EP0311614A1 - Process for the synthesis of methyl-tert-alkyl ethers with suppression of corrosion - Google Patents
Process for the synthesis of methyl-tert-alkyl ethers with suppression of corrosionInfo
- Publication number
- EP0311614A1 EP0311614A1 EP87903869A EP87903869A EP0311614A1 EP 0311614 A1 EP0311614 A1 EP 0311614A1 EP 87903869 A EP87903869 A EP 87903869A EP 87903869 A EP87903869 A EP 87903869A EP 0311614 A1 EP0311614 A1 EP 0311614A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- methanol
- oxygen
- column
- olefins
- synthesis
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 11
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 title claims description 14
- 238000005260 corrosion Methods 0.000 title abstract description 5
- 230000007797 corrosion Effects 0.000 title abstract description 5
- 230000001629 suppression Effects 0.000 title description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 105
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000001301 oxygen Substances 0.000 claims abstract description 23
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 23
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 21
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 21
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 4
- 150000001336 alkenes Chemical class 0.000 claims description 13
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 4
- 150000002170 ethers Chemical class 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000003456 ion exchange resin Substances 0.000 claims description 4
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical class C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 3
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 2
- 229910001882 dioxygen Inorganic materials 0.000 claims description 2
- 239000002737 fuel gas Substances 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000005194 fractionation Methods 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 3
- 238000000622 liquid--liquid extraction Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000000638 solvent extraction Methods 0.000 description 3
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical compound CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 description 2
- 229910000975 Carbon steel Inorganic materials 0.000 description 2
- 239000010962 carbon steel Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 229910052598 goethite Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
- C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
Definitions
- the present invention relates to a process for the preparation of methyl-tert-alkyl ethers by starting from methanol and branched C 4 -C 8 olefins, with the double bond being on a tertiary C atom.
- the branched olefins are isobutene and isoamylenes (2-methyl-butene-2 and 2-methyl-butene-1) and produced ethers are MTBE and TAME.
- methanol used in the synthesis of MTBE stored under an air atmosphere at the temperature of 20o C and under the pressure of 760 mm Hg' dissolves about 80 ppm weight/weight (w/w) of oxygen and 180 ppm w/w of nitrogen; the presence of this latter, however, does not create any problems.
- a certain amount of dissolved oxygen can be occasionally present also in the C 4 fraction containing liquified isobutene and isobutadiene, in particular when such a fraction has been stored at low temperatures, at which the vapour pressure of the mixture becomes lower than atmospheric.
- a last source of oxygen is the wash water, but, in as much as the process is normally run by feeding it with the water removed from the bottom of methanol recovery column, such an entry way is nullified. Occasional and short openings of water cycle do not normally cause negative effects.
- the object of the present invention is a process for the synthesis of methyl-tert-alkyl ethers by starting from methanol and branched C 4 -C 8 olefins, preferably isobutene, in hydrocarbon charges containing, besides said branched olefins, straight olefins and saturated hydrocarbons, which comprises reacting the branched olefins with an excess of methanol, relatively to the stoichiometric amount thereof, in a reaction section provided with an acidic catalyst in the form of an ionexchange resin of Amberlyst 15, Dowex 50 or Lewatit SPC type, at a temperature of from 50 to 80o C and furthermore comprising the separation of formed methyl-tert-aIkyI ether from the mixture of unreacted hydrocarbon components and from the excess of methanol, by distillation, and furthermore comprising the washing, with water, of the mixture of unreacted hydrocarbon components and excess methanol to the purpose of separating said
- the procedures for oxygen removal are those known in the art for the removal of inert gases dissolved in liquid products, such as, e.g., the use of a suitable stripper consisting of a distillation column, from the bottom of which the oxygen-free product is obtained, whilst oxygen is discharged as the overhead vent from the reflux accumulator.
- the oxygen removal can be obtained by a stripping with a stream of a suitable inert gas, such as nitrogen, methane, hydrogen, fuel gas, ethane or mixtures thereof.
- a suitable inert gas such as nitrogen, methane, hydrogen, fuel gas, ethane or mixtures thereof.
- the olefinic cut (1) has a content of dissolved oxygen lower than 1 ppm, whilst methanol, which is stored inside a tank under an air atmosphere, has an oxygen content ranging from 30 to 60 mg/l.
- the reaction product (4) containing an average amount of 27.8% of MTBE, which justifies an isobutene conversion of 92%, is fed to a fractionation tray column (11), in such an intermediate point, that the rectification section represents 40% of column. From the top of said fractionation column, the unconverted hydrocarbons are removed together with azeotropic methanol (6), from the bottom of the column a stream (5) being removed, which is constituted by practically pure MTBE.
- the column is operated under a pressure of 4.9 bars, the overhead, feed and bottom temperatures are respectively 4o C, 60o C and 125o C.
