EP0975563A1 - Entfernung von polymerisierungsinhibitoren aus mischungen von monomeren mittels dotierten aluminiumoxids - Google Patents

Entfernung von polymerisierungsinhibitoren aus mischungen von monomeren mittels dotierten aluminiumoxids

Info

Publication number
EP0975563A1
EP0975563A1 EP98902067A EP98902067A EP0975563A1 EP 0975563 A1 EP0975563 A1 EP 0975563A1 EP 98902067 A EP98902067 A EP 98902067A EP 98902067 A EP98902067 A EP 98902067A EP 0975563 A1 EP0975563 A1 EP 0975563A1
Authority
EP
European Patent Office
Prior art keywords
alumina
compound
alkaline
inhibitor
inhibitors
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.)
Withdrawn
Application number
EP98902067A
Other languages
English (en)
French (fr)
Inventor
Christophe Nedez
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.)
Rhodia Chimie SAS
Original Assignee
Rhodia Chimie SAS
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 Rhodia Chimie SAS filed Critical Rhodia Chimie SAS
Publication of EP0975563A1 publication Critical patent/EP0975563A1/de
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B63/00—Purification; Separation; Stabilisation; Use of additives

Definitions

  • the present invention relates to a new process for eliminating polymerization inhibitors from mixtures of monomers, in particular ethylenically unsaturated monomers.
  • ethylenic monomers In the polymerization industry for a large number of ethylenic monomers, an important problem relates to the storage and / or transport of these monomers. Indeed, one can observe an uncontrolled spontaneous polymerization of these monomers over time from free radicals.
  • polymerization inhibitors can be chosen from: picric acid, nitroaromatics, quinone derivatives (hydroquinone, benzoquinone), naphthols, amines (p-phenylenediamine, phenothiazine), phosphites, p-methoxyphenol, p- tertiobutylcatechol, ...
  • the inhibitor can be removed by adding a dilute solution, for example sodium hydroxide, the charge of monomers then being washed with water in order to remove all traces of caustic compounds, however, the treatment of liquid effluents also poses industrial problems,
  • a dilute solution for example sodium hydroxide
  • the inhibitor can be adsorbed using a compound such as alumina, silica gel, activated charcoal, calcium oxide, aluminum silicate, talc, sulfates of calcium, magnesium sulfates, copper sulfates, magnesium silicate clays, a resin ...
  • a compound such as alumina, silica gel, activated charcoal, calcium oxide, aluminum silicate, talc, sulfates of calcium, magnesium sulfates, copper sulfates, magnesium silicate clays, a resin ...
  • Adsorption is one of the most advantageous methods, since it does not have any of the disadvantages mentioned above.
  • activated alumina is preferred.
  • the object of the present invention is to provide a new alumina for the adsorption of polymerization inhibitors of ethylenically unsaturated monomers having improved adsorption capacities compared to the aluminas of the prior art.
  • the invention relates to a process for the adsorption of inhibitors of polymerization of ethylenically unsaturated monomers, in which these inhibitors are brought into contact with an alumina comprising at least one compound of an element chosen from the group formed by alkaline, alkaline earth and rare earth elements, the alkaline and alkaline earth elements being present in a content of at least 15 mmol per 100 g of alumina, and the rare earth elements in a content of at least 5 mmoles per 100 g of alumina.
  • these elements are present in a content of at most 400 mmol per 100 g of alumina, even more preferably of at most 300 mmol.
  • the content of alkaline and / or alkaline-earth elements is between 25 and 300 mmol per 100 g of alumina.
  • the alumina comprises at least one compound of one of the following elements: sodium, potassium, lithium, lanthanum and cerium.
  • This element compound can be an oxide, a hydroxide, a salt or a mixture thereof.
  • sulfates, nitrates, halides, acetates, formates, carbonates and the salts of carboxylic acids there may be mentioned, by way of example, sulfates, nitrates, halides, acetates, formates, carbonates and the salts of carboxylic acids.
  • the preferred compounds are hydroxides, nitrates and carbonates.
  • the alumina comprises a sodium compound in a content of between 15 and 250 mmol per 100 g of alumina, very particularly between 25 and 250 mmol per 100 g of alumina.
  • Alumina as suitable in the process according to the invention include aluminas having a sufficient surface area to achieve a high adsorption rate of polymerization inhibitors. Typically, these aluminas have a specific surface of at least 30 m 2 / g.
  • An alumina obtained from the treatment with the doping element of an alumina obtained by conventional methods such as the precipitation or gel method and the method for rapid dehydration of an aluminum hydroxide is used in the method according to the invention.
