CS248995B1 - Method of cyclohexane oxidation's catalyst recovery by air in cyclohexanone production process - Google Patents
Method of cyclohexane oxidation's catalyst recovery by air in cyclohexanone production process Download PDFInfo
- Publication number
- CS248995B1 CS248995B1 CS85488A CS48885A CS248995B1 CS 248995 B1 CS248995 B1 CS 248995B1 CS 85488 A CS85488 A CS 85488A CS 48885 A CS48885 A CS 48885A CS 248995 B1 CS248995 B1 CS 248995B1
- Authority
- CS
- Czechoslovakia
- Prior art keywords
- cyclohexane oxidation
- acids
- cobalt
- air
- oxidation catalyst
- Prior art date
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- 238000007254 oxidation reaction Methods 0.000 title claims description 23
- 238000000034 method Methods 0.000 title claims description 21
- 239000003054 catalyst Substances 0.000 title claims description 18
- 230000003647 oxidation Effects 0.000 title claims description 18
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 title claims description 15
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 title claims description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 238000011084 recovery Methods 0.000 title description 4
- 239000010941 cobalt Substances 0.000 claims description 10
- 229910017052 cobalt Inorganic materials 0.000 claims description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 10
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 8
- 125000005608 naphthenic acid group Chemical group 0.000 claims description 7
- 230000008929 regeneration Effects 0.000 claims description 7
- 238000011069 regeneration method Methods 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 239000008346 aqueous phase Substances 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 6
- 150000007524 organic acids Chemical class 0.000 claims description 5
- 235000005985 organic acids Nutrition 0.000 claims description 5
- 239000011541 reaction mixture Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 150000007513 acids Chemical class 0.000 claims description 4
- 235000010344 sodium nitrate Nutrition 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 230000001172 regenerating effect Effects 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000005341 cation exchange Methods 0.000 description 4
- 239000003729 cation exchange resin Substances 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 150000001868 cobalt Chemical class 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- -1 alkali metal salts Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 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
- 239000000463 material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000011328 necessary treatment Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- KQSJSRIUULBTSE-UHFFFAOYSA-M sodium;3-(3-ethylcyclopentyl)propanoate Chemical compound [Na+].CCC1CCC(CCC([O-])=O)C1 KQSJSRIUULBTSE-UHFFFAOYSA-M 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Landscapes
- Catalysts (AREA)
Description
Vynález rieši regeneráciu katalyzátora oxidácie cyklohexánu vzduchom v procese výroby cyklohexanónu zachytáváním kobaltu z vodné] fázy extrakcie vodorozpustných látok z reakčnej zmesi oxidácie na katexe.The invention solves the regeneration of the cyclohexane oxidation catalyst by air in the process of producing cyclohexanone by trapping cobalt from the aqueous phase of extracting water-soluble substances from the oxidation reaction mixture on the cation exchange resin.
Soli kobaltu po regenerácii katexu působením kyselinami, s výhodou zriedenou kyselinou dusičnou, sa kontaktujú s organickými kyselinami, s výhodou naftenovými kyselinami. Takto regenerovaný oxidačný katalyzátor sa použije v procese oxidácie cyklohexánu, čo zabezpečuje vyšší stupeň zhodnotenia drahého kovu a ochranu životného prostredia před kontamináciou ťažkým kovom.After cation exchange regeneration with acids, preferably dilute nitric acid, the cobalt salts are contacted with organic acids, preferably naphthenic acids. The oxidation catalyst thus recovered is used in the cyclohexane oxidation process, which provides a higher degree of recovery of the precious metal and protects the environment from heavy metal contamination.
Vynález rieši sposob regenerácie katalyzátora oxidácie cyklohexánu vzduchom v procese výroby cyklohexanónu.SUMMARY OF THE INVENTION The present invention provides a process for the regeneration of cyclohexane oxidation catalyst by air in the process of producing cyclohexanone.
Pre oxidáciu cyklohexánu vo výrobě cyklohexanónu sa ako katalyzátor majčastejšie používajú kobaltnaté soli vyšších organických kyselin, napr. nařténat kobaltnatý (polský pat. č. 95 098).For the oxidation of cyclohexane in the production of cyclohexanone, cobalt salts of higher organic acids, e.g. cobaltate (Polish Pat. No. 95 098).
V prve] fáze diskontinuálnej výroby katalyzátora sa připravuje nafténat sodný a v druhej sa pomocou roztoku dusičnanu kobaltnatého připravuje nafténat kobaltnatý. Ten sa rozpusta v cyklohexáne a po dekantácii vodou sa použije pre oxidáciu. Vodná fáza z přípravy katalyzátora sa vypúšťa do chemickej kanalizácie a spolu s inými odpadovými vodami je čištěná na čistiarni odpadových vod.In the first phase of discontinuous catalyst production, sodium naphthenate is prepared and in the second phase cobalt naphthenate is prepared using a cobalt nitrate solution. This is dissolved in cyclohexane and used for oxidation after decantation with water. The aqueous phase from the catalyst preparation is discharged into the chemical sewer and, together with other waste water, is treated in a waste water treatment plant.
