DE3638168A1 - Process for the reduction of the salt content of crude hydroxypivalaldehyde - Google Patents
Process for the reduction of the salt content of crude hydroxypivalaldehydeInfo
- Publication number
- DE3638168A1 DE3638168A1 DE19863638168 DE3638168A DE3638168A1 DE 3638168 A1 DE3638168 A1 DE 3638168A1 DE 19863638168 DE19863638168 DE 19863638168 DE 3638168 A DE3638168 A DE 3638168A DE 3638168 A1 DE3638168 A1 DE 3638168A1
- Authority
- DE
- Germany
- Prior art keywords
- water
- aldolization
- crude
- isobutyraldehyde
- salt content
- 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.)
- Granted
Links
- 150000003839 salts Chemical class 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 title claims description 14
- JJMOMMLADQPZNY-UHFFFAOYSA-N 3-hydroxy-2,2-dimethylpropanal Chemical compound OCC(C)(C)C=O JJMOMMLADQPZNY-UHFFFAOYSA-N 0.000 title abstract 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 claims abstract description 19
- 230000003197 catalytic effect Effects 0.000 claims abstract description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims abstract 2
- 239000012071 phase Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000012074 organic phase Substances 0.000 claims description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 238000005984 hydrogenation reaction Methods 0.000 description 6
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000010612 desalination reaction Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000010626 work up procedure Methods 0.000 description 2
- 238000005705 Cannizzaro reaction Methods 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical class CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 1
- 229940117969 neopentyl glycol Drugs 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/75—Reactions with formaldehyde
-
- 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
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/80—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
Abstract
Description
Die Erfindung betrifft ein Verfahren zur Entsalzung von Hydropivalin aldehyd, der im allgemeinen unter dem katalytischen Einfluß von Basen aus Isobutyraldehyd und Formaldehyd gewonnen wird. Für die Weiterver arbeitung zum reinen 2,2-Dimethyl-1,3-propandiol wird dieser Aldehyd im allgemeinen zunächst hydriert und der anfallende Hydrieraustrag fraktioniert. Bei beiden Weiterverarbeitungsstufen wirkt sich die An wesenheit von Salzen negativ aus. Während sie im ersten Fall eine Be legung des Kontaktes und damit eine Desaktivierung herbeiführen kön nen, ist durch ihre Anwesenheit bei der destillativen Aufarbeitung eine mehr oder weniger starke Produktzersetzung festzustellen.The invention relates to a process for the desalination of hydropivalin aldehyde, which is generally under the catalytic influence of bases is obtained from isobutyraldehyde and formaldehyde. For further processing This aldehyde becomes a pure 2,2-dimethyl-1,3-propanediol generally first hydrogenated and the resulting hydrogenation fractionated. The An affects both processing stages presence of salts negative. While in the first case she was a Be establishment of the contact and thus can bring about a deactivation due to their presence during the distillative workup notice a more or less strong product decomposition.
Als solche störenden Verbindungen treten die Aldolisationskatalysatoren selbst wie auch z. B. deren Formiate, Isobutyrate oder Hydroxipi valate auf. Letztere werden u. a. als Folge von Cannizzaro-Reaktionen oder durch Einwirkung von Sauerstoff auf das Reaktionsgemisch gebil det.The aldolization catalysts occur as such interfering compounds even as z. B. their formates, isobutyrates or hydroxipi valate on. The latter are u. a. as a result of Cannizzaro reactions or by the action of oxygen on the reaction mixture det.
Wegen der Labilität des Hydroxipivalinaldehyds wurden in der Literatur vornehmlich Verfahren beschrieben, bei denen die Entsalzung sich auf das wesentlich stabilere System des rohen 2,2-Dimethylpropan- 1,3-diols beschränkt. Ein wesentlicher Nachteil dieser Vorgehensweise besteht darin, daß die durch Salzbelegung hervorgerufenen Aktivitäts änderungen des Hydrierkontaktes nicht ohne weiteres kompensiert werden können.Because of the instability of the hydroxipivalaldehyde in the Literature primarily describes processes in which desalination the much more stable system of crude 2,2-dimethylpropane 1,3-diols limited. A major disadvantage of this approach is that the activity caused by salt occupancy Changes in the hydrogenation contact can not be compensated for easily can.
