US008231765B2

(12) United States Patent (10) Patent No.: US 8,231,765 B2

Amoros et al. (45) Date of Patent: Jul. 31, 2012

(54) PROCESS FOR THE PURIFICATION OF (56) References Cited

LACTAMIS
U.S. PATENT DOCUMENTS
(75) Inventors: Daniel Amoros, Venissieux (FR): 3,931,308 A * 1/1976 Sifniades ...................... 562,562
Philippe Leconte, Meyzieu (FR); Pierre 4,301,073. A 11/1981 Fuchs et al.
4,341,709 A 7, 1982 Hofen et al.
Coqueret, Francheville (FR) 4.457,807 A 7/1984 Rulkens et al.
4,720,328 A 1/1988 Corbinet al.
(73) Assignee: Rhodia Polyamide Intermediates, Saint 4,767,503 A * 8/1988 Crescentini et al. ............ 203/48
Fons (FR) 4,892,624 A 1/1990 Fuchs et al.
5,136,052 A 8/1992 Van Gysel et al.
5,241,066 A 8, 1993 Davis et al.
(*) Notice: Subject to any disclaimer, the term of this 5,458,740 A 10, 1995 Losier et al.
patent is extended or adjusted under 35 5,496.941 A 3, 1996 Ritz et al.
U.S.C. 154(b) by 488 days. 5,700,358 A 12/1997 Fuchs et al.
5,874,575 A * 2/1999 Fuchs et al. ................... 540,539
(21) Appl. No.: 12/155,065 (Continued)
(22) Filed: May 29, 2008 FOREIGN PATENT DOCUMENTS
DE 81846 5, 1971
(65) Prior Publication Data
(Continued)
US 2008/O23O368A1 Sep. 25, 2008
Primary Examiner — Virginia Manoharan
Related U.S. Application Data (74) Attorney, Agent, or Firm — SNR Denton US LLP
(62) Division of application No. 10/296.512, filed as (57) ABSTRACT
application No. PCT/FR01/01644 on May 28, 2001, A method and a plant are disclosed for purifying lactams,
now Pat. No. 7,384,518. particularly lactams obtained by cyclizing hydrolysis of ami
Foreign Application Priority Data nonitrile. The purification of e-caprolactam obtained by
(30) cyclizing hydrolysis of aminocapronitrile is described which
May 26, 2000 (FR) ...................................... OOO6784 includes eliminating the ammonia from the reaction medium
of the hydrolysis, then recovering the lactam from the
(51) Int. C. medium in purified form. The recovery is carried out by
BOID 3/34 (2006.01) performing at least a distillation of the lactam in the presence
CO7D 20/02 (2006.01)
of a base producing optionally a fronts fraction having com
CO7D 20/6 (2006.01)
pounds more Volatile than the lactam, a fraction having the
lactam to be recovered to the degree of desired purity and a
(52) U.S. Cl. ................ 203/35; 203/37; 203/43; 203/48; distillation tails having the lactam and compounds less Vola
203/72; 203/89; 203/98; 203/DIG. 25; 540/538; tile than the lactam. The distillation tails are treated by various
54O7540 processes such as evaporation in thin layers to recover the
(58) Field of Classification Search .................... 203/29, major part of the caprolactam and recycling the latter in the
203/34, 35, 37, 43,48, 72, 89,98, DIG. 25; purification process.
540/538,540
See application file for complete search history. 20 Claims, 2 Drawing Sheets

ra.
 US 8,231,765 B2
Page 2

U.S. PATENT DOCUMENTS DE 226,560 8, 1985

6,187,917 B1 2/2001 Mayer et al. DE 226,561 8, 1985
DE 226,562 8, 1985
6,635,151 B1 10/2003 Bocquenet et al. f
6,972,075 B2 12/2005 Luyken et al. DE 267 729 5, 1989
DE 19548 289 6, 1997
FOREIGN PATENT DOCUMENTS EP O 306874 3, 1989
DE 31 O6 350 12/1981 WO WO98/05636 2, 1998
DE 152914 12/1981 * cited by examiner
U.S. Patent Jul. 31, 2012 Sheet 1 of 2 US 8,231,765 B2
U.S. Patent Jul. 31, 2012 Sheet 2 of 2 US 8,231,765 B2

ŠA\ cy O
s

A d N
 US 8,231,765 B2
1. 2
PROCESS FOR THE PURIFICATION OF then a distillation in a basic medium. The distillation residue
LACTAMIS is treated to recover as much as possible of the caprolactam.
