DE1048567B - - Google Patents
Info
- Publication number
- DE1048567B DE1048567B DENDAT1048567D DE1048567DA DE1048567B DE 1048567 B DE1048567 B DE 1048567B DE NDAT1048567 D DENDAT1048567 D DE NDAT1048567D DE 1048567D A DE1048567D A DE 1048567DA DE 1048567 B DE1048567 B DE 1048567B
- Authority
- DE
- Germany
- Prior art keywords
- pentaerythritol
- reaction
- formaldehyde
- water
- alkali
- 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.)
- Pending
Links
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 12
- WXZMFSXDPGVJKK-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 10
- IKHGUXGNUITLKF-UHFFFAOYSA-N acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 230000005591 charge neutralization Effects 0.000 claims description 2
- 238000010924 continuous production Methods 0.000 claims description 2
- 230000001264 neutralization Effects 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- BDAGIHXWWSANSR-UHFFFAOYSA-N formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 235000015450 Tilia cordata Nutrition 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-L oxalate Chemical compound [O-]C(=O)C([O-])=O MUBZPKHOEPUJKR-UHFFFAOYSA-L 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002035 prolonged Effects 0.000 description 1
- 230000000717 retained Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/18—Polyhydroxylic acyclic alcohols
- C07C31/24—Tetrahydroxylic alcohols, e.g. pentaerythritol
- C07C31/245—Pentaerythritol
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
- B01J2231/341—1,2-additions, e.g. aldol or Knoevenagel condensations
- B01J2231/342—Aldol type reactions, i.e. nucleophilic addition of C-H acidic compounds, their R3Si- or metal complex analogues, to aldehydes or ketones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
- B01J2231/349—1,2- or 1,4-additions in combination with further or prior reactions by the same catalyst, i.e. tandem or domino reactions, e.g. hydrogenation or further addition reactions
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Die Erfindung bezieht sich auf ein Verfahren zur kontinuierlichen Herstellung \'on Pentaerythrit. Bekanntlich bildet sich Pentaerythrit bei längerer Einwirkung von Kalkwasser auf ein Gemisch von Formaldehyd und Acetaldehyd. Unangenehm sind dabei die langen Reaktionszeiten. Das Verfahren hat zudem den Nachteil, daß es nicht kontinuierlich durchgeführt werden kann.The invention relates to a process for the continuous production of pentaerythritol. As is well known Pentaerythritol is formed after prolonged exposure to lime water on a mixture of formaldehyde and acetaldehyde. The long response times are uncomfortable. The procedure also has the disadvantage that it cannot be carried out continuously.
Erfiudungsgemäß wird nun vorgeschlagen, Pentaerythrit in der Weise kontinuierlich herzustellen, daß Acetaldehyd und Formaldehyd im Verhältnis 1 bis 4 bzw. 1 bis 6 in Gegenwart eines ein Alkali ersetzenden Ionenaustauschers kontinuierlich mit Wasser zusammengebracht wird.According to the invention, it is now proposed to continuously produce pentaerythritol in such a way that Acetaldehyde and formaldehyde in the ratio 1 to 4 or 1 to 6 in the presence of an alkali-replacing one Ion exchanger is brought together continuously with water.
Die Reaktion wird zunächst etwa 30 Minuten lang bei einer Temperatur unter 16° C durchgeführt, anschließend wird das Reaktionsgemisch in ein Rohrschlangensystem übergeführt, wo es etwa 1 Stunde lang schnell auf 60° C erwärmt wird. Nach beendeter Umsetzung wird schnell abgekühlt und kontinuierlich mit Schwefelsäure neutralisiert, wobei darauf zu achten ist, daß der Wasscrstoffionenwert innerhalb eines pH-Wertes von 7,0 bis 7.5 bleibt.The reaction is first carried out for about 30 minutes at a temperature below 16 ° C, then the reaction mixture is transferred to a pipe coil system, where it is quickly heated to 60 ° C for about 1 hour. After the reaction is rapidly cooled and continuously neutralized with sulfuric acid, to make sure is that the Wasscrstoffionenwert within a p H -value of 7.0 to 7.5 remains.
