NO138208B - PROCEDURE FOR REMOVING NICKEL CARBONYL FROM RAW PROPIONIC ACID - Google Patents
PROCEDURE FOR REMOVING NICKEL CARBONYL FROM RAW PROPIONIC ACID Download PDFInfo
- Publication number
- NO138208B NO138208B NO245772A NO245772A NO138208B NO 138208 B NO138208 B NO 138208B NO 245772 A NO245772 A NO 245772A NO 245772 A NO245772 A NO 245772A NO 138208 B NO138208 B NO 138208B
- Authority
- NO
- Norway
- Prior art keywords
- propionic acid
- nickel carbonyl
- volume
- carbonyl
- nickel
- Prior art date
Links
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 title claims description 42
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims description 31
- 229910052759 nickel Inorganic materials 0.000 title claims description 26
- 235000019260 propionic acid Nutrition 0.000 title claims description 21
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 title claims description 21
- 238000000034 method Methods 0.000 title claims description 14
- -1 NICKEL CARBONYL Chemical class 0.000 title 1
- 239000007789 gas Substances 0.000 claims description 15
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 10
- 239000005977 Ethylene Substances 0.000 claims description 10
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 150000001728 carbonyl compounds Chemical class 0.000 description 5
- 230000006315 carbonylation Effects 0.000 description 5
- 238000005810 carbonylation reaction Methods 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229940117927 ethylene oxide Drugs 0.000 description 1
- 230000010006 flight Effects 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- NAVSKFYJNZQECG-UHFFFAOYSA-N nickel;propanoic acid Chemical compound [Ni].CCC(O)=O NAVSKFYJNZQECG-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
- C07C51/14—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on a carbon-to-carbon unsaturated bond in organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/487—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Oppfinnelsen vedrører en fremgangsmåte for fjerning av nikkelkarbonyl f ra rå propionsyré som .er oppnådd ved omsetning av etylen med karbonmonoksyd og vann i nærvær av nikkelkarbonyl ved behandling med bksygenholdige gasser. The invention relates to a method for removing nickel carbonyl from crude propionic acid which is obtained by reacting ethylene with carbon monoxide and water in the presence of nickel carbonyl by treatment with oxygen-containing gases.
■Fra den ålment tilgjengelige tyske patentsøknad nr.. ■From the widely available German patent application no.
N 599/12 o er det kjent -en fremgangsmåte ved hvilken .man Æra kar-bonyleringsprodukter spalter de deri inneholdende metallkarbonylforbindelser ved behandling med en blanding av hydrogen og karbonmonoksyd ved forhøyet temperatur. Ved en annen fremgangsmåte som" er kjent fra BRD-utlegningsskrift nr. 1 014 093 ekspanderes den reaksjonsblanding som.oppnås, ved fremstilling av propionsyré, og alt nikkelkarbonyl spaltes dervéd. Begge fremgangsmåter har den ulempe at ved spaltning av metallkarbonylforbindelsene får man av-leiringer på karveggene. "Dessuten er det teknisk brysomt å skille fra det metallslam som .da opptrer :i fin fordeling. I henhold til andre metoder som .er .beskrevet 1 US-patentskrift nr. 2 547 178 og BRD-utl.skrift nr. 1 107 212, oksyderes de :i karbonyleringsproduk-ter inneholdende metallkarbonylforbindelser fullstendig ved behandling med oksygerihbldige gasser. Bortsett fra at man må være meget omhyggelig med at ..oksydas jonen av metallkarbonylf orbindelsene fo-regår fullstendig, slik at. man unngår skadelige innvirkninger ved . den påfølgende behandling, må de bestående metallsalter gjenvinnes og opparbeides slik at disse igjen kan anvendes for karbonyleringen. pen samtidige anvendelse av metallsalter har imidlertid alltid den ulempe ved karbonyleringen at det inntrer en viss inhibering inn-til métallkarbonyiforbindelsene igjen har dannet seg. Endelig er det kjent fra BRD-patentskrift nr. 1 :279 667 at .man kan gjennomfø-re fjerning av metallkarbonyl ved behandling med oksygeriholdige gasser i nærvær av et surt medium qg stoffer med stor overflate. Bortsett fra de ovennevnte ulemper har denne "fremgangsmåte ytt.erli-gere den ulempe at den aktive overflate meget hurtig blir inaktiv på grunn av de høytkokende biprodukter som inneholdes i karbonyle-ringsproduktene. N 599/12 o a method is known in which the Æra carbonylation products split the metal carbonyl compounds they contain by treatment with a mixture of hydrogen and carbon monoxide at an elevated temperature. In another method which is known from BRD explanatory document no. 1 014 093, the reaction mixture that is obtained is expanded during the production of propionic acid, and all nickel carbonyl is split therefrom. Both methods have the disadvantage that when the metal carbonyl compounds are split, deposits are formed on the vessel walls. "Furthermore, it is technically difficult to separate from the metal sludge which appears in a fine distribution. According to other methods described in US Patent No. 2,547,178 and BRD Publication No. 1,107,212, the carbonylation products containing metal carbonyl compounds are oxidized completely by treatment with oxygen-containing gases. Apart from the fact that one must be very careful that the oxidation of the metal carbonyl compounds takes place completely, so that. one avoids harmful effects by . the subsequent treatment, the existing metal salts must be recovered and processed so that these can again be used for the carbonylation. however, the simultaneous use of metal salts always has the disadvantage of the carbonylation that a certain inhibition occurs until the metal carbonyl compounds have formed again. Finally, it is known from BRD patent document no. 1:279 667 that metal carbonyl can be removed by treatment with oxygen-containing gases in the presence of an acidic medium such as substances with a large surface area. Apart from the above-mentioned disadvantages, this method has the further disadvantage that the active surface very quickly becomes inactive due to the high-boiling by-products contained in the carbonylation products.