This treatment consists of further distillations and a treatment
The present application is a divisional of and claims pri with a strong acid of the caprolactamthus distilled before it is
ority under 35 U.S.C. S 120 to, U.S. patent application Ser. recycled in the extraction stage. This process makes it pos
No. 10/296,512, now U.S. Pat. No. 7,384,518, which was sible to improve the degree of recovery of the caprolactam but
filed on Jul. 30, 2003, which was a National Stage filing under requires the use of an acid for the treatment before recycling.
35 U.S.C. S371 of International Application No. PCT/FR01/ This recycling process is complex and requires a significant
01644, filed May 28, 2001, which claimed priority under 35 investment in order to carry out the acid treatment. Further
U.S.C. S 119 to Application No. 00/06784 filed in France on 10 more, this process cannot be transposed to the treatment of a
May 26, 2000. The entire contents of each of these applica caprolactam Synthesized by a novel reaction, which can gen
tions are hereby incorporated by reference in this application. erate entirely different impurities requiring novel purification
The invention relates more particularly to the purification processes.
ofe-caprolactam obtained by the cyclizing hydrolysis of ami One of the aims of the present invention is to overcome
nocapronitrile. 15 these disadvantages by providing a process and a plant for the
Several processes for the synthesis of e-caprolactam, a purification of a lactam resulting from the cyclizing hydroly
major chemical intermediate used in particular in the produc sis of an aminonitrile which make it possible to obtain a high
tion of polyamides and more particularly of polyamide-6, degree of recovery of lactam of high purity.
have been provided. One of the most widely used processes To this end, the invention provides a process for the puri
industrially consists of a Beckmann rearrangement of cyclo fication of lactam, more particularly of e-caprolactam,
hexanone oxime in the presence of sulphuric acidorofoleum. obtained by the cyclizing hydrolysis of an aminonitrile, more
Another process which forms the subject-matter of numer particularly of aminocapronitrile, which consists in removing
ous studies consists in obtaining e-caprolactam by the cycliz the ammonia from the hydrolysis reaction medium and in
ing hydrolysis of aminocapronitrile. This reaction, disclosed then recovering the lactam from the said medium in the puri
in French Patent 2 029 540, can be carried out in the liquid 25 fied form.
phase in the presence of Solvents and of catalysts or, as dis According to the invention, this recovery is carried out by
closed in U.S. Pat. No. 2.357,484, in the gas phase with employing at least one distillation of the lactam in the pres
alumina as catalyst. ence of a base, optionally producing a top fraction comprising
Patent EP 150295 also relates to a process for the cyclizing compounds which are more Volatile than the lactam, a frac
hydrolysis of aminocapronitrile in the gas phase in the pres 30 tion comprising the lactam to be recovered with the desired
ence of a catalyst based on copper and on Vanadium. degree of purity and a distillation bottom product comprising
The e-caprolactam obtained by these synthetic processes lactam and compounds which are less volatile than the lac
has to be purified in order to obtain a chemical intermediate or tam.
a monomer which makes it possible in particular to manufac Thus, the distillation bottom product or residue recovered
ture polymers exhibiting characteristics satisfactory for the 35 in the stage of purification by distillation predominantly com
manufacture of finished products, such as yarns, fibres, and prises lactam, the impurities being composed mainly of salts
the like. and of reaction by-products.