Die Entfernung der Salze aus dem Hydrieraustrag mittels eines Ionen austauschers ist in der DE-PS 9 67 552 dargelegt. Nach dem Verfahren der DE-OS 14 93 048 wird eine vorgeschaltete Behandlung des NPG-Roh produkts mittels eines Dünnschichtverdampfers vorgeschlagen. In der Beschreibung der US-PS 28 95 996 und nach dem modifizierten Verfahren der DE-AS 10 76 655 wird der Hydrieraustrag mittels einer Wasserdampf destillation vom salzhaltigen Rückstand abgetrennt und das wäßrige Destillat in einem nachfolgenden Aufarbeitungsschritt getrennt. Die Azeotropdestillation des Rohprodukts und nachfolgende Destillationen werden in der US-PS 28 65 819 geschildert. Nach der JP 69/10 767 wird der Hydrieraustrag zunächst in einser Extraktionsstufe mit z. B. Ethern vorbehandelt.The removal of the salts from the hydrogenation discharge by means of an ion exchanger is set out in DE-PS 9 67 552. After the procedure DE-OS 14 93 048 is an upstream treatment of the NPG raw product proposed using a thin film evaporator. In the Description of US-PS 28 95 996 and according to the modified method DE-AS 10 76 655 is the hydrogenation discharge by means of a water vapor Distillation separated from the saline residue and the aqueous Distillate separated in a subsequent work-up step. The Azeotropic distillation of the crude product and subsequent distillations are described in US-PS 28 65 819. According to JP 69/10 767 the hydrogenation discharge initially in one extraction stage with z. B. ethers pretreated.
Die Nachteile dieser Vefahren sind darin zu sehen, daß sie wegen der Labilität des Hydroxipivalinaldehyds erst nach dessen Hydrierung zum Neopentylglykol sinnvoll angewandt werden können und größtenteils system freie Hilfsstoffe bei einem Einsatz von energieintensiven mehrstu figen Apparatesystemen benötigen. Es bestand daher ein Interesse an einem Verfahren, bei dem die Reduzierung des Salzgehaltes im Hydroxi pivalinaldehyd, wie er bei der alkalisch katalysierten Aldolisation von Isobutyraldehyd und Formaldehyd anfällt, ohne Zusatz von systemfremden Hilfsstoffen ermöglicht wird.The disadvantages of these processes are that they are due to the Lability of the hydroxipivalaldehyde only after its hydrogenation to Neopentylglycol can be used sensibly and mostly system free auxiliaries when using energy-intensive multis need apparatus systems. There was therefore an interest in a process in which the reduction of the salt content in the hydroxy pivalinaldehyde as used in the alkaline catalyzed aldolization of Isobutyraldehyde and formaldehyde are obtained without the addition of extraneous systems Auxiliary substances is made possible.
Erfindungsgemäß wird die sich damit ergebende Aufgabe entsprechend den Angaben der Patentansprüche gelöst.According to the invention, the resulting task is accordingly Disclosed claims.
Überraschenderweise ist die Reduzierung des Salzgehaltes von rohem Hy droxipivalinaldehyd mit einem gelösten Wasseranteil von ca. 5 bis 10%, wie er bei der alkalisch katalysierten Aldolisation von Isobutyraldehyd und Formaldehyd anfällt, durch Behandlung mit 0,5 bis 20 Gewichts prozent, bevorzugt 2 bis 8 Gewichtsprozent, Wasser möglich. Der Einsatz größerer Wasseranteile ist zwar möglich, beinhaltet aber gleichzeitig unerwünscht hohe Produktverluste.Surprisingly, the reduction in the salt content of raw Hy droxipivalaldehyde with a dissolved water content of approx. 5 to 10%, as in the alkaline catalyzed aldolization of isobutyraldehyde and formaldehyde is obtained by treatment with 0.5 to 20 weight percent, preferably 2 to 8 percent by weight, of water possible. The stake Larger proportions of water are possible, but also include undesirably high product losses.
