Classifications

• • 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
  • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J19/24—Stationary reactors without moving elements inside
  • B01J19/2455—Stationary reactors without moving elements inside provoking a loop type movement of the reactants
  • B01J19/2465—Stationary reactors without moving elements inside provoking a loop type movement of the reactants externally, i.e. the mixture leaving the vessel and subsequently re-entering it
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
  • B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
• • 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
  • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J19/24—Stationary reactors without moving elements inside
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/465—Preparation of carboxylic acid esters by oligomerisation
• • 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
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/00049—Controlling or regulating processes
  • B01J2219/00051—Controlling the temperature
  • B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
  • B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
  • B01J2219/00094—Jackets
• • 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
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/00049—Controlling or regulating processes
  • B01J2219/00182—Controlling or regulating processes controlling the level of reactants in the reactor vessel
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/10—Process efficiency

Definitions

• the present invention relates to a process for obtaining an oligomeric composition of lactic acid, said composition can be used to prepare in particular an oligomeric composition of lactic acid esters or alternatively for obtaining lactide which is the precursor of choice for obtaining polylactides used as biomaterials.
• lactic acid composition is intended to mean in particular any aqueous solution of lactic acid, whatever its method of production and its characteristics, said solution possibly, for example, having a dry matter (MS) and a purity of lactic acid. very variable.
• MS dry matter
• a purity of lactic acid very variable.
• These may in particular be commercial solutions with 50, 80, 88 or 90% dry matter, it being understood that such solutions are in fact mixtures of water, monomers, dimers and higher oligomers of Lactic acid.
• the transformation of the lactic acid composition into an oligomeric lactic acid composition is carried out by elimination of water which can advantageously be carried out by simple evaporation, in one or more stages, at a temperature ranging from 100 ° C to 170 ° C, at atmospheric pressure or under reduced pressure, until an oligomeric composition having an average degree of polymerization (DPM) of between 2 and 30 approximately and preferably ranging from 3 to 10.
• DPM average degree of polymerization
• obtaining an oligomeric composition having such a DPM has the advantage of providing (having) a limited water content and consequently facilitates its subsequent esterification.
• the DPM is calculated by the following formula:
• T corresponds to the mass of monomeric lactic acid (CH3-C ⁇ OHCOOH, 90.08 g / mole) contained in 100 g of oligomeric composition of lactic acid.
• This mass is determined after saponification (20 min at 100 ° C.) with excess sodium hydroxide, of a sample of determined weight (0.1 g to 0.3 g) of the oligomeric composition. After neutralization of the mixture
• This reaction is rapidly analyzed by the high performance liquid chromatography (HPLC) technique with refractometric detection. This analysis can be carried out on a cation exchange column of the “SHODEX SH 1011” type using N / 100 sulfuric acid as eluent.
• HPLC high performance liquid chromatography
• the determination of the lactic acid oligomers and their distribution in the lactic acid oligomeric composition can be carried out by GPC on a Shodex KF 802.5 column (300 mm ⁇ 8 mm) with THF at a flow rate of 1 ml / min before calibration.
• PE6 range: 14,500 to 350 daltons with refractonitric detection.
• the Applicant has found a continuous process for obtaining an oligomeric composition of lactic acid rich in dimer and in trimer, from a lactic acid composition by elimination of water from said lactic acid composition, characterized in that this elimination is carried out in an adiabatic reactor provided with a circulation loop equipped with heating means, that a lactic acid composition is continuously introduced into a reaction medium at the bottom of the vessel in circulation, said reaction medium being brought to a temperature ranging from 120 ° C to 180 ° C and, preferably ranging from 130 ° C to 150 ° C, and that the pure water is removed in vapor form.
• the oligomerization reactor is loaded at the start with a determined quantity of an oligomeric composition of lactic acid at the bottom of the tank obtained in particular by a batch process.
• the volume quantity introduced at the start can be between 20% and 80% of the volume of the reactor, and preferably close to 50%.
• the circulation of the reaction medium is advantageously ensured by a centrifugal pump placed on the circulation loop having an hourly flow making it possible to circulate between 20 and 100 times the reaction mass.
• the reaction medium is brought to a temperature as defined above by means of a heat exchanger placed on the circulation loop.
• the elimination of water according to the present invention is carried out at a pressure equal to or less than atmospheric pressure; It will generally operate under a pressure ranging from 100 mbar to 200 mbar.
• the water leaving the reactor in vapor form passes through a decongestion zone which may consist of a demister or a distillation column.
