DE1243663B - Process for the purification of saturated alcohols - Google Patents
Process for the purification of saturated alcoholsInfo
- Publication number
- DE1243663B DE1243663B DEW37716A DEW0037716A DE1243663B DE 1243663 B DE1243663 B DE 1243663B DE W37716 A DEW37716 A DE W37716A DE W0037716 A DEW0037716 A DE W0037716A DE 1243663 B DE1243663 B DE 1243663B
- Authority
- DE
- Germany
- Prior art keywords
- double bond
- calculated
- distillation
- continuous
- hypochlorite
- 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
- 238000000034 method Methods 0.000 title claims description 12
- 150000001298 alcohols Chemical class 0.000 title claims description 7
- 238000000746 purification Methods 0.000 title claims description 5
- 229920006395 saturated elastomer Polymers 0.000 title claims description 5
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 24
- 238000004821 distillation Methods 0.000 claims description 12
- 239000000460 chlorine Substances 0.000 claims description 11
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052801 chlorine Inorganic materials 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 239000008346 aqueous phase Substances 0.000 claims description 6
- 238000005660 chlorination reaction Methods 0.000 claims description 6
- 150000001299 aldehydes Chemical class 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 238000007086 side reaction Methods 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims 3
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical group CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims 2
- NUJGJRNETVAIRJ-UHFFFAOYSA-N octanal Chemical compound CCCCCCCC=O NUJGJRNETVAIRJ-UHFFFAOYSA-N 0.000 claims 2
- 239000012074 organic phase Substances 0.000 claims 2
- 239000012071 phase Substances 0.000 claims 2
- 230000009183 running Effects 0.000 claims 2
- 238000003786 synthesis reaction Methods 0.000 claims 2
- WCASXYBKJHWFMY-NSCUHMNNSA-N 2-Buten-1-ol Chemical compound C\C=C\CO WCASXYBKJHWFMY-NSCUHMNNSA-N 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 239000003518 caustics Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 claims 1
- 229910001919 chlorite Inorganic materials 0.000 claims 1
- 229910052619 chlorite group Inorganic materials 0.000 claims 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical class OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 claims 1
- 238000001944 continuous distillation Methods 0.000 claims 1
- 230000009089 cytolysis Effects 0.000 claims 1
- WCASXYBKJHWFMY-UHFFFAOYSA-N gamma-methylallyl alcohol Natural products CC=CCO WCASXYBKJHWFMY-UHFFFAOYSA-N 0.000 claims 1
- 239000002994 raw material Substances 0.000 claims 1
- 239000011541 reaction mixture Substances 0.000 claims 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- 239000000047 product Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000007792 addition Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 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
- C07C31/02—Monohydroxylic acyclic alcohols
- C07C31/12—Monohydroxylic acyclic alcohols containing four carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/03—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2
- C07C29/04—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
-
- 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
- C07C31/02—Monohydroxylic acyclic alcohols
- C07C31/10—Monohydroxylic acyclic alcohols containing three carbon atoms
-
- 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
- C07C31/02—Monohydroxylic acyclic alcohols
- C07C31/125—Monohydroxylic acyclic alcohols containing five to twenty-two carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/02—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/02—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen
- C07C47/06—Acetaldehyde
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
DEUTSCHESGERMAN
PATENTAMTPATENT OFFICE
PATENTSCHRIFTPATENT LETTERING
Int. Cl.: Int. Cl .:
C07cC07c
Deutsche Kl.: 12Ο-5/Θ2 German class: 12Ο-5 / Θ2
Nummer:Number:
Aktenzeichen:File number:
Anmeldetag:Registration date:
W37716IVb/12o 9. Oktober 1964W37716IVb / 12o October 9, 1964
6. Juli 1967
11. Januar 1968July 6, 1967
January 11, 1968
Auslegetag:
Ausgabetag:Display day:
Issue date:
Patentschrift stimmt mit der Auslegeschrift übereinThe patent specification corresponds to the patent specification
Bei der Herstellung synthetischer Alkohole treten in den Rohprodukten Verunreinigungen auf, vor allem olefinisch ungesättigte Alkohole, deren Siedepunkt sich nur wenig von dem der gesättigten Alkohole unterscheidet und die sich durch die nachfolgende Destillation im allgemeinen nicht restlos entfernen lassen. Da der Verbleib solcher Verbindungen im destillierten Produkt jedoch über dessen Qualität entscheidet, sind' Methoden entwickelt .worden, die es gestatten, solche Verunreinigungskomponenten auf anderem Wege zu entfernen. : In the production of synthetic alcohols, impurities occur in the crude products, especially olefinically unsaturated alcohols whose boiling point differs only slightly from that of the saturated alcohols and which in general cannot be completely removed by the subsequent distillation. However, since the whereabouts of such compounds in the distilled product determines its quality, methods have been developed which allow such impurity components to be removed by other means. :
So ist es bekannt, daß bei der Reinigung von Glykolen Zusätze von möglichst alkalischem Hypochlorit verwendet werden.It is known, for example, that in the purification of glycols, additions of hypochlorite, which is as alkaline as possible, are used be used.