  • the deposition of the compound of the doping element on or in alumina can be carried out by any method known to those skilled in the art. It can be carried out, for example, by impregnation of the alumina already prepared with the alkaline elements, of rare earths or alkaline-earth or precursors of these elements, or by mixing of the alkaline elements, of rare earths or alkaline-earth or precursors with alumina during the shaping of these materials. These elements can also be introduced into alumina by coprecipitation of alumina and alkaline, rare earth or alkaline-earth elements or their precursors.
  • the alumina used in the process according to the invention is prepared by:
  • the impregnation is carried out in a known manner by bringing the alumina into contact with a solution, a sol or a gel comprising at least one alkaline element, of rare earths or alkaline earths in the form of oxide or salt or one of their precursors.
  • the operation is generally carried out by soaking the alumina in a determined volume of solution of at least one precursor of an alkaline element, of rare earths or alkaline earth elements.
  • solution of a precursor of one of these elements is meant a solution of a salt or compound of the element, or of at least one, of the alkaline, rare earth or alkaline-earth elements, these salts and compounds which may be thermally decomposable into oxides.
  • the salt concentration of the solution is chosen according to the quantity of element to be deposited on the alumina. According to a preferred mode, these elements are deposited by dry impregnation, that is to say that the impregnation is done with just the volume of solution necessary for said impregnation, without excess.
  • the heat treatment is carried out at a temperature determined as a function either of the temperature of use of the alumina or of the specific surface desired. It may also be possible to carry out a heat treatment to obtain at least partial thermal degradation of the compound, for example in the form of oxide. However, this degradation is not compulsory, and by way of example, it is not necessary in particular when using compounds such as chlorides, nitrates or hydroxides.
  • the heat treatment can, for example, be carried out at a temperature between 150 and 1000 ° C, preferably between 300 and 800 ° C.
  • the adsorption process according to the invention is suitable when the polymerization inhibitor is chosen, for example, from: picric acid, nitroaromatics, quinone derivatives (hydroquinone, benzoquinone), naphthols, amines (p - phenylenediamine, phenothiazine), phosphites, p-methoxyphenol, p-tertiobutylcatechol. Particularly good results are obtained for the adsorption of p-tertiobutyicatechol.
  • the alumina is brought into contact with said mixture of ethylenically unsaturated monomer and inhibitor, for example at room temperature.
  • the monomer charge can be based on any type of ethylenically unsaturated monomer such as in particular: styrene, butadiene, isoprene, vinyl chloride, vinylidene chloride, tetrafluoroethylene, trifluorochlorethylene, chloroprene, allyl alcohol, vinyl ether, vinyl ester (acetate of vinyl), alkyl acrylates and methacrylates (methacrylate, butylacrylate, ethylacrylate, 2-ethylhexyiacrylate, methylmethacrylate, ethylmethacrylate, 2-ethylhexylmethacrylate, ...), acrolein, acrylonitrile, acrylamide, amine vinyl.
  • the mixture of ethylenically unsaturated monomer and inhibitor comprises 2 to 2000 ppm by weight per volume of inhibitor, preferably 5 to 1500 ppm.
  • This alumina has an intrinsic sodium level of 11 mmoles of Na per 100 g of alumina.
  • This starting alumina is impregnated with sodium at different rates.
  • the impregnation is carried out dry using a sodium hydroxide solution.
  • the impregnated alumina is then dried overnight at 130 ° C, then calcined at 470 ° C for 2 hours.
  • This starting alumina is also impregnated with potassium at different rates.
  • the impregnation is carried out dry using a solution of potassium carbonate.
  • the impregnated alumina is then dried overnight at 130 ° C., then calcined at 470 ° C. for 1 hour 30 minutes.
  • the starting alumina is also impregnated with lithium at different rates.
  • Impregnation is carried out dry using a lithium nitrate solution.
  • the impregnated alumina is then dried overnight at 130 ° C., then calcined at 470 ° C. for 1 hour 30 minutes.
  • the starting alumina is also impregnated with cerium at different rates.
  • the impregnation is carried out dry using a solution of cerium nitrate.
  • the impregnated alumina is then dried overnight at 130 ° C, then calcined at 450 ° C for 2 hours.
  • the starting alumina is also impregnated with lanthanum at different rates.
  • the impregnation is carried out dry using a lanthanum nitrate solution.
  • the impregnated alumina is then dried overnight at 130 ° C, then calcined at 450 ° C for 2 hours.
  • alumina samples tested are pretreated under a stream of nitrogen air at 300 ° C for 2 hours in order to remove any trace of moisture after their storage and in order to be able to compare their effectiveness under identical conditions.
  • 1 g of alumina (dry extract) thus pretreated is introduced into 200 ml of a cyclohexane solution containing 500 ppm (w / v) of p-tertiobutylcatechol (TBC).
  • TBC p-tertiobutylcatechol