• a decongestion zone which may consist of a demister or a distillation column.
• lactic acid compositions called "industrial”, “technical”, “food” or “pharmaceutical” quality.
• a composition of lactic acid in water at 88% by weight of lactic acid will be used.
• the oligomerization can be carried out in the presence of a homogeneous acid catalyst such as H 2 SO 4 , H3PO, *, methane sulfonic acid, paratoluenesulforic acid, used in an amount by weight ranging from 0.1% to 1% relative to the amount of dry lactic acid.
• a homogeneous acid catalyst such as H 2 SO 4 , H3PO, *, methane sulfonic acid, paratoluenesulforic acid
• oligomeric lactic acid composition according to the present invention has a DPM ranging from 3 to 10.
• the method according to the present invention has the advantage of obtaining linear oligomers with a narrow distribution of molecular weights, without loss of raw material, that is to say with almost absence of lactic acid in the recovered water.
• This method can be implemented by means of a device as shown diagrammatically in FIG. 1.
• This device is characterized in that it comprises: - an adiabatic reactor (1) consisting of at least one distillation column element equipped with heating mantles (me), with a circulation loop (2) provided with a heat exchanger heat (3) and a centrifugal pump (4); a supply of lactic acid composition (5).
• an adiabatic reactor (1) consisting of at least one distillation column element equipped with heating mantles (me), with a circulation loop (2) provided with a heat exchanger heat (3) and a centrifugal pump (4); a supply of lactic acid composition (5).
• the water leaving the reactor (1) in vapor form is introduced into a decongestion zone (6) from which it leaves in (7) then passes through an exchanger (8) where it is condensed.
• the oligomeric composition of lactic acid comes out in (9).
• the reactor is equipped with a level regulator (10) by differential pressure measurement.
• the supply of lactic acid composition is immersed in the reaction medium loaded beforehand in the reactor.
• This process according to the invention has great flexibility.
• the speed of circulation of the reaction medium can be varied widely, which er ⁇ rame an excellent distribution of calories within the reaction medium and avoids overheating, which allows a narrow distribution of the molecular weights of the oligomers to be achieved.
• the decongestion zone makes it possible to reduce the rate of evaporation of lactic acid, which makes it possible to ensure the productivity of the industrial process.
• the oligomerization reactor (1) consists of 2 distillation column elements (height: 0.8 meters, diameter: 180 mm) equipped with their heating mantles (e) to ensure the system's suitability.
• the reaction medium is circulated by a centrifugal pump (4) delivering 1 m3 / h, which reaction medium passes through an electric exchanger (3) with a surface area of 0.15 m 2 and delivering a maximum heating power equal to 6 kW.
• the reactor is equipped with a level regulator (10) by differential pressure measurement with nitrogen injection.
• the reactor is filled to 50% of its volume.
• the removed water passes through a distillation column element (6) of 4 theoretical plates and is recovered after condensation in a condenser (8) with an area equal to 1 m 2 .
• Starting lactic acid It has a total lactic acid content - LAT - of 88.7 and a free water content of 13.3%.
• the LAT corresponds to the T of the formula (1) mentioned above.
• the mass of monomeric lactic acid T contained in 100 g of oligomeric lactic acid compositions is determined according to the method described above.
• the temperature of the reactor is approximately 133 ° C., one begins to introduce 6.2 kg / h of the lactic acid composition into the reaction medium previously obtained.
• the pressure is maintained at 100 mbar.
• the water is recovered at an average flow rate of 1.6 kg / h.
• the oligomer is taken from the centrifugal pump (4) at a flow rate of 4.6 kg / h.
• the oligomer production was carried out for 50 hours.
• Example 2 (not in accordance with the invention): In a reactor identical to that of Example 1, but the introduction of lactic acid takes place in the headspace of the reactor, and the water elimination circuit is direct, that is to say does not include column (6) of 4 theoretical plates. We work identically. When the reactor temperature reaches 133 ° C, lactic acid is introduced at a rate of 6.26 kg / h. The water is recovered at a flow rate of 1.88 kg / h, and the oligomer at a flow rate of 4.38 kg / h grading 115% LAT. It can be seen that the aqueous stream contains approximately 18% of entrained lactic acid.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)

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• 2002
  • 2002-02-08 FR FR0201549A patent/FR2835832B1/fr not_active Expired - Fee Related
• 2003
  • 2003-01-31 KR KR10-2004-7012270A patent/KR20040089610A/ko not_active Application Discontinuation
  • 2003-01-31 WO PCT/FR2003/000305 patent/WO2003066187A1/fr active Application Filing
  • 2003-01-31 BR BRPI0307487A patent/BRPI0307487A2/pt not_active IP Right Cessation
  • 2003-01-31 MX MXPA04007669A patent/MXPA04007669A/es active IP Right Grant
  • 2003-01-31 CN CNA200610055069XA patent/CN1846825A/zh active Pending
  • 2003-01-31 US US10/503,375 patent/US20050080201A1/en not_active Abandoned
  • 2003-01-31 CN CNA038035790A patent/CN1630545A/zh active Pending
  • 2003-01-31 EP EP03717364A patent/EP1476237A1/fr not_active Withdrawn
  • 2003-01-31 AU AU2003222349A patent/AU2003222349A1/en not_active Abandoned
  • 2003-01-31 JP JP2003565607A patent/JP2005516999A/ja not_active Abandoned
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