Numerous purification processes have been provided for This distillation bottom product is subjected, according to
the treatment of the caprolactam obtained by the Beckmann the invention, to a treatment which consists in separating most
rearrangement of cyclohexanone oxime. 40 of the lactam present in the distillation bottom product and in
Processes for the purification of the caprolactam obtained recycling the said separated lactam in any stage of the puri
by the cyclizing hydrolysis of aminocapronitrile have also fication process or in the medium obtained after the cyclizing
been provided. Thus, U.S. Pat. No. 5,496.941 discloses a hydrolysis.
process which consists in separating the products with low According to the invention, this treatment of the distillation
boiling points and the products with high boiling points from 45 bottom product consists either of a recovery of the lactamby,
the hydrolysis reaction medium. This separation is obtained for example, thin-layer evaporation of the lactam or crystal
in particular by distillation of the caprolactam. lization of the latter or of a separation of the lactam from the
The caprolactam thus recovered is subjected to a hydroge other impurities, for example by extraction of most of the
nation, then either to a treatment through ion-exchange resins impurities with water.
or to a distillation in the presence of Sulphuric acid, and, 50 The crystallization of the lactam can be carried out accord
finally, to a distillation in the presence of a base. ing to conventional crystallization processes with, as solvent,
Other purification processes have been provided. Thus, either water or an aqueous solution Saturated with lactam or
Patent WO 98/05636 provides a process for the purification the lactam itself. It is advantageously carried out in a single
by liquid/liquid extraction using a solvent with an acidic stage. However, if necessary, two or more crystallization
nature or by a treatment through resins. 55 stages can be employed.
In these processes, a final distillation of the caprolactam is A crystallization process and the conditions for its imple
generally provided in order to obtain a product which satisfies mentation are disclosed, for example, in Patents EP 943 608
the criteria of purity required, in particular for its use as and U.S. Pat. No. 4,882,430.
monomer in the manufacture of polyamides, such as polya The lactam thus obtained is recycled in the device for
mide-6. 60 distillation in a basic medium, either by direct feeding to the
However, this final distillation results in a high loss of distillation column at a predetermined level or by addition to
caprolactam, which is very harmful to the general economics the stream of reaction medium entering the said column, or at
of the process. another stage of the process for the purification and recovery
Thus, in the case of the purification of a caprolactam of the lactam or even in the medium resulting from the cycliz
obtained by the Beckmann rearrangement reaction, U.S. Pat. 65 ing hydrolysis.
No. 4.301.073 provides a process for purifying the caprolac According to a second embodiment of the invention, the
tam which comprises a stage of extraction by a solvent and distillation bottom product is treated in a thin-film or thin
 US 8,231,765 B2
3 4
layer evaporation process. The vaporized lactam is recycled distillation process comprising several distillation columns
in the distillation device under conditions similar to those of mounted in series in order to carry out the Successive separa
the embodiment employing the crystallization. The evapora tion of the various products.
tion of the lactam is obtained by heating at a temperature These plants for the implementation of the purification
between 130° C. and 150° C. under a pressure of less than 10 process by distillation in a basic medium oran acidic medium
mbar. and then a basic medium are also Subject-matters of the
Finally, in a third embodiment, the distillation bottom present invention.
product can be treated with water to dissolve the impurities, in In a first embodiment in accordance with the invention
particular the salts, the lactam recovered after separation by which is suitable for carrying out the treatment in a basic
settling advantageously being recycled in the process for the 10 medium of the lactam to be purified, the plant comprises a
purification of the lactam by distillation in an acidic medium first distillation column to which the lactam to be purified is
and then in a basic medium. fed with a predetermined amount of base. In this column,
These processes for the treatment of the distillation bottom known as the dehydration column, the water is removed in the
product make it possible to recover at least 90% by weight, form of a top fraction, the distillation bottom product, com
15 prising the lactam and the base, being fed to a second distil
advantageously at least 95%, of the lactam present in the said lation column.
bottom product. The losses of lactam in the purification pro In this second distillation column, the products which are
cess are thus restricted to less than 3% by weight of the more volatile than the lactam are removed in the form of a top
participating lactam. fraction and the separated lactam is fed to a third distillation
The process of the invention thus makes it possible to column.
