EP0851849A1 - Procede de separation de solides contenus dans des solutions aqueuses de 1,4-butynediol - Google Patents

Procede de separation de solides contenus dans des solutions aqueuses de 1,4-butynediol

Info

Publication number
EP0851849A1
EP0851849A1 EP96946351A EP96946351A EP0851849A1 EP 0851849 A1 EP0851849 A1 EP 0851849A1 EP 96946351 A EP96946351 A EP 96946351A EP 96946351 A EP96946351 A EP 96946351A EP 0851849 A1 EP0851849 A1 EP 0851849A1
Authority
EP
European Patent Office
Prior art keywords
butynediol
aqueous
solvent
solids
column
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.)
Ceased
Application number
EP96946351A
Other languages
German (de)
English (en)
Inventor
Gerald Flood
Gerald Klossek
Wernfried Vondung
Edmund Klausmann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP0851849A1 publication Critical patent/EP0851849A1/fr
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • C07C29/86—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by liquid-liquid treatment
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C33/04—Acyclic alcohols with carbon-to-carbon triple bonds
    • C07C33/042—Acyclic alcohols with carbon-to-carbon triple bonds with only one triple bond
    • C07C33/044—Alkynediols
    • C07C33/046—Butynediols

Definitions

  • the present invention relates to a method for separating solids from aqueous 1,4-butynediol solutions.
  • 1,4-butynediol is produced on an industrial scale from acetylene and aqueous formaldehyde solution on copper contacts (Weissmel, Arpe, Industrial Organic Chemistry, 2nd edition, Verlag Chemie, p. 94). Butynediol is an important intermediate from which 1,4-butanediol can be prepared by hydrogenation, which is used as an alcohol component in polyesters and can be converted to tetrahydrofuran by ring closure.
  • butynediol is obtained as an aqueous solution that contains small amounts of solids. Side reactions in the production of butynediol between CO 2 and formaldehyde or other intermediate stages of the reaction lead to the formation of red-colored polymers which are insoluble in aqueous butynediol solution.
  • the polymeric solid covers all parts of the plant, such as tube walls and reactor walls, with a film that is mechanically difficult to remove.
  • the polymeric solid remains suspended, its sedimentation is uneconomical in view of the low concentration, especially since the addition of sedimentation aids is prohibited because of subsequent process steps on highly selective catalysts, since these have a negative effect on the selectivity of the catalysts.
  • the butynediol solution also contains solid particles which can be attributed to the abrasion of the catalyst.
  • the amount of catalyst wear is generally 20 to 80% by weight of the solid in the aqueous solution.
  • the concentration of the solid in the aqueous butynediol solution is about 1 to 1000 ppm.
  • the catalyst wear leads to mechanical problems, particularly in pumps.
  • the solids mentioned prove the catalyst for the hydrogenation, which generally follows the butynediol production, to give butene or butanediol.
  • the solid can only be removed by time-consuming and costly shutdown of plants and mechanical cleaning of affected plant parts. It was therefore an object of the present invention to provide a process which allows solids to be separated economically from aqueous 1,4-butynediol solutions.
  • the process should be usable on an industrial scale. In particular, it should be suitable to remove low-concentration solids.
  • a process for the separation of solids from aqueous butynediol solutions which is characterized in that a solids-containing aqueous butynediol solution is trickled through a column and brought into contact with a solvent which has a lower density than the solids-containing butynediol solution and with this forms a second phase, the solvent rising in countercurrent to the aqueous butynediol solution, the solid accumulating at the interface between the aqueous butynediol and the solvent, and the solid being removed from the column by removing a mixture of aqueous butynediol and solvent away.
  • aqueous butynediol solutions to be used according to the invention have a butynediol content which can vary within wide limits. In general, it is 25 to 75% by weight, preferably 40 to 60% by weight and particularly preferably 45 to 55% by weight.
  • the solids content of the aqueous butynediol solution used is generally between 1 and 1000 ppm, but in individual cases it can also be significantly higher, e.g. up to 5% by weight.
  • the process according to the invention is particularly advantageous for solids contents of 2 to 500 ppm.