Die Zugabe des Wassers erfolgt sinnvollerweise nach Abtrennung der aus der Aldolisation herrührenden Wasserphase, wobei die Dosierung in einem Schritt erfolgen kann. Vorteilhaft ist jedoch die Unterteilung der Gesamtwassermenge in mehrere Portionen. Man erreicht auf diese Weise bei gleichem Wassereinsatz einen deutlich höheren Entsalzungs grad, wenn nach jeder intensiven Durchmischung eine Abtrennung der je weiligen Wasserphase vorgenommen wird. The water is expediently added after the water has been separated off the aldolization-derived water phase, the dosage in one Step can take place. However, the subdivision is advantageous the total amount of water in several servings. You can reach this Way with the same water use a significantly higher desalination degree, if after each intensive mixing a separation of each because of the water phase.
Die Abtrennung der Wasserphase erfolgt nach dem Stand der Technik, z. B. entweder in entsprechenden Abscheidern oder durch Einsatz von Separatoren.The water phase is separated according to the prior art, e.g. B. either in appropriate separators or by using Separators.
Auf Grund der bei diesen Trennverfahren erforderlichen Dichteunter schiede zwischen der organischen und der wäßrigen Phase, ist durch ge eignete Reaktionsführung darauf zu achten, daß die Dichte der organi schen Phase beispielsweise bei 50°C den Wert von 1,1 g/ml, vorzugs weise von 1,0 g/ml, nicht überschreitet. In einfacher Weise kann dieses beispielsweise durch Reaktionsführung bei der Aldolisation wie z. B. Begrenzung des Isobutyraldehydumsatzes bzw. durch Zugabe eines höheren Überschusses an Isobutyraldehyd oder durch Abmischung des Reaktionsaustrags mit wenig wasserlöslichen organischen Stoffen wie Isobutyraldehyd und/oder Isobutanol erfolgen.Due to the density required in these separation processes difference between the organic and the aqueous phase, is by ge suitable reaction procedure to ensure that the density of the organi rule phase at 50 ° C, the value of 1.1 g / ml, preferred of 1.0 g / ml, not exceeding. In a simple way, this for example by carrying out the reaction in the aldolization such as e.g. B. Limiting the isobutyraldehyde conversion or by adding a higher excess of isobutyraldehyde or by mixing the Reaction discharge with poorly water-soluble organic substances such as Isobutyraldehyde and / or isobutanol take place.
Bei der Durchmischung des vom Reaktionswasser abgetrennten Aldoli sats werden im allgemeinen Temperaturen von 20 bis 70°C eingehalten. Neben einer Reduzierung der Löslichkeit der im Aldolisat vorhandenen Salze ist zur Einstellung niedrigerer Temperatur als 20°C unnötige Energie in Form von Kühlung aufzubringen. Bei Einstellung von höherer Temperatur als 70°C ist mit erhöhten Verlusten von z. B. Isobutyral dehyd zu rechnen, wenn keine teueren Druckapparate verwendet werden.When mixing the Aldoli separated from the water of reaction Sats are generally kept at temperatures from 20 to 70 ° C. In addition to reducing the solubility of those present in the aldolisate Salts are unnecessary for setting temperatures lower than 20 ° C Applying energy in the form of cooling. When setting higher Temperature than 70 ° C is associated with increased losses of e.g. B. Isobutyral Expect dehydration if no expensive pressure equipment is used.