Spracovanie kobaltu, ktorý odchádza v odpadových vodách z přípravy katalyzátora, rieši spósob pódia AO číslo 243 575.The treatment of cobalt leaving wastewater from the preparation of the catalyst is solved by the method of stage AO No. 243 575.
Je charakteristický tým, že segregované odpadové vody z procesu přípravy oxidačného katalyzátora obsahu jílce katióny kovu, napr. kobaltnatý, nikelnatý alebo chrornitý sa recyklují! do procesu na reakcní s prebytkom alkalických solí používaných vyšších organických, kyselin, najčastejšie nafténových kyselin. Po oddělení vodnej vrstvy, ktorá obsahuje už len stopové množstvá uvedených fažkých kovov, sa organická fáza spracuje vyššie opísaným postupom. Tento spósob regenerácie kovov je zameraný na samotný proces přípravy katalyzátora. Nerieši však problém regenerácie katalyzátora, ktorý sa po oxidácii cyklohexánu dostává do vedlejších odpadových produktov.It is characterized in that the segregated waste water from the process of preparing the oxidation catalyst of the hilt content of the metal cations, e.g. cobalt, nickel or chromium are recycled! into a process for reacting with an excess of the alkali salts of the used higher organic acids, most often naphthenic acids. After separation of the aqueous layer which contains only trace amounts of the above-mentioned heavy metals, the organic phase is treated as described above. This method of metal recovery is focused on the catalyst preparation process itself. However, it does not solve the problem of the regeneration of the catalyst which, after oxidation of cyclohexane, enters the by-products.
Podlá polského patentu č. 67 767 sa prevádza regenerácia kobaltu z destilačných zvyškov procesu oxidácie uhlovodíkov ich spálením, pričom sa vzniknuté oxidy kobaltu a železa spracujú posobením minerálnymi kyselinami na příslušné soli. Kobaltnatá sol' sa získá po odstranění železa kysličníkom vápenatým a ďalších nutných úpravách. Takto získaná sol sa opat použije na nrípravu katalyzátora. Nevýhodou tohto postupu sú materiálovo a technicky náročné operácie, čo negativným sposobom ovplyvňuje ekonomiku procesu.According to Polish patent no. 67 767, cobalt is recovered from the distillation residues of the hydrocarbon oxidation process by incineration, whereby the cobalt and iron oxides formed are treated with mineral acids to form the corresponding salts. The cobalt salt is obtained after the removal of iron by calcium oxide and other necessary treatments. The salt thus obtained is used to prepare the catalyst. The disadvantage of this procedure is material and technically demanding operations, which negatively affects the economics of the process.
Pri spósobe podlá vynálezu je vodná fáza z extrakcie reakčnej zmesi oxidácie cyklohexánu prepúšťaná cez katex, ktorý sa následné regeneruje posobením kyselinami alebo ich sofami. Regenerát sa po úpravě pH zásadami použije na přípravu oxidačného katalyzátora tým, že sa zmieša s organickými kyselinami, s výhodou s nafténovými kyselinami a ďalej sa spracuje známým postupom. Výhodné je regenerovat solami kyselin, najma solami alkalických kovov, kde je možné utvořit uzavretý cyklus regenerácia-príprava katalyzátora, ako je to uvedené v příkladu 5.In the process of the invention, the aqueous phase from the extraction of the cyclohexane oxidation reaction mixture is passed through a cation exchanger which is subsequently regenerated by acid impaction or salts thereof. After the pH has been adjusted with bases, the regenerator is used for the preparation of the oxidation catalyst by mixing with organic acids, preferably naphthenic acids, and further processing according to a known method. It is preferable to regenerate acid salts, especially alkali metal salts, where it is possible to form a closed regeneration-catalyst preparation cycle, as described in Example 5.
Výhodou uvedeného postupu je vyšší stupeň zhodnocovania drahého kovu, jeho recykláciou do oxidačného procesu a ochrana životného prostredia před kontamináclou ťažkým kovom. Ďalšie podrobnosti a výhody sú dokumentované na príkladoch.The advantage of this process is a higher degree of recovery of the precious metal, its recycling to the oxidation process and the protection of the environment from heavy metal contamination. Further details and advantages are illustrated by examples.
Příklad 1Example 1
Vodná fáza z extrakcie reakčnej zmesi oxidácie cyklohexánu obsahujúca ióny Co2+ sa prepúšťalia cez kolonu priemeru 25 mm naplnenú katexom (100 ml Wofatit KS 10). Po vyčerpaní kapacity katexu (4,5 g Co na 100 ml katexu) sa tento regeneroval 10 %-ným roztokom kyseliny chlorovodíkovej v množstve 110 ml. V regeneráte bolo stanovené zhruba 80 % množstva zachyteného kobaltu na iónomeniči.The aqueous phase from the extraction of the cyclohexane oxidation reaction mixture containing Co 2+ ions was passed through a 25 mm diameter column packed with cation exchange resin (100 ml Wofatit KS 10). After exhaustion of the cation exchange capacity (4.5 g of Co per 100 ml of cation exchanger), this was regenerated with a 10% solution of 110 ml of hydrochloric acid. About 80% of the amount of cobalt captured on the ion exchanger was determined in the regenerate.