  • the solid is separated off in a column, which includes all those apparatuses in which the butynediol solution can be passed from top to bottom (trickle mode) in countercurrent to the solvent.
  • a column which includes all those apparatuses in which the butynediol solution can be passed from top to bottom (trickle mode) in countercurrent to the solvent.
  • glass columns such as those used for chromatography, come into consideration;
  • metal columns in particular come into consideration.
  • the butynediol solution to be purified is preferably added laterally to the upper part of the column.
  • Conventional distributor internals such as pipe distributors have proven themselves for uniform distribution in the column.
  • the butynediol solution is generally added to the column in such a way that the flow rate in the column is 0.1 to 0.4 m / min.
  • the butynediol solution is brought into contact with a solvent which has a lower density than the butynediol solution and forms a second phase with it.
  • the solvents do not have to be completely immiscible with the butynediol solution to be cleaned.
  • Preferred solvents are those which dissolve no more than 10% by weight, particularly preferably no more than 3% by weight, in the butynediol solution.
  • ethers such as methyl tert. butyl ether, ketones such as butyl methyl ketone, aromatic hydrocarbons such as benzene and aliphatic or cycloaliphatic hydrocarbons such as cyelohexane.
  • the butynediol solution is preferably brought into contact with a C 4 -C 16 alcohol, particularly preferably a C 6 -C 10 alcohol.
  • alkanols such as hexanol, heptanol, octanol,
  • 2-ethylhexanol and decanol can be considered, where the alkanols can be straight-chain or branched and these can also be used in the form of isomer mixtures.
  • the solvent is preferably introduced into the lower part of the column, with manifold internals having proven successful, as with the butynediol solution.
  • the flow rate of the solvent in the column is generally chosen so that it is 0.15 to 0.4 m / min.
  • the ratio of the volumes of the aqueous butynediol solution and the solvent is generally 0.1: 1 to 10: 1, preferably 0.5: 1 to 3.5: 1.
  • the column can be operated at 0 to 100 ° C., preferably at 20 to 50 ° C.
  • packed columns are preferably used.
  • the packing is arranged between the feed lines of the butynediol solution and the solvent.
  • ceramic rings, metal rings, pall rings and Raschig rings can be considered as fillers.
  • the solvent rises in the column.
  • the solid is enriched at the interface between drops of the aqueous butynediol solution and the solvent.
  • a solvent phase forms at the top of the column.
  • the solid is strongly enriched at the interface of the solvent phase at the top of the column with the butynediol solution.
  • a mixture of solid, butynediol and solvent is therefore advantageously drawn off at this interface and the solid is thus removed.
  • the solvent is advantageously removed from the column via an overflow and returned to the process.
  • the height of the interface between the butynediol solution and the solvent in the column can be regulated by regulating the outflow of the butynediol solution at the bottom of the column.
  • the mixture containing the enriched solid is withdrawn from the column and placed in a separation container.
  • the solvent can be removed from the separation container and returned to the column.
  • the solid in the separation container in the butynediol solution is so strongly enriched that it can be separated using methods known per se, such as filtration, centrifugation or evaporation of the liquid, preferably by sedimentation.
  • the remaining butynediol solution can be returned to the column or processed further.
  • the process according to the invention also removes low-concentration solids from aqueous butynediol solutions in an economical manner.
  • a column (15 cm in diameter in Examples 1-11, 30 cm in Examples 12-15) with a packing of 15 mm ceramic rings in Examples 1-11 and 2.5 cm metal rings in Examples 12 to 15 was continuously used aqueous, 50 wt. % butin diol solution charged above the packing, n-octanol in Examples 1-11 and 14 and 15 and n-decanol in Examples 12 and 13 were added to the column below the packing.
  • n-octanol in Examples 1-11 and 14 and 15 and n-decanol in Examples 12 and 13 were added to the column below the packing.
  • 0.5% by weight of the fed-in butynediol solution in the form of a mixture of alcohol, butynediol solution and solid was removed from the column.
  • the alcohol was discharged from the column via an overflow.
  • the table gives further parameters of the separation attempts.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Indole Compounds (AREA)
  • Extraction Or Liquid Replacement (AREA)