Man var derfor stilt overfor den tekniske oppgave å fjerne nikkelkarbonyl fra rå propionsyré hvorved det så langt som mulig skulle unngås metallavleiringer og hvorved man skulle kunne gjenvinne nikkelkarbonyl som sådant. One was therefore faced with the technical task of removing nickel carbonyl from crude propionic acid whereby metal deposits were to be avoided as far as possible and whereby nickel carbonyl as such was to be recovered.
Man har nå funnet at man på en mer fordelaktig måte enn tidligere kan fjerne nikkelkarbonyl fra rå propionsyré som er oppnådd ved omsetning av etylen med karbonmonoksyd og vann i nærvær av nikkelkarbonyl, ved behandling med oksygenholdige gasser,når man gjennomfører behandlingen i motstrøm i en overrislingskolonne, hvorved man pr. m nikkelkarbonylholdig, rå propionsyré anvender .5-20"Nm" gassblanding som inneholder 90-97 volum% inertgass og It has now been found that nickel carbonyl can be removed from crude propionic acid obtained by reacting ethylene with carbon monoxide and water in the presence of nickel carbonyl in a more advantageous way than before, by treatment with oxygen-containing gases, when the treatment is carried out in countercurrent in a sprinkler column , whereby one per m nickel carbonyl-containing, crude propionic acid uses .5-20"Nm" gas mixture containing 90-97 volume% inert gas and
.3-10 volum% oksygen. .3-10 volume% oxygen.
Den nye fremgangsmåte har den fordel at det ikke opptrer noen metallutskillinger på utstyret. The new method has the advantage that no metal deposits occur on the equipment.
Den nye fremgangsmåte er bemerkelsesverdig, da det var å vente at nikkelkarbonylet ved behandlingen av nikkelkarbonylholdig, rå propionsyré med molekylært oksygen-holdige gasser oksyderes fullstendig slik som ved fremgangsmåten i henhold til tek-nikkens stand og at de tilsvarende nikkelsalter oppnås. The new method is remarkable, as it was to be expected that the nickel carbonyl in the treatment of nickel carbonyl-containing crude propionic acid with molecular oxygen-containing gases is completely oxidized as in the method according to the state of the art and that the corresponding nickel salts are obtained.
Den rå propionsyré fremstilles ved omsetning av etylen med karbonmonoksyd og vann i nærvær av nikkelkarbonyl. , vanligvis anvender man etylen og karbonmonoksyd i molforholdet 1: (0,8-2) ,.' spesielt, i molforholdet 1: (1-1,5). Videre anvender man fordelak-Jtig pr. mol etylen 1,5-2,5 mol vann. Som katalysator anvendes sam-tidig nikkelkarbonyl i en mengde av 0,5-3 vekt%, beregnet som nikkelmetall, på etylen-basis. Vanligvis utføres reaksjonen ved temperaturer på 250-320°C, spesielt 270-300°C.. Videre anvender man fordelaktig.trykk på.lOO-300 atm., spesielt 200-^250 atm. The crude propionic acid is produced by reacting ethylene with carbon monoxide and water in the presence of nickel carbonyl. , usually ethylene and carbon monoxide are used in the molar ratio 1: (0.8-2) ,.' in particular, in the molar ratio 1: (1-1.5). Furthermore, one applies the benefit acc-Jtig per mol ethylene 1.5-2.5 mol water. At the same time, nickel carbonyl is used as a catalyst in an amount of 0.5-3% by weight, calculated as nickel metal, on an ethylene basis. Usually the reaction is carried out at temperatures of 250-320°C, especially 270-300°C. Furthermore, a pressure of 100-300 atm., especially 200-^250 atm is advantageously used.