Weiterhin gehört es zum Stande der Technik, daß sich Verbindungen der genannten Art durch Chloreinwirkung angreifen lassen. Sie werden hierbei in einer solchen Weise verändert, daß sie bei der nachfolgenden Destillation dem zu erzeugenden Produkt nicht mehr folgen. Eine solche Chlorierung kann beispielsweise durch eine Behandlung mit einer wäßrigen Lösung von Chlor vorgenommen oder es können Chemikalien zugesetzt werden, aus denen die erforderliche Chlormenge in Freiheit gesetzt wird. So ist z. B. möglich, den zu reinigenden Alkohol mit einer auf seinen Doppelbindungsgehalt berechneten Menge an Hypochloritlösung zu versetzen. Durch Zugabe einer in bezug auf das vorhandene Hypochlorit mindestens stöchiometrischen Mineralsäuremenge wird in dieser Mischung das für die chlorierende Behandlung erforderliche Chlor in Freiheit gesetzt.Furthermore, it is part of the state of the art that compounds of the type mentioned are formed by the action of chlorine attack. They are changed in such a way that they are used in the following Do not follow the distillation of the product to be produced. Such chlorination can for example made by treatment with an aqueous solution of chlorine or it chemicals can be added from which the required amount of chlorine is released. So is z. B. possible to use the alcohol to be cleaned to add an amount of hypochlorite solution calculated on its double bond content. Through An amount of mineral acid which is at least stoichiometric in relation to the hypochlorite present is added in this mixture the chlorine required for the chlorinating treatment is set free.
Bei der Durchführung des Verfahrens zeigt es sich jedoch, daß ζ. Β. bei entsprechend behandeltem Butanol nach der anschließenden Destillation der Doppelbindungsgehalt durchaus nicht im gewünschten Maß zurückgeht. Auch läßt sich1 der von diesem Doppelbindungsgehalt abhängige Schwefelsäuretest, der ein einfaches Kriterium der Produktreinheit darstellt, nicht auf völlig farblose herabdrücken.When carrying out the process, however, it turns out that ζ. Β. in the case of appropriately treated butanol, the double bond content does not decrease to the desired extent after the subsequent distillation. Also can be one of the dependent of this double bond content of sulfuric acid test, which is a simple criterion of product purity, not depress a completely colorless.
Weiterhin kann beobachtet werden, daß bei der Chlorierung in fühlbarem Umfang Nebenreaktiönen auftreten. Teilweise handelt es sich hierbei um Dehydrierungsvorgänge, deren Produkte entweder direkt oder nach Kondensation in der zwischengeschalteten Alkaliwäsche in die Destillation gelängen und diese in unübersichtlicher Weise verseuchen. Zum anderen entstehen bei der Chlorierung chlorhaltige Nebenprodukte mit niedrigem Siedepunkt, die dem zu erzeugenden Alkohol hartnäckig durch die Destillation folgen. Dadurch tritt eine Beeinflussung der Qualität des aus der Destillation gewonnenen Alkohols auf, die nicht tragbar ist.It can also be observed that in the Chlorination to a noticeable extent side reactions occur. Some of these are dehydration processes, their products either directly or after condensation in the intermediate Alkali wash get into the distillation and contaminate it in a confusing way. On the other hand Chlorination results in chlorine-containing by-products with a low boiling point, which lead to stubbornly following the producing alcohol through the distillation. This affects the quality of the alcohol obtained from the distillation, which is unsustainable.
Verfahren zur Reinigung gesättigter AlkoholeProcess for purifying saturated alcohols
Patentiert für:
Wacker-Chemie G. m. b. H.,
München 22, Prinzregentenstr. 22Patented for:
Wacker-Chemie G. mb H.,
Munich 22, Prinzregentenstr. 22nd
Als Erfinder benannt:Named as inventor:
Dr. Jobst Poßberg, Köln-Longerich; Hans Brunner, BurghausenDr. Jobst Poßberg, Cologne-Longerich; Hans Brunner, Burghausen
■ 2 ■ . ' '■ 2 ■. ''
Es wurde nun ein Verfahren gefunden, mit dem es gelingt, sämtliche bei der Doppelbindungschlorierung mit saurer, wäßriger Hypochloritlösung auftretenden Nebenreaktionen zu unterdrücken. Das Verfahren, kann kontinuierlich oder absatzweise durchgeführt werden.A process has now been found with which it is possible to achieve all of the double bond chlorination to suppress side reactions occurring with acidic, aqueous hypochlorite solution. The Process, can be carried out continuously or batchwise.
Die vorliegende Erfindung betrifft daher ein Verfahren' zur Reinigung von gesättigten Alkoholen unter Verwendung einer wäßrigen, säurehaltigen Hypochloritlösung und ist dadurch gekennzeichnet, daß in einem pH-Bereich der wäßrigen Phase von 3,5 bis 5 gearbeitet und weniger als die stöchiometrisch erforderliche Säuremenge zugesetzt wird.The present invention therefore relates to a method ' for the purification of saturated alcohols using an aqueous, acidic Hypochlorite solution and is characterized in that in a pH range of the aqueous phase from 3.5 to 5 worked and less than the stoichiometrically required amount of acid is added.