Abstract

L'invention concerne un procédé de séparation de solides contenus dans des solutions aqueuses de butynediol. Une solution aqueuse de butynediol contenant des solides est guidée de façon à s'écouler à travers une colonne et est mise en contact avec un solvant dont la densité est inférieure à celle de la solution de butynediol contenant les solides et qui forme une seconde phase avec ladite solution de butynediol. Le solvant monte à contre-courant de la solution aqueuse de butynediol. Le solide s'enrichit au niveau de l'interface entre le butynediol et le solvant. Le solide est extrait de la colonne par élimination d'un mélange de diol aqueux de butynediol et de solvant.
EP96946351A 1995-09-23 1996-09-13 Procede de separation de solides contenus dans des solutions aqueuses de 1,4-butynediol Ceased EP0851849A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE1995135450 DE19535450A1 (de) 1995-09-23 1995-09-23 Verfahren zur Abtrennung von Feststoffen aus wäßrigen 1,4-Butindiollösungen
DE19535450 1995-09-23
PCT/EP1996/004027 WO1997011044A1 (fr) 1995-09-23 1996-09-13 Procede de separation de solides contenus dans des solutions aqueuses de 1,4-butynediol

Publications (1)

Publication Number Publication Date
EP0851849A1 true EP0851849A1 (fr) 1998-07-08

Family

ID=7773011

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96946351A Ceased EP0851849A1 (fr) 1995-09-23 1996-09-13 Procede de separation de solides contenus dans des solutions aqueuses de 1,4-butynediol

Country Status (11)

Country Link
US (1) US5973213A (fr)
EP (1) EP0851849A1 (fr)
JP (1) JPH11513373A (fr)
KR (1) KR19990063656A (fr)
CN (1) CN1196717A (fr)
AU (1) AU7129496A (fr)
CA (1) CA2230118A1 (fr)
DE (1) DE19535450A1 (fr)
EA (1) EA000507B1 (fr)
MY (1) MY135760A (fr)
WO (1) WO1997011044A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102005042185A1 (de) * 2005-09-06 2007-03-08 Basf Ag Verfahren zur Abtrennung von polymeren Nebenprodukten aus 1,4-Butindiol
DE102005042184A1 (de) * 2005-09-06 2007-03-08 Basf Ag Verfahren zur Abtrennung von polymeren Nebenprodukten aus 1,4-Butindiol
EP2785672B1 (fr) 2011-11-28 2016-10-26 Invista Technologies S.à.r.l. Traitement caustique d'une alimentation de colonne de recyclage de formaldéhyde
CN104043385A (zh) * 2014-06-09 2014-09-17 新疆美克化工股份有限公司 一种b3d反应催化剂评价实验装置的反应釜

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2421407C2 (de) * 1974-05-03 1985-06-27 Basf Ag, 6700 Ludwigshafen Verfahren zur Herstellung von Butindiol
US4083882A (en) * 1976-08-26 1978-04-11 Celanese Corporation Production of 1,4-butanediol
US4127734A (en) * 1978-01-16 1978-11-28 E. I. Du Pont De Nemours And Company Preparation of butynediol using bismuth modified spheroidal malachite
US4180687A (en) * 1978-04-24 1979-12-25 E. I. Du Pont De Nemours And Company Reaction of formaldehyde in butynediol
US4294998A (en) * 1978-06-28 1981-10-13 E. I. Du Pont De Nemours And Company Preparation of high purity 1,4-butanediol
DE3561879D1 (en) * 1984-10-12 1988-04-21 Basf Ag Process for the production of alkane diols

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9711044A1 *

Also Published As

Publication number Publication date
KR19990063656A (ko) 1999-07-26
JPH11513373A (ja) 1999-11-16
CA2230118A1 (fr) 1997-03-27
EA199800323A1 (ru) 1998-10-29
DE19535450A1 (de) 1997-03-27
AU7129496A (en) 1997-04-09
WO1997011044A1 (fr) 1997-03-27
US5973213A (en) 1999-10-26
MY135760A (en) 2008-06-30
EA000507B1 (ru) 1999-10-28
CN1196717A (zh) 1998-10-21

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