Roher Hydroxipivalinaldehyd mit einer Dichte von 0,96 g/ml und einem Salzgehalt von 540 ppm (ber. als NaOOCH) wurde bei Raumtemperatur mit den aus der folgenden Tabelle ersichtlichen Wassermengen intensiv durchmischt. In der sich abscheidenden organischen Phase wurden die aufgelisteten Salzgehalte berechnet als Natriumformiat bestimmt.Raw hydroxipivalaldehyde with a density of 0.96 g / ml and a Salinity of 540 ppm (calculated as NaOOCH) was measured at room temperature the amounts of water shown in the following table mixed up. In the separating organic phase, the listed salinity calculated as sodium formate.
Wasseranteil (%)Salzgehalt (ppm) 2230 4130 8 95Water content (%) Salinity (ppm) 2230 4130 8 95
Durch wiederholtes Waschen mit jeweils geringeren Wassermengen und Ab trennung der Wasserphase wurden ausgehend vom selben Produkt wie oben folgende Werte erzielt:By repeated washing with smaller amounts of water and Ab Separation of the water phase were based on the same product as above achieved the following values:
WasseranteilSalzgehalt (ppm) 2 × 2%40 3 × 1% 9Salinity (ppm) 2 × 2% 40 3 × 1% 9
Claims (6)
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19863638168 DE3638168A1 (en) | 1986-11-08 | 1986-11-08 | Process for the reduction of the salt content of crude hydroxypivalaldehyde |
| IT8748587A IT1212045B (en) | 1986-11-08 | 1987-11-06 | PROCEDURE FOR THE REDUCTION OF THE CONTENT IN RAW HYDROXIPIVALIC ALDEHYDE SALTS |
| JP62279452A JPS63135347A (en) | 1986-11-08 | 1987-11-06 | Method of reducing content of crude hydroxypivaline aldehyde salt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19863638168 DE3638168A1 (en) | 1986-11-08 | 1986-11-08 | Process for the reduction of the salt content of crude hydroxypivalaldehyde |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| DE3638168A1 true DE3638168A1 (en) | 1988-05-19 |
| DE3638168C2 DE3638168C2 (en) | 1989-01-19 |
Family
ID=6313515
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19863638168 Granted DE3638168A1 (en) | 1986-11-08 | 1986-11-08 | Process for the reduction of the salt content of crude hydroxypivalaldehyde |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPS63135347A (en) |
| DE (1) | DE3638168A1 (en) |
| IT (1) | IT1212045B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10392335B2 (en) | 2016-01-07 | 2019-08-27 | Mitsubishi Gas Chemical Company, Inc. | Method for producing hydroxypivalaldehyde |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1793512B2 (en) * | 1968-09-27 | 1974-07-18 | Basf Ag, 6700 Ludwigshafen | Process for the preparation of 2,2-dimethyl-3-hydroxypropanal |
| DE2547540A1 (en) * | 1974-10-30 | 1976-05-13 | Charbonnages Ste Chimique | METHOD FOR PRODUCING HYDROXYPIVALDEHYDE |
-
1986
- 1986-11-08 DE DE19863638168 patent/DE3638168A1/en active Granted
-
1987
- 1987-11-06 JP JP62279452A patent/JPS63135347A/en active Pending
- 1987-11-06 IT IT8748587A patent/IT1212045B/en active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1793512B2 (en) * | 1968-09-27 | 1974-07-18 | Basf Ag, 6700 Ludwigshafen | Process for the preparation of 2,2-dimethyl-3-hydroxypropanal |
| DE2547540A1 (en) * | 1974-10-30 | 1976-05-13 | Charbonnages Ste Chimique | METHOD FOR PRODUCING HYDROXYPIVALDEHYDE |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3638168C2 (en) | 1989-01-19 |
| IT8748587A0 (en) | 1987-11-06 |
| JPS63135347A (en) | 1988-06-07 |
| IT1212045B (en) | 1989-11-08 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| OP8 | Request for examination as to paragraph 44 patent law | ||
| D2 | Grant after examination | ||
| 8363 | Opposition against the patent | ||
| 8330 | Complete renunciation |