Příklad 2Example 2
Vodná fáza z extrakcie reakčnej zmesi oxidácie cyklohexánu obsahujúca ióny Co2+ sa prepúšťala cez kolonu priemeru 25 mm naplnenú katexom (100 ml IMAC-C-14). Po vyčerpaní kapacity katexu (6,5 g Co na 100 mililitrov· katexu) ia praní vodou sa tento regeneroval 10 %-ným roztokom kyseliny dusičné) v množstve 200 ml. V regeneráte bolo zhruba 70 % zachyteného množstva kobaltu na katexe.The aqueous phase from the extraction of the cyclohexane oxidation reaction mixture containing Co 2+ ions was passed through a 25 mm diameter cation exchange column (100 mL IMAC-C-14). After exhaustion of the cation exchange capacity (6.5 g of Co per 100 ml of cation exchange resin) and washing with water, this was regenerated with 10% nitric acid solution (200 ml). In the regenerate, about 70% of the cobalt was retained on the cation exchange resin.
Příklad 3Example 3
Regenerát získaný spósobom podlá příkladu 1, s obsahom chloridu kobaltnatého zhruba 8 % hmotnostných, bol zalkalizovaný hydroxidom sodným na pH 11. Vypadnutý z roztoku hydroxid kobaltnatý sa po oddělení zmiešal s ekvivalentným množstvom nafténových kyselin za vzniku nafténatu kobaltnatého, ktorý sa použil ako katalyzátor oxidácie cyklohexánu podlá známého postupu.The regeneration obtained according to Example 1, with a cobalt chloride content of about 8% by weight, was basified with sodium hydroxide to pH 11. The precipitated cobalt hydroxide solution after separation was mixed with an equivalent amount of naphthenic acids to form cobalt naphthenate which was used as a cyclohexane oxidation catalyst. according to a known procedure.
Příklad 4Example 4
Regenerát získaný spósobom podlá příkladu 2, s obsahom Co(NO3)2 zhruba 15 % hmotnostných, bol zneutralizovaný hydroxidom sodným a použitý na přípravu oxidačného katalyzátora reakciou s nafténovými kyselinami podlá známého postupu.The regenerator obtained according to Example 2, having a Co (NO3) 2 content of about 15% by weight, was neutralized with sodium hydroxide and used to prepare the oxidation catalyst by reaction with naphthenic acids according to a known procedure.
Příklad 5!Example 5!
Katex nasýtený kobaltom zachyteným z vod extrakcie oxidačnej zmesi sa regeneroval 200 ml 2 M NaNCb a v jeho roztoku sa získalo 2,4 g kobaltu. Tento roztok sa miešal so zmesou nafténových kyselin alkalizovaných 30 %-ným roztokom NaOH na pH 8,6, pri teplote 80 °C. Po vylúčení nafténatu kobaltnatého a jeho oddělení od vodnej vrstvy, sa vodná vrstva obsahujúca NaNO3 a stopy nezreagovaného Co(NO3)2, po doplnění NaNO3 na 2 M roztok znova použila na regeneráciu nasýteného katexu,The cation exchanger saturated with cobalt trapped from the oxidation mixture extraction waters was regenerated with 200 ml of 2 M NaNCl 3 and 2.4 g of cobalt was obtained in its solution. This solution was stirred with a mixture of naphthenic acids basified with 30% NaOH to pH 8.6 at 80 ° C. After the cobalt naphthenate has been separated and separated from the aqueous layer, the aqueous layer containing NaNO3 and traces of unreacted Co (NO3) 2, after the NaNO3 has been made up to a 2 M solution, is reused to regenerate the saturated cation exchange resin,
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS85488A CS248995B1 (en) | 1985-01-24 | 1985-01-24 | Method of cyclohexane oxidation's catalyst recovery by air in cyclohexanone production process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS85488A CS248995B1 (en) | 1985-01-24 | 1985-01-24 | Method of cyclohexane oxidation's catalyst recovery by air in cyclohexanone production process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CS48885A1 CS48885A1 (en) | 1985-12-16 |
| CS248995B1 true CS248995B1 (en) | 1987-03-12 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS85488A CS248995B1 (en) | 1985-01-24 | 1985-01-24 | Method of cyclohexane oxidation's catalyst recovery by air in cyclohexanone production process |
Country Status (1)
| Country | Link |
|---|---|
| CS (1) | CS248995B1 (en) |
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1985
- 1985-01-24 CS CS85488A patent/CS248995B1/en unknown
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| Publication number | Publication date |
|---|---|
| CS48885A1 (en) | 1985-12-16 |
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