Die anfallende Lösung wird nach kurzem Absitzenlassen filtriert und zur Kristallisation eingedampft. Es bilden sich Pentaerythritkristalle in einer Ausbeute von 60%.The resulting solution is filtered after allowing it to sit for a short time and evaporated to crystallize. Pentaerythritol crystals are formed in a yield of 60%.
Erfindungsgemäß konnte noch festgestellt werden, daß mit steigender Wasserverdünnung auch die Ausbeuten an Pentaerythrit steigen. Zur Verminderung der Vcrdampfungskosten wird vorteilhaft an Stelle von Wasser als Verdünnungsmittel mit einer gesättigten Pentacrythritlösung in Wasser gearbeitet.According to the invention, it was also possible to establish that the higher the water dilution, the higher the yields increase in pentaerythritol. To reduce the evaporation costs it is advantageous in place worked of water as a diluent with a saturated pentacrythritol solution in water.
Das nicht umgesetzte Formaldehyd kann bei dem erfindungsgemäßcn Verfahren durch geeignete Operationen wieder zurückgewonnen werden und für weitere Ansätze Verwendung finden.In the process according to the invention, the unreacted formaldehyde can be removed by suitable operations can be recovered and used for further approaches.
Gegenüber dem bekannten Verfahren wird mittels des erfindungsgemäßen Verfahrens eine neue technische Wirkung erzielt, die sich aus folgenden Ulx-rlegungen ergibt:Compared to the known method, the method according to the invention is a new technical one Effect achieved, which results from the following Ulx-rlegungen:
Die Herstellung von reinem, völlig von NaOH befreitem Pentaerythrit ist äußerst schwierig. Bei den bisher bekanntgewordenen Verfahren sind zudem die Mengen an Alkali, die als Kondensationsmittel zugesetzt werden, immer verloren, weil bei der Neutralisierung die Lauge in Form von Alkaliforniiat. Alkalioxalat oder Alkalichlorid ausfällt. Dagegen hat das vorgeschlagene Verfahren den Vorzug, daß die Lauge eben infolge der Anwendung der Ionenaustauscher erhalten bleibt und jeweils wieder für «.lic neuen IJmsetzungen angesetzt werden kann. Diidii roh $:λ<\ ein hcträchtliciuT technischer Fortschritt ermöglicht. The production of pure pentaerythritol that has been completely freed from NaOH is extremely difficult. In the processes that have become known up to now, the amounts of alkali that are added as a condensing agent are also always lost, because the alkali in the form of alkali metal during the neutralization. Alkali oxalate or alkali chloride precipitates. On the other hand, the proposed method has the advantage that the alkali is retained precisely as a result of the use of the ion exchanger and can be used again for new compositions. Diidii raw $: λ <\ a real technical progress enables.