restrict the losses of lactam to a very low level during the In this third column, the lactam is distilled and recovered as
purification by basic distillation. These losses have only a a top fraction, and the distillation bottom product can advan
very slight affect on the economics of the process and in tageously be treated according to the processes of the inven
particular the quality of the lactam recovered is of a very high tion in order to recover most of the lactam. The lactam recov
level. 25 ered from the distillation bottom product is advantageously
According to the invention, the medium comprising the recycled in the second distillation column.
lactam to be recovered can be the reaction medium for the According to a second embodiment in accordance with the
cyclizing hydrolysis of aminonitrile after evaporation of the invention, the plant also comprises three distillation columns
ammonia. The said reaction medium could be subjected to a mounted in series. The first columnis, as in the first embodi
hydrogenation before the evaporation of the ammonia. 30 ment, a dehydration column which makes it possible to
This reaction medium, participating in the basic distilla remove most, preferably all, of the water.
tion, may have been Subjected to several preliminary treat In the second column, the least volatile compounds, and in
ments after evaporation of the ammonia. particular less volatile than the lactam, are separated and
In an embodiment of the invention, the hydrolysis reaction constitute a distillation bottom product, and the lactam recov
medium is treated to remove the products which are respec
35 ered at the column top is fed to the third column.
In this final column, the purified lactam is collected in the
tively less volatile and more volatile than the lactam. This form, advantageously, of an intermediate fraction by with
treatment, disclosed in U.S. Pat. No. 5,496,941, consists in drawal, either in the vapour phase or in the liquid phase. The
evaporating the ammonia, the water and the other Volatile top fraction, composed of the compounds which are more
products and in then distilling the lactam. The hydrolysis 40 volatile than the lactam, is removed and the distillation bot
reaction medium treated by the basic distillation of the tom product is preferably recycled in the second column.
present invention will thus be the lactam recovered by distil In this embodiment, the distillation bottom product from
lation. the second column is advantageously treated in order to
In another embodiment, in particular when the cyclizing recover the lactam according to the process of the invention.
hydrolysis is carried out in the vapour phase, only the ammo 45 The lactam thus recovered is advantageously recycled in the
nia is extracted from the reaction medium, which may or may second column.
not have been subjected to a hydrogenation prior to the Preferably, the basic compound is added to the medium to
removal of the ammonia. be treated before it is fed to the first dehydration stage.
The lactam recovered by distillation or a ammonia-free However, the invention also relates to a process which
reaction medium can be subjected to a hydrogenation or an 50 consists in treating the medium comprising the lactam to be
oxidizing treatment, for example, before being fed to the purified by distillation in an acidic medium and more particu
basic distillation. larly in sulphuric acid medium, followed by distillation in a
In another embodiment, the process for the purification of basic medium. Such a treatmentis, according to the invention,
the lactam can comprise a treatment through an ion-exchange employed in a plant in accordance with the second embodi
resin in an acidic medium or a distillation in the presence of a 55 ment described above.
strong acid, for example Sulphuric acid. In this second embodiment, the acid is added to the
The process for the purification and recovery of the lactam medium to be treated before it is fed to the dehydration
can also comprise one or more Successive crystallizations of column, the base being added to the top fraction produced in
the lactam, the lactam thus crystallized forming the medium the second distillation column before it is fed to the third
fed to the basic distillation in accordance with the invention. 60 distillation column.
Consequently, the distillation process in accordance with The salts generated by the presence of the acid, for example
the invention is a stage in a lactam purification process which amine Sulphates or Sulphates originating from the neutraliza
can be combined with numerous other known treatments of tion of the base, are removed and bled off in the distillation
lactams used in the numerous disclosed purification pro bottom product produced in the second distillation column.
CCSSCS. 65 This distillation bottom product is advantageously Subjected
According to another characteristic of the invention, the to a lactam recovery treatment which, in the present case, can
purification process of the invention can be employed in a advantageously be:
 US 8,231,765 B2
5 6
either a washing of the distillation bottom product with lactam, for example a thin-film or thin-layer evaporation pro
water to dissolve the salts, such as ammonium and/or cess at a temperature of less than 150° C. and under a pressure
amine Sulphates, the organic phase, after separation of of between 5 and 10 mbar.
the aqueous phase and the organic phase composed of In another preferred embodiment of the invention, this
the lactam, preferably being recycled in the medium fed 5 distillation bottom product is subjected to a crystallization
to the dehydration column or recycled in the second process in order to recover the lactam, more particularly
column, or alternatively subjected to another treatment, caprolactam.
