Depolimerizacion quimica del

PET con KOH

UNI mayo 2007

 Reciclado Químico PET

 Paszun, D.; Spychaj, T. Chemical Recycling of Poly(ethylene

terephthalate). Ind. Eng. Chem. Res. 1997 4) Cudmore, W. J. G.
Polyethylene Terephthalate Saponification.
 U.S. Patent 4,578,502, 1986. (5) Doerr, M. L. Process for
Minimizing Formation of Low Molecular Weight Oligomers during
Hydrolytic Depolymerization of Condensation Polymers. U.S.
Patent 4,578,510, 1986.
 (6) Rosen, B. I. Preparation of Purified Terephthalic Acid from
Waste Polyethylene Terephthalate. U.S. Patent 5,095,145, 1992.

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 Reciclado Químico PET

 The difficulties of recycling P.E.T.-type polyesters are due mainly to the coloring and
to the foreign substances that are found mixed, with these products, and to the
difficulty of elimination of the water marks in the recycled product.
 One of the best forms of recovery is a depolymerization and recovery from
terephthalic acid and glycol in the form of raw materials that can result in new
polyesters of the same purity as the products produced from new raw materials.
 The breakdown of the P.E.T. and of the polyesters having terephthalic acid as a
dibasic acid is described in the prior art as being performed in an aqueous soda
solution containing 3 to 20% by weight of soda, at a pressure of 1.38 to 2.07 MPa
(200 to 300 PSI) and at a temperature between 180.degree. and 320.degree. C.,
preferably between 210.degree. and 250.degree. C. (U.S. Pat. No. 3,317,519).
In batch installations, this process results in a considerable use of energy, and
requires a material that must withstand the pressure. The hydrolysis periods are
long, from 3 to 5 hours, and the amount of soda used is on the order of 1.5 in
comparison with the theory

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 Reciclado Químico PET

 The US Patnet 5354666 offres a process that involves reacting a polyol

polyterephthalate with an alkali metal or alkaline-earth metal hydroxide in the
absence of water or in the presence of water in an amount at most equal by weight
to that of the alkali metal or alkaline-earth metal hydroxide. The operation is
performed advantageously above 120.degree. C. The pressure is advantageously
equal to normal atmospheric pressure or close to it. There is no compelling
advantage to operating under pressure, the reaction speed already being elevated at
normal pressure. The reaction is generally fast, most often between 1 and 60
minutes, for example 15, minutes. The alkali metal or alkaline-earth metal hydroxide
can be used in stoichiometric proportion in relation to the polyterephthalate, i.e., in
the amount necessary to produce the desired salt. Although it is possible to produce
the monoacid terephthalate of the selected metal, it is preferred to produce the
terephthalate entirely salified, which requires two alkali metal atoms or one alkaline-
earth metal atom per terephthalic group present. It is also possible to perform the
operation with an excess or a deficiency of hydroxide, for example an excess or a
deficiency up to 50% or more. For example, it is possible to perform the operation
with 50 to 300% of the theoretical amount of hydroxide, preferably 50 to 150%. By
way of example, it is possible to use the hydroxides of sodium, potassium,
calcium, barium or magnesium, or the oxides of the same metals, by hydrating
them.

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 Reciclado Químico PET

 The US Patent 5354666 gives as example 1: 1178 kg of support of X-ray films of

glycol polyterephthalate, cleared of silver and of gelatin, are mixed cold with 500 kg
of soda at 100.degree. C. with agitation, then 100 liters of water are introduced into
the mixture. The mixture is distributed in a screw exchanger where the temperature
is 160.degree. C., the introduction speed being calculated so that the temperature of
160.degree. C. is reached at mid-course. The product is collected in an agitated
vessel in which the amount of water necessary to arrive at a final concentration of
30% by weight of disodic terephthalate is found. The solution is brought to
70.degree. C. and is extracted by 10% by weight of butanol. The extraction ended,
the juice is passed over a column of activated charcoal which eliminates the
remainder of the impurities and the bleached solution is then precipitated by addition
of sulfuric acid up to a pH of 2.5-3 and the terephthalic acid recovered (yield: 1000
kg) is appropriately washed and dried. Acid index 675; Ash 10 ppm; 5% solution in
dimethylformamide--color: alpha 10; Maximum H.sub.2 O 0.5% Purity: 99.9% .

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 Reciclado Químico PET

 The US Patent 5,395,858, 1995., ya se vió.

 The Us patent 5,045,122, profuce sla acido tereftalico dicolviendo el PET en una
solucion alcoholixca del hidróxido..
 En US Patent 5328982 Ester bonds are hydrolyzed in the conversion of substantially
amorphous polyesters to their monomeric components, by being contacted with a
mixture of (a) an alcohol, such as methanol, or glycol, (b) a polar aprotic solvent
such as N-methyl-pyrrolidone or dimethyl sulfoxide and (c) an alkoxide or hydroxide
such as sodium hydroxide. No es nuetsro proceso.

CINETICA DEPOLIMERIZACION CON SOLUCION ALCALINA

 In the past there were no detailed data available about product characterization and
reaction kinetics, which were necessary for developing the process of
depolymerization of PET in alkaline solutions.
 Trabajos previos concluyero que It was concluded in this study that potassium
hydroxide possessed better activity than sodium hydroxide for the depolymerization
of PET.

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 Reciclado Químico PET

 T Therefore, the detailed reaction kinetics of the PET depolymerization in a potassium

hydroxide solution was investigated using a pressurized autoclave in the present study.
The kinetic data under the reaction temperatures below the PET melting point were
obtained. Furthermore, the reaction kinetic models were discriminated
 mThe reactants of PET flakes, potassium hydroxide, and water were charged into the
reactor at room temperature and then heated directly to the temperatures specified for
conducting hydrolytic reactions. After the required time interval for the depolymerization
reaction was reached, the vessel was quickly removed from the heating mantle and
immersed in an ice bath. The temperature of the vessel was quenched to ambient
conditions so as to interrupt the progress of the PET hydrolysis. The residual flakes and
the alkaline solution were removed from the bomb and were separated by filtration. The
flakes were further washed, dried, and weighed.
• After the depolymerization reactions, the products of terephthalic potassium salt and
ethylene glycol, besides the unreacted potassium hydroxide, were dissolved in the
solution liquid phase. The liquids were separated from the solution by filtration. Sulfuric
acid was added into the filtrate to neutralize the potassium hydroxide. The solid TPA
was precipitated and was separated again by filtration. The solid product was further
washed by deionized water, dried at 80 °C, and ground until a fine owder was obtained.
The remaining liquid, mainly composed of water and ethylene glycol, was directly used
for analysis.

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