Während die Hypochloritmenge ihrerseits im allgemeinen stöchiometrisch auf die im Rohalkohpl vorhandene Doppelbindungsmenge abgestimmt wird, ist eine Säuremenge von vorzugsweise 40 bis 70% des stöchiometrisch errechneten Bedarfs, bezogen auf die anwesende Hypochloritmenge, ausreichend. Unter diesen Bedingungen beschränkt sich der Angriff des freigesetzten Chlors ausschließlich auf die Chlorierung der Doppelbindung, und es treten keinerlei unerwünschte Nebenerscheinungen ein. Die Destillation eines so vorbehandelten Produktes ergibt einen Alkohol, der höchsten Qualitätsansprüchen genügt. Er ist nicht nur weitgehend frei von olefinisch ungesättigten Verbindungen. Unerwarteterweise zeigt sich auch, daß der Gehalt an sonstigen Verunreinigungen, wie z. B. Aldehyden, nach einer derartigen Behandlung des Rohproduktes im Destillat ungewöhnlich niedrig liegt. Auch tritt bei einer Arbeitsweise mit unterstöchiometrischer Säurezugabe, bei welcher der pH-Wert der wäßrigen Phase zwischen 3,5 und 5,0 liegt, in destilliertem Reinalkohol praktisch kein organisch gebundenes Chlor auf.While the amount of hypochlorite in turn is generally stoichiometric to that in the Rohalkohpl existing amount of double bonds is matched, an amount of acid of preferably 40 to 70% of the stoichiometrically calculated requirement, based on the amount of hypochlorite present, sufficient. Under Under these conditions, the attack of the released chlorine is limited exclusively to the chlorination the double bond, and there are no undesirable side effects. The distillation a product pretreated in this way results in an alcohol that meets the highest quality standards. Not only is it largely free of olefinically unsaturated substances Links. Unexpectedly it also shows that the content of other impurities, such as B. aldehydes, after such a treatment of the crude product in the distillate unusually low located. Also occurs when working with substoichiometric Acid addition at which the pH of the aqueous phase is between 3.5 and 5.0, there is practically no organically bound chlorine in distilled pure alcohol.
. 709 724/214. 709 724/214
Claims (1)
Einrichtungen für die kontinuierliche Zugabe von 35 Nach Schichtentrennung des erhaltenen Produktes Hypochloritlösung und verdünnter Schwefelsäure und azeotroper Entwässerung der organischen Phase sowie zur Messung des Redoxpotentials und des wurde in diskontinuierlicher Destillation ein Produkt pH-Wertes der Lösung. Die Verweilzeit des Roh- erhalten, das folgende Analysenwerte aufwies:
butanols in diesem Behälter betrug weniger als . , ' . ,
1 Stunde. Der Ablauf wurde nach einer kontinuier- 40 -Olefinische Doppelbindung 151 ppm
liehen Laugebehandlung einem Schichtenscheider zu- . - (gerechnet als C8-Alkohol)The crude butanol pretreated in this way was then added to the required sulfuric acid, whereby an amount of 1.01 / hour. at a continuous pH of about 4 was maintained. The HypoBetrieb is fed to the cleaning device. This chlorite was used in a stoichiometric amount, based on a container with a pump, based on the double bond present.
Equipment for the continuous addition of hypochlorite solution and dilute sulfuric acid and azeotropic dehydration of the organic phase as well as for measuring the redox potential and the pH value of the solution became a product in discontinuous distillation. The residence time of the raw material, which had the following analytical values:
butanols in this container was less than. , '. ,
1 hour. The flow was 151 ppm after a continuous 40 -olefinic double bond
lent lye treatment to a layer separator. - (calculated as C 8 alcohol)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEW37716A DE1243663B (en) | 1964-10-09 | 1964-10-09 | Process for the purification of saturated alcohols |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEW37716A DE1243663B (en) | 1964-10-09 | 1964-10-09 | Process for the purification of saturated alcohols |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1243663B true DE1243663B (en) | 1967-07-06 |
Family
ID=7601569
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEW37716A Pending DE1243663B (en) | 1964-10-09 | 1964-10-09 | Process for the purification of saturated alcohols |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1243663B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4089886A (en) * | 1977-07-21 | 1978-05-16 | Celanese Corporation | Methanol purification |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE812425C (en) * | 1949-02-24 | 1951-08-30 | Hellmuth Holz Dr | Process for the removal of water-insoluble organic impurities from aqueous solutions of organic solvents |
| DE1014975B (en) * | 1954-11-24 | 1957-09-05 | Ici Ltd | Process for cleaning glycol |
-
1964
- 1964-10-09 DE DEW37716A patent/DE1243663B/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE812425C (en) * | 1949-02-24 | 1951-08-30 | Hellmuth Holz Dr | Process for the removal of water-insoluble organic impurities from aqueous solutions of organic solvents |
| DE1014975B (en) * | 1954-11-24 | 1957-09-05 | Ici Ltd | Process for cleaning glycol |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4089886A (en) * | 1977-07-21 | 1978-05-16 | Celanese Corporation | Methanol purification |
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