Such as thin-layer evaporation or crystallization, It is also possible to treat this distillation bottom product
or an evaporation of the lactam carried out in a thin-film or 10 with water in order to extract the salts, more particularly the
thin-layer evaporator, Sulphates, originating from the neutralization of the free bases
or a crystallization of the lactam from water, an aqueous present in the hydrolysis medium. The organic phase recov
ered, comprising the lactam, is either recycled in the dehy
lactam Solution or lactam.
These treatments can be combined, in particular the wash dration stage of
column or the second column, or Subjected to a further
separation of the lactam, Such as a thin-film or thin
ing with water can be carried out prior to the evaporation or 15 layer evaporation or a crystallization.
the crystallization. According to the invention, a base chosen from the group
According to a characteristic of the invention, the lactam is consisting of alkali metal hydroxides, alkaline earth metal
advantageously e-caprolactam obtained by the cyclizing hydroxides and metal carbonates, for example sodium
hydrolysis of aminocapronitrile either in the vapour phase or hydroxide, lithium hydroxide, potassium hydroxide, magne
in the liquid phase, with or without solvent. sium hydroxide, calcium hydroxide, Sodium carbonate, mag
The aminonitrile is, for example, produced by partial nesium carbonate, lithium carbonate or mixed carbonates,
hydrogenation of adiponitrile. This reaction is disclosed in can be used as basic compound. Preferably, an aqueous
particular in U.S. Pat. Nos. 4,601,859, 2,762,835, 2,208,598, sodium hydroxide solution is used. The amount of base added
DE 4235466 and U.S. Pat. No. 5,981,790. can vary within wide limits. Advantageously, it is between
The ammonia present in the cyclizing hydrolysis reaction 25 0.05 and 2 g of base per 1 kg of caprolactam or lactam.
medium is removed by distillation or flashing. As indicated above, this base is added either to the medium
The reaction medium fed in the process of the invention can to be treated fed to the dehydration stage or to the top fraction
comprise at least 99.9% by weight of lactam. This concentra resulting from the second column of the second embodiment
tion range is given only by way of indication. Thus, media of the plant, before it is fed to the third column.
comprising less lactam can also be purified by the process of 30 According to the invention, it is also possible to add an
the invention. acid, preferably sulphuric acid, to the medium fed to the
By way of nonlimiting indication, the operating conditions dehydration stage. The amount of acid added is determined as
of the various columns of the second embodiment of the plant to a function of the amount of free bases present in the medium
according to the invention are given below. be treated. This amount of free bases is determined by
35 potentiometric titration of the medium. The amount of acid
The first dehydration stage is carried out at a temperature of
between 100° C. and 130° C. approximately at a pressure of added is between 0.5 mol of acid per mole of free bases and
one mole of acid per mole of free bases, preferably between
between 50 mbar and 200 mbar approximately. 0.7 and 0.9 mol of acid per mole of free bases. This concen
The dehydrated fraction is fed to a second distillation col tration range makes it possible to obtain meltable salts and a
umn in which the second stage of separation of the products 40 weak corrosive action of the medium.
with high boiling point is carried out by production of a Other advantages and details of the invention will become
distillation bottom product. more clearly apparent in the light of the detailed description
The operating conditions of this column are a column of examples, made with reference to the appended figures, in
bottom temperature of less than 150° C. and a pressure of which:
between 5 and 10 mbar. 45 FIG. 1 represents a block diagram of a first embodiment of
The top fraction thus produced comprises less than 100 the plant of the invention, and
ppm of impurities with a higher boiling point than the lactam. FIG. 2 represents a block diagram of a second embodiment
This top fraction is fed to a further distillation column, the of the plant of the invention.
operating conditions of which are a column bottom tempera
ture of less than 150° C. and a pressure of between 5 and 10 50 EXAMPLE 1.
mbar.