- Oxygen dissolved in stream (4) fed to column (11) is only partly eliminated as an overhead vent from reflux accumulator (12); most of oxygen remains dissolved in stream (6), which is fed to a perforated-trays column
- MTBE synthesis and fractionation are carried out under analogous operating conditions as of Example 1, with the variant that methanol is treated as reported in Figure 2.
- Stream (2) which contains an amount of oxygen ranging from 30 to 60 mg/l, is delivered to the upper section of a stripping column (18), to the bottom of which a stream of nitrogen (16), containing an oxygen level lower than 150 ppm, is sent in countercurrent flow.
- the oxygen-depleted methanol, stream (3) is recovered from the bottom of the column, with oxygen levels constantly lower than 1 mg/l, and is sent to the reaction, after to it recycled methanol (9) being added.
- the oxygen-enriched stripping gas (17) is sent to blowdown.
- column (13) has been, operating for 8000 hours with no drawbacks, and an inspection thereof showed the complete absence of polymerization phenomena.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT20573/86A IT1190017B (it) | 1986-05-27 | 1986-05-27 | Processo per la sintesi di eterimetilteralchilici con soppressione della corrosione |
| IT2057386 | 1986-05-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0311614A1 true EP0311614A1 (en) | 1989-04-19 |
Family
ID=11169005
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP87903869A Ceased EP0311614A1 (en) | 1986-05-27 | 1987-05-07 | Process for the synthesis of methyl-tert-alkyl ethers with suppression of corrosion |
Country Status (12)
| Country | Link |
|---|---|
| EP (1) | EP0311614A1 (it) |
| JP (1) | JPH01502748A (it) |
| BR (1) | BR8707693A (it) |
| CS (1) | CS273639B2 (it) |
| DD (1) | DD260924A5 (it) |
| ES (1) | ES2006491A6 (it) |
| GR (1) | GR870748B (it) |
| HU (1) | HUT47892A (it) |
| IT (1) | IT1190017B (it) |
| PL (1) | PL150602B1 (it) |
| WO (1) | WO1987007260A1 (it) |
| YU (1) | YU95287A (it) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5237109A (en) * | 1991-10-10 | 1993-08-17 | Phillips Petroleum Company | Etherification process |
| RU2544553C1 (ru) * | 2013-12-25 | 2015-03-20 | Открытое акционерное общество "Газпромнефть-Московский НПЗ" (ОАО "Газпромнефть-МНПЗ") | Способ получения высокооктановой добавки к автомобильному бензину |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1259337A (en) * | 1982-09-20 | 1989-09-12 | Joe Van Pool | Combined ether and alkylate production |
-
1986
- 1986-05-27 IT IT20573/86A patent/IT1190017B/it active
-
1987
- 1987-05-07 BR BR8707693A patent/BR8707693A/pt unknown
- 1987-05-07 HU HU873325A patent/HUT47892A/hu unknown
- 1987-05-07 WO PCT/EP1987/000257 patent/WO1987007260A1/en not_active Application Discontinuation
- 1987-05-07 JP JP62503688A patent/JPH01502748A/ja active Pending
- 1987-05-07 EP EP87903869A patent/EP0311614A1/en not_active Ceased
- 1987-05-13 GR GR870748A patent/GR870748B/el unknown
- 1987-05-15 CS CS354287A patent/CS273639B2/cs unknown
- 1987-05-22 ES ES8701707A patent/ES2006491A6/es not_active Expired
- 1987-05-25 DD DD87303104A patent/DD260924A5/de not_active IP Right Cessation
- 1987-05-25 PL PL1987265892A patent/PL150602B1/pl unknown
- 1987-05-26 YU YU00952/87A patent/YU95287A/xx unknown
Non-Patent Citations (1)
| Title |
|---|
| See references of WO8707260A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CS273639B2 (en) | 1991-03-12 |
| CS354287A2 (en) | 1990-08-14 |
| WO1987007260A1 (en) | 1987-12-03 |
| JPH01502748A (ja) | 1989-09-21 |
| PL150602B1 (en) | 1990-06-30 |
| GR870748B (en) | 1987-09-23 |
| YU95287A (en) | 1988-06-30 |
| IT1190017B (it) | 1988-02-10 |
| DD260924A5 (de) | 1988-10-12 |
| IT8620573A0 (it) | 1986-05-27 |
| PL265892A1 (en) | 1988-07-21 |
| ES2006491A6 (es) | 1989-05-01 |
| BR8707693A (pt) | 1989-08-15 |
| HUT47892A (en) | 1989-04-28 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| 17P | Request for examination filed |
Effective date: 19881025 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE DE FR GB IT NL SE |
|
| 17Q | First examination report despatched |
Effective date: 19910322 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION HAS BEEN REFUSED |
|
| 18R | Application refused |
Effective date: 19911208 |
|
| RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: PESCAROLLO, ERMANNO Inventor name: TROTTA, ROBERTO Inventor name: ANCILLOTTI, FRANCESCO |