Verfahren zur kontinuierlichen
Herstellung von PentaerythritProcess for continuous
Manufacture of pentaerythritol
Anmelder:
Wilhelm Schemu th,
■ Hamburg 39, Wilerstr. 11Applicant:
Wilhelm Schemu th,
■ Hamburg 39, Wilerstr. 11
1 1 basischer Ionenaustauscher wird in einem geeigneten Kolben mit SOOccm Wasser aufgeschlämmt. Dazu läßt man im Laufe einer Stunde 1 Mol Acetaldehyd und 5 Mol Formaldehyd zufließen. Die Temperatiir soll bei diesem Verfahren 15° C nicht übersteigen. Nach dem Eintragen wird der Kolbeninhalt noch etwa 2 Stunden auf 20 bis 30° C erwärmt. Nach Absaugen des Austauschers und Ansäuern der Reaktionslösung mit verdünnter Schwefelsäure destilliert man das Wasser ab und isoliert das auskristallisierendc Pentaerythrit in bekannter Weise. Der Austauscher wird durch Behandeln mit verdünnter Salzsäure von den Foinylionen befreit; anschließend kann die Ameisensäure aus dem Filtrat durch Kotizentrierung gewonnen werden. Der Austauscher wird schließlich mit Natronlauge wieder in seine OH-Form übergeführt, um für weitere Umsetzungen Verwendung zu finden.1 liter of basic ion exchanger is suspended in a suitable flask with 50 ounces of water. For this purpose, 1 mol of acetaldehyde and 5 mol of formaldehyde are allowed to flow in over the course of one hour. The temperature should not exceed 15 ° C in this process. After entering the contents of the flask warmed to 20 to 30 ° C for another 2 hours. After suctioning off the exchanger and acidifying the reaction solution The water is distilled off with dilute sulfuric acid and the crystallizing out is isolated Pentaerythritol in a known manner. The exchanger is made by treating with dilute hydrochloric acid freed from the foinyl ions; then the formic acid can be removed from the filtrate by coticentering be won. The exchanger is finally restored to its OH form with caustic soda transferred to be used for further implementations.
Folgende Arbeitsweise läßt sich mit Vorteil anwenden: Die Reaktionslösung wird nach dem Abfiltrieren des Austauschers destilliert. Die Destillation erfolgt mit Hilfe eine.' Kolonne in der Weise, daß praktisch nur reines Wasser abdestilliert und der Forinaldelivd .sich im Destillierkolben ansammelt. Nach dem Aiiskristallisieren und dem Abfiltriercn des Prntaervllirits wird .las Fiitrat angesäuert und mit Methanol versetzt. Durch diese Operation ist es inög Hch. den gesamten nicht umgesetzten Formaldehyd in Form von Parafonnaldehyd zurückzugewinnen, der für neue Unisitzungen wieder eingesetzt wird. Die Ausbeute au Pentaerythrit beträgt bei dieser Arbeits weise, bezogen auf Fonnaldehvd. 85 bis OO0O.The following procedure can be used with advantage: The reaction solution is distilled after the exchanger has been filtered off. The distillation is done with the help of a. ' Column in such a way that practically only pure water is distilled off and the Forinaldelivd collects in the still. After it has crystallized out and filtered off the proteolite, the filtrate is acidified and mixed with methanol. Through this operation it is inög Hch. to recover all unconverted formaldehyde in the form of parafonnaldehyde, which is used again for new university sessions. The yield from pentaerythritol is in this way of working, based on Fonnaldehvd. 85 to OO 0 O.
309 129.-271309 129-271
Claims (2)
Beihefte zu Angewandte Chemie, Nr. 31 (1939), S. 14.Considered publications:
Supplements to Angewandte Chemie, No. 31 (1939), p. 14.
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1048567B true DE1048567B (en) | 1959-01-15 |
Family
ID=589728
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT1048567D Pending DE1048567B (en) |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1048567B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1105404B (en) * | 1958-02-24 | 1961-04-27 | Union Chimique Belge Sa | Process for the production of pentaerythritol |
| DE1166170B (en) * | 1960-02-18 | 1964-03-26 | Montedison Spa | Process for the continuous production of pentaerythritol |
| US4122290A (en) * | 1977-01-22 | 1978-10-24 | Bayer Aktiengesellschaft | Process for the preparation of trimethylolalkanes |
-
0
- DE DENDAT1048567D patent/DE1048567B/de active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1105404B (en) * | 1958-02-24 | 1961-04-27 | Union Chimique Belge Sa | Process for the production of pentaerythritol |
| DE1166170B (en) * | 1960-02-18 | 1964-03-26 | Montedison Spa | Process for the continuous production of pentaerythritol |
| US4122290A (en) * | 1977-01-22 | 1978-10-24 | Bayer Aktiengesellschaft | Process for the preparation of trimethylolalkanes |
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