The lactam, in particular e-caprolactam, produced as inter A medium resulting from the cyclizing hydrolysis of an
mediate fraction exhibits a degree of purity which satisfies the aminocapronitrile obtained by hemihydrogenation of adi
criteria required for polyamide manufacture, in particular for ponitrile was treated by hydrogenation before distillation
textile applications. Preferably, this intermediate fraction is 55 (stripping) of the ammonia. The resulting medium was
withdrawn in the vapour phase from the column in order to treated by passing through an ion-exchange resin. The con
obtain a very low concentration of products with a high boil ditions for carrying out these treatments are disclosed in the
ing point. However, it is also possible to withdraw this inter abovementioned patents or patent applications and in particu
mediate fraction in the liquid phase, without departing from lar in Patent Applications WO 98/05636 and FR 2786 180.
the scope of the invention. 60 This medium comprises approximately 65% by weight of
The distillation bottom product obtained in the column caprolactam and exhibits the following purity characteristics
bottom is recycled, in an embodiment of the invention, in the Permanganate number (PNo): 35
second distillation column. Content of volatile bases (N): 1.8 med/kg
In a preferred embodiment of the invention in accordance UV number (N): 0.5
with the process for the purification of the lactam of the 65 These characteristics are determined according to stan
invention, the distillation bottom product collected in the dardized procedures disclosed in Standard ISO 8660 for the
second column bottom is fed to a stage for separation of the permanganate number (PNo), Standard ISO 8661 for the
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7 8
content of volatile bases (N) and Standard ISO 7059 for the column 31 also operating under reflux 32, 33, after addition,
UV number (N). With reference to FIG. 1, this medium is, via the pipe 39, to this top fraction of 0.6 g of pure sodium
in accordance with the invention, fed via the pipe 1 to the first hydroxide, in the form of a concentrated solution, per kg of
distillation column 2, after addition, via the pipe 3, of 0.6 g of caprolactam.
pure Sodium hydroxide, in the form of a concentrated solu- 5 The top fraction 34 from the third column 31, composed of
tion, per kg of caprolactam. compounds with a lower boiling point than that of caprolac
The column 2 has a bottom temperature of less than 130°C. tam, is removed.
and a pressure of 70 mbar. The distillation bottom product 35 is recycled, in the
The top fraction 4 is composed of water. embodiment illustrated, in the second column 26.
The distillation bottom product 5 comprises an amount of 10 The purified caprolactam is drawn off from this third col
water of less than 0.5% by weight. umn 31 in the form of an intermediate fraction 40. This
This distillation bottom product 5 is fed to a second column withdrawal operation is carried out either in the gaseous form
6 operating under reflux 7, 8. The top fraction 9, composed at the lower part of the column or in the liquid form in the
essentially of caprolactam and of compounds with a lower upper part of the column. The characteristics of the caprolac
boiling point than that of caprolactam, is removed. The 15 tam produced are:
amount of caprolactam removed represents 0.5% by weight Permanganate number (PNo): 2
of the caprolactam fed in. The distillation bottom product 10, Content of volatile bases (N): 0.25 med/kg
comprising the caprolactam, is fed to a third column 11 also UV number (N): 0.03
operating under reflux 12, 13. According to the process of the invention, the distillation
The top fraction 14 is composed of caprolactam of con bottom product 30 from the second column 26, composed
formable purity. predominantly of caprolactam and comprising, as impurities,
The purity characteristics are: compounds with a higher boiling point than that of caprolac
Permanganate number (PNo): 1.5 tam and salts formed by the neutralization of the free bases by
Content of volatile bases (N): 0.28 med/kg the sulphuric acid, is fed to a scraped-film evaporator 36
UV number (N): 0.025 25 operating under a pressure of 10 mbar and a temperature of
The distillation bottom product 15, composed predomi 150° C. The evaporated caprolactam is recycled, in the
nantly of caprolactam and comprising, as impurities, com embodiment illustrated, via the pipe 37 in the second column
pounds with a higher boiling point than that of caprolactam, is 26.
fed to a scraped-film evaporator 16 operating undera pressure The non-evaporated products are removed via the pipe 38.