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
EP98902067A 1997-01-22 1998-01-13 Entfernung von polymerisierungsinhibitoren aus mischungen von monomeren mittels dotierten aluminiumoxids Withdrawn EP0975563A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9700624A FR2758553B1 (fr) 1997-01-22 1997-01-22 Procede d'elimination d'inhibiteurs de polymerisation de melanges de monomeres a l'aide d'une alumine dopee
FR9700624 1997-01-22
PCT/FR1998/000052 WO1998032716A1 (fr) 1997-01-22 1998-01-13 Procede d'elimination d'inhibiteurs de polymerisation de melanges de monomeres a l'aide d'une alumine dopee

Publications (1)

Publication Number Publication Date
EP0975563A1 true EP0975563A1 (de) 2000-02-02

Family

ID=9502847

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98902067A Withdrawn EP0975563A1 (de) 1997-01-22 1998-01-13 Entfernung von polymerisierungsinhibitoren aus mischungen von monomeren mittels dotierten aluminiumoxids

Country Status (9)

Country Link
EP (1) EP0975563A1 (de)
JP (1) JP2000508348A (de)
KR (1) KR20000070329A (de)
CN (1) CN1248235A (de)
AU (1) AU5870698A (de)
BR (1) BR9806987A (de)
FR (1) FR2758553B1 (de)
NO (1) NO993556L (de)
WO (1) WO1998032716A1 (de)

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3240830A (en) * 1962-05-04 1966-03-15 Phillips Petroleum Co Separation of inhibitor and water from monomeric materials
FR1361512A (fr) * 1963-04-11 1964-05-22 Electrochimie Soc Procédé de purification de produits éthyléniques facilement polymerisables
IT1245845B (it) * 1990-09-17 1994-10-25 Montedipe Srl Processo per la depurazione di un monomero vinilaromatico.

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9832716A1 *

Also Published As

Publication number Publication date
BR9806987A (pt) 2000-03-14
AU5870698A (en) 1998-08-18
NO993556L (no) 1999-09-20
FR2758553A1 (fr) 1998-07-24
CN1248235A (zh) 2000-03-22
WO1998032716A1 (fr) 1998-07-30
NO993556D0 (no) 1999-07-20
JP2000508348A (ja) 2000-07-04
KR20000070329A (ko) 2000-11-25
FR2758553B1 (fr) 1999-04-16

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