 1992-01-22 | The Boc Group, Inc. | Verfahren zur Herstellung von Alkylenoxid |
EP0646558A1 (de) * | 1993-09-30 | 1995-04-05 | The Boc Group, Inc. | Verfahren zur Herstellung von Kohlenwasserstoffteiloxidationsprodukten |
EP0719768A1 (de) * | 1994-12-28 | 1996-07-03 | ARCO Chemical Technology, L.P. | Rückgewinnung von Olefin und Sauerstoff in einer Wasserstoffperoxid-Epoxidation |
WO2002014298A1 (en) * | 2000-08-11 | 2002-02-21 | Dow Global Technologies Inc. | Process for the continuous production of an olefinic oxide |
DE10155470A1 (de) * | 2001-11-12 | 2003-05-22 | Basf Ag | Verfahren zur Synthese von Propylenoxid unter Propen-Rückgewinnung |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3000188A (en) * | 1956-11-15 | 1961-09-19 | Kellogg M W Co | Gas separation |
DE19835907A1 (de) | 1998-08-07 | 2000-02-17 | Basf Ag | Verfahren zur Umsetzung einer organischen Verbindung mit einem Hydroperoxid |
-
2002
- 2002-10-23 DE DE10249378A patent/DE10249378A1/de not_active Withdrawn
-
2003
- 2003-10-22 MY MYPI20034019A patent/MY139768A/en unknown
- 2003-10-23 AT AT03769439T patent/ATE399160T1/de not_active IP Right Cessation
- 2003-10-23 WO PCT/EP2003/011736 patent/WO2004037802A1/de active IP Right Grant
- 2003-10-23 US US10/532,096 patent/US7408073B2/en not_active Expired - Fee Related
- 2003-10-23 DE DE50310044T patent/DE50310044D1/de not_active Expired - Lifetime
- 2003-10-23 MX MXPA05004183A patent/MXPA05004183A/es active IP Right Grant
- 2003-10-23 AU AU2003278127A patent/AU2003278127A1/en not_active Abandoned
- 2003-10-23 CN CNB2003801018500A patent/CN1329384C/zh not_active Expired - Lifetime
- 2003-10-23 CA CA002503449A patent/CA2503449A1/en not_active Abandoned
- 2003-10-23 EP EP03769439A patent/EP1558596B1/de not_active Expired - Lifetime
-
2005
- 2005-04-22 ZA ZA200503273A patent/ZA200503273B/en unknown
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0467538A1 (de) * | 1990-07-09 | 1992-01-22 | The Boc Group, Inc. | Verfahren zur Herstellung von Alkylenoxid |
EP0646558A1 (de) * | 1993-09-30 | 1995-04-05 | The Boc Group, Inc. | Verfahren zur Herstellung von Kohlenwasserstoffteiloxidationsprodukten |
EP0719768A1 (de) * | 1994-12-28 | 1996-07-03 | ARCO Chemical Technology, L.P. | Rückgewinnung von Olefin und Sauerstoff in einer Wasserstoffperoxid-Epoxidation |
WO2002014298A1 (en) * | 2000-08-11 | 2002-02-21 | Dow Global Technologies Inc. | Process for the continuous production of an olefinic oxide |
DE10155470A1 (de) * | 2001-11-12 | 2003-05-22 | Basf Ag | Verfahren zur Synthese von Propylenoxid unter Propen-Rückgewinnung |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7863468B2 (en) | 2005-06-29 | 2011-01-04 | Basf Aktiengesellschaft | Process for producing propylene oxide |
WO2018015430A1 (en) | 2016-07-20 | 2018-01-25 | Basf Se | A process for preparing propylene oxide |
US10435381B2 (en) | 2016-07-20 | 2019-10-08 | Basf Se | Process for preparing propylene oxide |
RU2740395C2 (ru) * | 2016-07-20 | 2021-01-13 | Басф Се | Способ получения пропиленоксида |
WO2018197234A1 (en) | 2017-04-24 | 2018-11-01 | Basf Se | Propene recovery by scrubbing with a solvent/water mixture |
US11180467B2 (en) | 2017-04-24 | 2021-11-23 | Basf Se | Propene recovery by scrubbing with a solvent/water mixture |
Also Published As
Publication number | Publication date |
---|---|
AU2003278127A1 (en) | 2004-05-13 |
DE10249378A1 (de) | 2004-05-06 |
ZA200503273B (en) | 2006-11-29 |
CN1329384C (zh) | 2007-08-01 |
MY139768A (en) | 2009-10-30 |
EP1558596B1 (de) | 2008-06-25 |
CA2503449A1 (en) | 2004-05-06 |
CN1705652A (zh) | 2005-12-07 |
US20060058539A1 (en) | 2006-03-16 |
EP1558596A1 (de) | 2005-08-03 |
ATE399160T1 (de) | 2008-07-15 |
MXPA05004183A (es) | 2005-06-08 |
DE50310044D1 (de) | 2008-08-07 |
US7408073B2 (en) | 2008-08-05 |
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