of 10 mbar and a temperature of 150° C. 30 The balance by weight of the caprolactam fed to the first
The evaporated caprolactam is recycled via the pipe 17 to column 22 and that produced in the form of an intermediate
the third column 11. fraction 40 from the third column 31 shows that 98.9% of the
The non-evaporated products are removed via the pipe 18. participating caprolactam is recovered with a high and Suit
The balance by weight of the caprolactam fed to the first able degree of purity.
column 2 and that produced at the top 14 of the third column 35
11 shows that 99.1% of the participating caprolactam is EXAMPLE 3
recovered with a high and Suitable degree of purity.
Example 2 is repeated, with the difference that the distil
EXAMPLE 2 lation bottom product30 from the second columnistreated by
40 addition of water in order to obtain a solution comprising
An aminocapronitrile hydrolysis medium after distillation approximately 80% by weight of caprolactam. The mixture is
(stripping) of the ammonia is treated in a plant in accordance Subjected to stirring. After mixing, two liquid phases are
with the invention, represented diagrammatically by FIG. 2, formed. The lower phase is an aqueous phase which com
according to a second embodiment of the process for the prises 60% by weight of amine Sulphates, corresponding to
purification of caprolactam. 45 approximately 70% of the amount of amines present in the
The characteristics of this medium are as follows: caprolactam charged to the dehydration column in the puri
Permanganate number (PNo): 381 fication process. The upper phase, composed essentially of
Content of Volatile bases (N): 232 med/kg caprolactam, is recycled in the first distillation column.
UV number (N, 12 By this process, 99% of the caprolactam charged in the
Furthermore, the concentration of free bases, determined 50 distillation column is recovered with a high degree of purity,
by potentiometric titration, is equal to 189 med per kg of suitable for use of this product in the manufacture of polya
medium or Solution. mide, in particular for textile applications.
With reference to FIG. 2, this medium is, in accordance
with the invention, fed via the pipe 21 to the first distillation EXAMPLE 4
column 22, after addition, via the pipe 23, of 0.8 mol of 55
Sulphuric acid, in the form of a concentrated Solution, per Example 2 is repeated, with the difference that the distil
mole of free bases present in the medium to be treated. lation bottom product30 from the second columnistreated by
The column 22 has a bottom temperature of less than 130° a process of crystallization in one stage of the caprolactam.
C. and a pressure of 70 mbar. The top fraction 24 is composed The distillation bottom product is concentrated under reduced
of water. 60 pressure in order to obtain a concentration by weight of water
The distillation bottom product 25 comprises an amount of of approximately 8%.
water of less than 0.5% by weight. The concentrated solution is at a temperature of 40°C. and
This distillation bottom product 25 is fed to a second col is then cooled to a temperature in the region of 20°C. with a
umn 26 operating under reflux 27, 28. rate of cooling of approximately 10°C. per hour. The crystals
The top fraction 29 resulting from this second column 26, 65 formed are recovered by filtration through a sintered glass
composed essentially of caprolactam and compounds with a filter. The aqueous mother liquors recovered are stored for
lower boiling point than that of caprolactam, is fed to a third possible recycling.
 US 8,231,765 B2
9 10
The Solid cake of caprolactam crystals is washed with a 9. The process according to claim 7, wherein the acidic
saturated aqueous Solution of caprolactam. The degree of medium comprises between 0.5 and 1 mol of at least one
washing as wet base is advantageously between 1 and 5. acidic compound per mole of free base present in the lactam
The recovered caprolactam has a sufficient purity to be to be purified.
recycled in the distillation process. 10. The process according to claim 7, wherein the acidic
By this process, 99% of the caprolactam charged in the medium comprises between 0.7 and 0.9 mol of at least one
distillation column is recovered with a high degree of purity, acidic compound per mole of free base present in the lactam
to be purified.
suitable for use of this product in the manufacture of polya 11. The process according to claim 1, wherein in the step of
mide, in particular for textile applications. 10 recovering the lactam from the reaction medium by at least
one distillation of said lactam in the presence of a base,
The invention claimed is: wherein the base comprises between 0.05 g and 2 g of at least
1. A process for the purification of lactams obtained from a one base per 1 kg of lactam.
hydrolysis reaction medium comprising an aminonitrile, a 12. The process according to claim 1, wherein the base
lactam, ammonia and a solvent used in the cyclizing hydroly comprises alkali metal hydroxides.
