US3215743A - Process for oxidizing olefins containing at least 3 carbon atoms to aldehydes and ketones - Google Patents
Process for oxidizing olefins containing at least 3 carbon atoms to aldehydes and ketones Download PDFInfo
- Publication number
- US3215743A US3215743A US15074A US1507460A US3215743A US 3215743 A US3215743 A US 3215743A US 15074 A US15074 A US 15074A US 1507460 A US1507460 A US 1507460A US 3215743 A US3215743 A US 3215743A
- Authority
- US
- United States
- Prior art keywords
- ketones
- aldehydes
- catalyst
- salt
- grams
- 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.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims description 21
- 150000001299 aldehydes Chemical class 0.000 title claims description 20
- 150000002576 ketones Chemical class 0.000 title claims description 15
- 150000001336 alkenes Chemical class 0.000 title description 8
- 125000004432 carbon atom Chemical group C* 0.000 title description 4
- 230000001590 oxidative effect Effects 0.000 title description 4
- 239000003054 catalyst Substances 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 150000001728 carbonyl compounds Chemical class 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 230000001965 increasing effect Effects 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- -1 CARBONYL GROUP Chemical group 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 150000001721 carbon Chemical class 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 239000004711 α-olefin Substances 0.000 claims description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 32
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 30
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 22
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 17
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 17
- 101150003085 Pdcl gene Proteins 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 229910000510 noble metal Inorganic materials 0.000 description 14
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 230000003028 elevating effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- YXFQHOWTCLONDT-UHFFFAOYSA-N propanal;propan-2-one Chemical compound CCC=O.CC(C)=O YXFQHOWTCLONDT-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B35/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving a change in the type of bonding between two carbon atoms already directly linked
- C07B35/04—Dehydrogenation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
- C07C45/35—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in propene or isobutene
Definitions
- the present invention relates to a process for oxidizing olefins containing at least 3 carbon atoms to aldehydes and ketones.
- ketones are almost exclusively obtained (see Angewandte Chemie, 1959, vol. 71, page 179).
- propylene is oxidized in the aforesaid manner, only 1 part of propionaldehyde is obtained per 200 parts of acetone formed, and the oxidation of butene-l yields only about 0.5% of butyraldehyde calculated on the methylethylketone formed.
- the quantity of aldehyde formed in the first 2 to 3 hours is larger but it then drops to the aforesaid values given as examples.
- the portion of aldehyde formed can be considerably enlarged as compared with ketone, by using a catalyst which contains, per liter of catalyst, more than about 0.5 mol of a noble metal salt, advantageously palladium chloride, in addition to a salt, advantageously the halide, of such metals as are capable of forming several stable valence stages.
- a noble metal salt advantageously palladium chloride
- a salt advantageously the halide
- the amount of noble metal salt to be added according to the invention shall exceed 0.25 mol, which corresponds, for example, to 45 grams PdCl per liter of catalyst and shall be advantageously above 0.5 mol, which corresponds to about 90 grams PdCl per liter of catalyst.
- the upper limit is given by the solubility of the noble metal compound at the working temperature used.
- the ratio of aldehyde to ketone may, however, become again unfavorable.
- the catalyst shall also contain a redox compound, for example a copper or iron salt, as described in the aforesaid specification.
- the formation of aldehyde increases with the amount of noble metal compound added and with the temperature.
- higher temperatures favor the formation of aldehyde only when the minimum quantity of noble metal compound to be added according 3,215,743 Patented Nov. 2, 1965 to the invention is used.
- an elevated pressure may, how ever, also be advantageous at lower temperatures.
- the ratio of propionaldehyde formed to acetone formed is, for example, as follows:
- the catalyst used may be solid or liquid. If in catalysts containing halogen compounds losses in halogen occur, the lost proportion has to be replaced, for example, by the addition of hydrochloric acid.
- the process may be carried out in a liquid or solid phase, for example, in the manner described in the aforesaid copending patent, applications or in commonly owned copending U.S. patent application Ser. No. 855,975 filed on November 30, 1959 (now US, 3,119,874 granted January 28, 1964), and under the conditions described therein.
- compounds yielding anions for example hydrogen chloride
- the process may be carried out at a temperature within the range of 20 to 200 C. or more, preferably at a temperature ranging from 50 to 170 C.
- EXAMPLE 1 A reaction tube in upright position was charged with 100 cc. of an aqueous catalyst containing 100 grams of PdCl and 400 grams of CuCI ZH O per liter of liquid. 4 liters of propylene and 1 liter of oxygen were then introduced per hour into the catalyst through a frit and the acetone and propionaldehyde which formed were isolated by a water wash. At a temperature of 85 C., propionaldehyde and acetone were obtained in a ratio of 1:42; at 100 C. in a ratio of 1:3.6; at 120 C. and 1 atmosphere gage in a ratio of 1:29. In the last instance, the conversion of propylene to the sum of aldehyde ketone amounted to 23%, calculated on the propylene which had been put through. The gases that had not been reacted could be returned to the process and re-used.
- Example 2 The apparatus of Example 1 was charged with 100 cc. of catalyst liquid containing, per liter, grams of PdCl and 320 grams of CuCl .2H O and the process was carried out as described in Example 1.
- the ratio of propionaldehyde to acetone was 1:7.2 at 20 C.; 1:43 at 85 C., 1:3.5 at 100 (3.; 1:20 at 120 C.
- Example 3 The apparatus of Example 1 was charged. with an aqueous catalyst solution containing, per liter, 220 grams of PdCl and 440 grams of CuCl .2H O and the process was carried out as described in Example 1. Propionaldehyde and acetone were obtained at 85 C. in a ratio of 1:4.0.