Den således fremstilte, rå propionsyré inneholder vanligvis 80-90 vekt% propionsyré, 8-16 vekt% vann, 0,3-0,7 vekt% nikkelpropionat, 0,2-0,4 vekt% nikkelkarbonyl, videre 0,6-1 vekt% oppløste gasser, .f.eks. etan , .etylen , karbonmonoksyd og karbondioksyd, videre opptil 0,7. vekt% høytkokende.andeler. The crude propionic acid produced in this way usually contains 80-90% by weight propionic acid, 8-16% by weight water, 0.3-0.7% by weight nickel propionate, 0.2-0.4% by weight nickel carbonyl, further 0.6-1 % by weight of dissolved gases, e.g. ethane, .ethylene, carbon monoxide and carbon dioxide, further up to 0.7. wt% high boiling.proportions.
Den rå, nikkelkarbonylholdige propionsyré behandles for-trinnsvis. pr. m 3 med. 8-15Nm 3 gassblanding,som inneholder 93-96 volum% inertgass og 4-7 volum% oksygen. Egnete inertgasser er eksempelvis nitrogen, karbondioksyd eller karbonmonoksyd. Det er også fordelaktig å anvende avgass fra propionsyrefremstillingen, slik den forefinnes etter fjerning av nikkelkarbonyl. Den.inneholder eksempelvis 4,2 volum% etylen, 45,9 volum% karbonmonoksyd, 10,8 volum% karbondioksyd og opptil 39,1 volum% av andre inertgasser, f.eks. nitrogen. The crude, nickel carbonyl-containing propionic acid is preferably treated. per m 3 incl. 8-15Nm 3 gas mixture, which contains 93-96 volume% inert gas and 4-7 volume% oxygen. Suitable inert gases are, for example, nitrogen, carbon dioxide or carbon monoxide. It is also advantageous to use off-gas from the propionic acid production, as it exists after removal of the nickel carbonyl. It contains, for example, 4.2% by volume of ethylene, 45.9% by volume of carbon monoxide, 10.8% by volume of carbon dioxide and up to 39.1% by volume of other inert gases, e.g. nitrogen.
Behandlingen utføres, som nevnt, i motstrøm i en overrislingskolonne. Den utfører fordelaktig slik at man ved toppen av en kolonne som hensiktsmessig er forsynt med innsatser for god gjennomblanding, f^eks. Raschig- eller Pall-ringer, tilfører den . nikkelkarbonylholdige propionsyré og tilfører den nevnte gassblanding nedenfra. Vanligvis -utføres behandlingen ved temperaturer på 0-200°C, spesielt ved temperaturer på 50-100°C. Vanligvis anvender man normaltrykk eller forhøyet trykk, opp til 10 atmosfærer overtrykk. The treatment is carried out, as mentioned, in countercurrent in a sprinkler column. It is advantageously carried out so that at the top of a column which is suitably provided with inserts for good thorough mixing, e.g. Raschig or Pall rings, it adds . nickel carbonyl-containing propionic acid and supplies the aforementioned gas mixture from below. Usually - the treatment is carried out at temperatures of 0-200°C, especially at temperatures of 50-100°C. Usually normal pressure or elevated pressure is used, up to 10 atmospheres overpressure.
Den ved fremgangsmåten i henhold til oppfinnelsen fremstilte propionsyré egner seg for fremstilling av estere eller for behandling av forstoffer. The propionic acid produced by the method according to the invention is suitable for the production of esters or for the treatment of precursors.
Fremgangsmåten i henhold ±il oppfinnelsen skal anskuelig-gjøres ved hjelp av følgende eksempler. The method according to the invention shall be illustrated by means of the following examples.
EKSEMPEL 1 EXAMPLE 1
I en med Pall-ringer fylt kolonne av rustfritt stål med 300 mm diameter og 12 m lengde tilføres ved toppen 3804 kg rå propionsyré (sammensetning, se tabellen) pr. time, slik man får den ved syntesen av propionsyré etter ekspandering og fraskillelse av avgassen. I kolonnesumpen innføres pr. time 40 Nm 3 av en blan- In a stainless steel column filled with Pall rings with a diameter of 300 mm and a length of 12 m, 3804 kg of raw propionic acid (composition, see the table) are fed at the top per hour, as obtained from the synthesis of propionic acid after expansion and separation of the exhaust gas. In the column total, per hour 40 Nm 3 of a mixed
3 3 ding av 30 m .nitrogen og 10 m luft. I kolonnesumpen utgjør tem-peraturen 80°C, på toppen 78°C. Trykket svinger mellom 0,6 og 1 atm., overtrykk. De oppnådde resultater sees av følgende tabell. 3 3 ding of 30 m .nitrogen and 10 m air. In the bottom of the column the temperature is 80°C, at the top 78°C. The pressure fluctuates between 0.6 and 1 atm., overpressure. The results obtained can be seen in the following table.