15
sis of an aminonitrile, the process consisting in: 13. The process according to claim 1, wherein the lactam is
e-caprolactam.
a. removing ammonia and optionally solvent from the 14. The process according to claim 1, wherein the amino
hydrolysis reaction medium; and nitrile is aminocapronitrile.
b) recovering the lactam from the reaction medium by 15. The process according to claim 1, wherein at least 90%
distilling said lactam at least once in the presence of a by weight of the lactam present in said bottom product is
base and recovering: recovered.
(i) optionally a top fraction comprising compounds 16. The process according to claim 1, wherein at least 95%
which are more volatile than the lactam, by weight of the lactam present in said bottom product is
(ii) a fraction comprising the lactam having higher recovered.
purity of the lactam than was present in the reaction 25 17. The process of claim 1, wherein the base is selected
mixture and from the group consisting of alkali earth metal hydroxide,
(iii) a distillation bottom product comprising lactam and alkaline earth metal hydroxides and metal carbonates.
compounds with a higher boiling point than the lac 18. The process of claim 1 wherein the base is selected
tam, from the group consisting of Sodium hydroxide, lithium
c. treating said distillation bottom product and recovering 30
hydroxide, potassium hydroxide, magnesium hydroxide, cal
said lactam from said distillation bottom product, and cium hydroxide, Sodium carbonate, magnesium carbonate,
lithium carbonate and mixtures thereof.
d. recycling said recovered lactam from said distillation 19. The process of claim 1, wherein the base comprises
bottom product, wherein treating said distillation bot Sodium hydroxide.
tom product consists of evaporating a thin-layer of the 20. A process for the purification of lactams obtained from
lactam, crystallizing the lactam, or separating the lactam 35
a hydrolysis reaction medium comprising an aminonitrile, a
from impurities by extracting the lactam with water. lactam, ammonia and a solvent used in the cyclizing hydroly
2. The process according to claim 1, wherein the step of sis of an aminonitrile, the process consisting in:
treating said distillation bottom product includes crystalliz a. removing ammonia and optionally solvent from the
ing the lactam from a solvent selected from the group con hydrolysis reaction medium and
sisting of water, aqueous lactam Solutions and lactams. 40
b) recovering the lactam from the reaction medium by
3. The process according to claim 1, wherein the step of distilling said lactam at least once in the presence of a
treating said distillation bottom product includes evaporating base and recovering:
a thin-layer of the lactam. (i) optionally a top fraction comprising compounds
4. The process according to claim3, wherein evaporating a which are more volatile than the lactam,
thin-layer of the lactam is performed by heating the lactam at 45
(ii) a fraction comprising the lactam having higher
a temperature of between 130° C. and 150° C. under a pres purity of the lactam than was present in the reaction
sure of less than 10 mbar.
mixture and
5. The process according to claim3, wherein evaporating a (iii) a distillation bottom product comprising lactam and
thin-layer of the lactam is performed by heating the lactam at compounds with a higher boiling point than the lac
a temperature of less than 150°C. under a pressure of between 50
tam,
5 and 10 mbar.
6. The process according to claim 1, wherein the step of c. treating said distillation bottom product and recovering
treating said distillation bottom product includes washing the said lactam from said distillation bottom product, and
distillation bottom product with water, and recovering the d. recycling said recovered lactam from said distillation
lactam in an organic phase. 55
bottom product, wherein treating said distillation bot
7. The process according to claim 1, wherein said lactam is tom product consists of evaporating a thin-layer of the
distilled in an acidic medium, prior to the distillation in a lactam, crystallizing the lactam, or separating the lactam
basic medium. from impurities by extracting the lactam with water, and
8. The process according to claim 7, wherein the acidic wherein the losses of the lactamare less than 3% by weight.
medium comprises Sulphuric acid. k k k k k