- Example 4 The apparatus of Example 1 was charged with 100 cc. of a catalyst containing, per liter, 160 grams of PdCl and 320 grams of CuCl .2H O. A mixture of 4 liters/ hour of butene-l and 1 liter/hour of oxygen was introduced into the catalyst liquid. The ratio of butyraldehyde t-o methylethylketone was 1:11 at 20 C.; 1:6.7 at 85 C.; 124.8 at 100 C.
- EXAMPLE 5 A long reaction tube 30 mm. in diameter and provided with a heating jacket was charged with 200 cc. of active carbon which was impregnated with a solution of 40 grams of CuCl .2H O and increasing amounts of PdCl Water which was constantly kept at 85 C. with the help of a thermostat was passed through the heating jacket. A mixture of 20 liters/ hour of propylene and 40 liters/ hour of air was conducted through an evaporator disposed before the reaction tube and then in a downward direction through the catalyst. Into the evaporator which Was heated by means of an oil bath, ce/hour of 011 N- hydrochloric acid were introduced dropwise at a uniform rate, evaporated and introduced into the catalyst together with the gas current.
- the reaction mixture leaving the reaction tube was freed from water in a cooler and samples were continuously taken in order to be analyzed by gas-chromatography.
- the carbonyl compounds, propionaldehyde and acetone, which. had been formed were isolated from the reaction mixture by washing with water and finally a remainder of the said carbonyl compounds was absorbed with hydroxylamine.
- the concentration of propionaldehyde in the reaction product increased as the content of PdCl in the catalyst was increased, i.e., from 1.6% of propionaldehyde at a PdCl content of 2 grams to 12.4% of propionaldehyde at a PdCl content of 20 grams.
- the following table clearly shows the shift from ketone t-o aldehyde occurring in the reaction product in dependence on the PdCl content of the catalyst.
- EXAMPLE 7 A mixture of 7.5 liters of propylene and 30 liters of air was introduced per hour, at 85 C., into a catalyst solu tion of 50 grams of PdCl and 200 grams of CuCl .2H O in 500 cc. of water to which 10 cc. of concentrated hydrochloric acid had been added.
- the reaction mixture was examined in a manner analogous to that described in the preceding examples. It contained 14% of propionaldehyde, calculated on acetone, in the first 24 working hours. The portion of aldehyde then gradually dropped by about 50% and maintained that value in a permanent test lasting 600 hours.
- EXAMPLE 8 A heatable tube 10 mm. in diameter was charged with 30 cc. of silica gel which was impregnated with 10 cc. of a solution of 250 grams/liter of CuCl .2H O and varying amounts of PdCl per liter. 'The reaction temperature was about C. 2 normal liters (N.T.P.) of propylene and 1 normal liter (N.T.P.) of oxygen were introduced per hour. The oxygen-containing compounds which had formed, particularly acetone and propionaldehyde, were isolated from the gas mixture leaving the reaction zone by washing with water.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF28004A DE1136685B (de) | 1959-03-21 | 1959-03-21 | Verfahren zur Oxydation von Olefinen mit 3 und mehr C-Atomen zu Aldehyden und Ketonen |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3215743A true US3215743A (en) | 1965-11-02 |
Family
ID=7092697
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US15074A Expired - Lifetime US3215743A (en) | 1959-03-21 | 1960-03-15 | Process for oxidizing olefins containing at least 3 carbon atoms to aldehydes and ketones |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US3215743A (de) |
| CH (1) | CH397630A (de) |
| DE (1) | DE1136685B (de) |
| GB (1) | GB938838A (de) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4720474A (en) * | 1985-09-24 | 1988-01-19 | Catalytica Associates | Olefin oxidation catalyst system |
| US4723041A (en) * | 1985-09-24 | 1988-02-02 | Catalytica Associates | Olefin oxidation catalyst system |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2376269A1 (fr) * | 1976-09-06 | 1978-07-28 | Thepenier Henri | Elements de construction avec dispositifs multiples d'accrochages et d'assemblages par mortaises profilees coordonnees reliees entre elles a l'aide de clavettes. production de facades en tout genre par dispositifs de cliches |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE713791C (de) * | 1934-07-19 | 1941-11-14 | Bernh Draeger | UEberfuehrung von in Gasgemischen in geringen Mengen enthaltenem Kohlenoxyd in Kohlendioxyd durch Oxydation |
| FR891209A (fr) * | 1942-10-17 | 1944-03-01 | Procédé de préparation d'acétaldéhyde en vue de la fabrication de l'acide acétique, para et métaldéhyde, aldol, etc. |
-
1959
- 1959-03-21 DE DEF28004A patent/DE1136685B/de active Pending
-
1960
- 1960-03-15 US US15074A patent/US3215743A/en not_active Expired - Lifetime
- 1960-03-18 CH CH304660A patent/CH397630A/de unknown
- 1960-03-21 GB GB9966/60A patent/GB938838A/en not_active Expired
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE713791C (de) * | 1934-07-19 | 1941-11-14 | Bernh Draeger | UEberfuehrung von in Gasgemischen in geringen Mengen enthaltenem Kohlenoxyd in Kohlendioxyd durch Oxydation |
| FR891209A (fr) * | 1942-10-17 | 1944-03-01 | Procédé de préparation d'acétaldéhyde en vue de la fabrication de l'acide acétique, para et métaldéhyde, aldol, etc. |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4720474A (en) * | 1985-09-24 | 1988-01-19 | Catalytica Associates | Olefin oxidation catalyst system |
| US4723041A (en) * | 1985-09-24 | 1988-02-02 | Catalytica Associates | Olefin oxidation catalyst system |
Also Published As
| Publication number | Publication date |
|---|---|
| CH397630A (de) | 1965-08-31 |
| GB938838A (en) | 1963-10-09 |
| DE1136685B (de) | 1962-09-20 |
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