Etter 6 måneders løpetid er det ikke mulig .å fastslå noen vesent-lig avleiring av nikkelmetall i kolonnen. After 6 months' duration, it is not possible to determine any significant deposit of nickel metal in the column.
EKSEMPEL 2 EXAMPLE 2
Man behandler rå propionsyré som beskrevet i -eksempel 1,. men anvender en blanding av 30 Nm 3av en for nikkelkarbonyl befridd avgass fra propionsyresyntesen, som inneholder-4,2 volum% etylen, 45,9 volum% karbonmonoksyd, 10,8 volum% karbondioksyd og 39,1 volum% inertgasser, samt 8 Nm 3luft pr. time. Etter 6 måneders løpetid kan det ikke fastslåes noen nikkelavieiringer. Raw propionic acid is treated as described in example 1. but uses a mixture of 30 Nm 3 of a nickel carbonyl-free off-gas from the propionic acid synthesis, which contains-4.2 vol% ethylene, 45.9 vol% carbon monoxide, 10.8 vol% carbon dioxide and 39.1 vol% inert gases, as well as 8 Nm 3 air per hour. After the 6-month term, no nickel flights can be determined.
SAMMENLIKNINGSEKSEMPEL COMPARISON EXAMPLE
Man arbeider som angitt i eksempel 1, men anvender bare 40 m 3 nitrogen. Etter 1-3 måoneder er avleiringene av nikkel så sterke at man må stoppe driften og gjøre rent. One works as indicated in example 1, but only uses 40 m 3 of nitrogen. After 1-3 months, the deposits of nickel are so strong that you have to stop the operation and clean.
Claims (2)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19712134684 DE2134684C3 (en) | 1971-07-12 | 1971-07-12 | Process for removing nickel carbonyl from crude propionic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| NO138208B true NO138208B (en) | 1978-04-17 |
| NO138208C NO138208C (en) | 1978-07-26 |
Family
ID=5813388
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO245772A NO138208C (en) | 1971-07-12 | 1972-07-10 | PROCEDURE FOR REMOVING NICKEL CARBONYL FROM RAW PROPIONIC ACID |
Country Status (12)
| Country | Link |
|---|---|
| AT (1) | AT316500B (en) |
| BE (1) | BE786052A (en) |
| CA (1) | CA986950A (en) |
| DE (1) | DE2134684C3 (en) |
| DK (1) | DK133276C (en) |
| FI (1) | FI56669C (en) |
| FR (1) | FR2145516B1 (en) |
| GB (1) | GB1389432A (en) |
| IT (1) | IT961335B (en) |
| NL (1) | NL172054C (en) |
| NO (1) | NO138208C (en) |
| SE (1) | SE390534B (en) |
-
0
- BE BE786052D patent/BE786052A/en unknown
-
1971
- 1971-07-12 DE DE19712134684 patent/DE2134684C3/en not_active Expired
-
1972
- 1972-06-16 FI FI173572A patent/FI56669C/en active
- 1972-07-07 FR FR7224641A patent/FR2145516B1/fr not_active Expired
- 1972-07-10 NO NO245772A patent/NO138208C/en unknown
- 1972-07-10 IT IT5145072A patent/IT961335B/en active
- 1972-07-10 CA CA146,780A patent/CA986950A/en not_active Expired
- 1972-07-11 DK DK344872A patent/DK133276C/en active
- 1972-07-11 AT AT593472A patent/AT316500B/en not_active IP Right Cessation
- 1972-07-11 GB GB3233372A patent/GB1389432A/en not_active Expired
- 1972-07-12 NL NL7209625A patent/NL172054C/en not_active IP Right Cessation
- 1972-07-12 SE SE917472A patent/SE390534B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| FI56669C (en) | 1980-03-10 |
| DE2134684B2 (en) | 1979-12-06 |
| NL7209625A (en) | 1973-01-16 |
| NL172054C (en) | 1983-07-01 |
| IT961335B (en) | 1973-12-10 |
| DE2134684A1 (en) | 1973-02-01 |
| AT316500B (en) | 1974-07-10 |
| GB1389432A (en) | 1975-04-03 |
| NO138208C (en) | 1978-07-26 |
| FR2145516A1 (en) | 1973-02-23 |
| FI56669B (en) | 1979-11-30 |
| BE786052A (en) | 1973-01-10 |
| DK133276C (en) | 1976-09-20 |
| DE2134684C3 (en) | 1980-08-14 |
| NL172054B (en) | 1983-02-01 |
| SE390534B (en) | 1976-12-27 |
| FR2145516B1 (en) | 1976-08-06 |
| CA986950A (en) | 1976-04-06 |
| DK133276B (en) | 1976-04-20 |
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