% conversion oxime for caprolactam

Sistem katalis untuk pengaturan ulang Beckmann dan metode untuk mempersiapkan kaprolaktamnya

Abstrak

diterjemahkan dari bahasa Cina

本 发明 公开 了 一种 用于 贝克曼 重 催化剂 的 催化剂 体系 ， 其 特征 在于 ， 该 催化剂 体系 含有

酸性 离子 液体 酸 ZSM-5 分子筛。

The present invention discloses a catalyst system for the Beckmann rearrangement, wherein the catalyst
system comprises an ionic liquid and an acidic ZSM-5 zeolite. Further, the present invention also provides
a method for the preparation of caprolactam, characterized in that the method comprises contacting
cyclohexanone oxime with a catalyst system described above, the contacting conditions comprise: a
temperature of 50-200 deg.] C, time 0.1 -24h. The inventive process is a simple operation, carried out
under normal pressure, the reaction conditions are milder, under preferred reaction conditions, the
conversion and selectivity of cyclohexanone oxime to caprolactam can be up to 95% or more.

Klasifikasi

Y02P20 / 52 Perbaikan yang berkaitan dengan produksi produk selain klorin, asam adipat, kaprolaktam,
atau klorodifluorometana, misalnya bahan kimia massal atau bahan kimia atau farmasi menggunakan
katalis, misalnya katalis selektif

CN103288735B

Cina

Unduh PDF Temukan Seni Sebelumnya Serupa

Bahasa lainnyaCinaPenemu 曲 良 龙董维 正王 月金 芃 澔南方陈健

Aplikasi di seluruh dunia

2012 CN

Aplikasi acara CN 201210049919

2012-02-29
Aplikasi diajukan oleh 北京 安 耐吉 能源 工程 技术 有限公司, 北京 华 福 工程 有限公司

2012-02-29

Prioritas ke CN 201210049919

2013-09-11

Publikasi CN103288735A

2015-03-04

Aplikasi dikabulkan

2015-03-04

Publikasi CN103288735B

InfoKutipan paten (6) Peristiwa hukum Dokumen serupa Aplikasi Prioritas dan TerkaitTautan
eksternalEspacenetBerkas GlobalBahas

Deskripsi

diterjemahkan dari bahasa Cina

- Beckmann rearrangement catalyst system and a method for preparing caprolactam species

FIELD

[0001] The present invention relates to a Beckmann rearrangement catalyst system, and a method for
preparing caprolactam by using the catalyst system used.

Background technique

[0002] Caprolactam is an important chemical raw materials, mainly used as fibers of nylon 6 and
monomer resin production, with widespread use in the textile, leather and plastics industries. Traditional
production process, caprolactam cyclohexanone oxime by Beckmann rearrangement reaction,
rearrangement use more 30% S03 oleum as a catalyst, carried out at 100-130 ° C, was added aqueous
ammonia and a large amount after the reaction . This process has several disadvantages: a large amount
of (1) by-product ammonium sulfate (2-5 t / t caprolactam) and the low value; (2) serious corrosion of
equipment; (3) the subsequent purification process is complicated caprolactam; (4 ) with vigorous
exothermic reaction, heat transfer difficulties; (5) a large amount of acidic waste water, pollution of the
environment.

[0003] Thus, the development of an environmentally friendly, pollution-free, solid waste, and easily
separated from the reaction system became clean catalytic process research trends in the art. Although
the molecular sieve and the metal oxide solid acid catalyst in a gas phase Beckmann rearrangement
reaction to some extent solve the above problem, but the harsh reaction conditions (300-500 ° C
temperatures) and rapid deactivation of the catalyst such that rearrangement products and by-products
are more frequent catalyst regeneration.

[0004] The room temperature ionic liquid (the RTIL) refers to salts which are liquid at room temperature
and is mainly composed of an organic cation consisting of inorganic or organic anion, compared with
solid materials which are liquid, compared with a conventional liquid substance they are ions. Thus, the
conventional organic solvent, water and supercritical fluid as compared to ionic liquids have many
unique properties. Specifically, the ionic liquid has the following characteristics: (1) very low vapor
pressure, less volatile, are not flammable, low toxicity; (2) a low melting point, a wide liquid range, good
chemical and thermal stability; (3 ) good solubility, good conductivity, wide electrochemical window; (4)
inexpensive, easy to prepare and simple post-treatment, can be recycled; (5) having a larger polarity of
regulated, low viscosity, high density.

[0005] Studies have shown that the first step protonic acid catalyzed Beckmann rearrangement reaction
of the oxime is partially protonated nitrogen-oxygen bond, followed by an intermediate iminium form a
ring, and the ionic strength of the liquid inside the Coulomb attraction can be enhanced this positive
charge stability intermediates. Thus, in the ionic liquid solvent is more common Beckmann
rearrangement reaction suitably carried out ratio.

[0006] Despite the Beckmann rearrangement in the ionic liquid without the advantages and
environmentally friendly and mild conditions. But conversion and selectivity of caprolactam
cyclohexanone oxime the process for still to be improved.

SUMMARY
[0007] The object of the present invention is to provide a catalyst for Beckmann reaction system and a
method for using the preparation of the catalyst system of caprolactam, cyclohexanone oxime
conversion of the process of the present invention and the selectivity of caprolactam compared high.

[0008] To achieve the above object, the present invention provides a catalyst system for the Beckmann
rearrangement, wherein the catalyst system comprises an ionic liquid and an acidic ZSM-5 zeolite.

[0009] Further, the present invention further provides a process for the preparation of caprolactam,
characterized in that the method comprises contacting cyclohexanone oxime with a catalyst system
described above, the contacting conditions comprise: a temperature of 50-200 ° C, time is 0.l-24h.

[0010] The process of the present invention is simple in operation, carried out under atmospheric
pressure, relatively mild reaction conditions, preferably under reaction conditions, conversion and
selectivity of cyclohexanone oxime to caprolactam can be up to 95% or more.

Detailed ways

[0011] The following detailed description of specific embodiments of the present invention. It should be
understood that the specific embodiments described herein are only to illustrate and explain the present
invention and are not intended to limit the present invention.

[0012] The present invention provides a catalyst system for the Beckmann rearrangement, it
characterized in that the catalyst system comprises an ionic liquid and an acidic ZSM-5 zeolite.

[0013] In the present invention, the term "acidic ionic liquid" and "ZSM-5 zeolite" are concepts known in
the art.

[0014] The present inventors have found that, while using acidic ionic liquid, and zeolite ZSM-5, and with
suitable reaction conditions cyclohexanone oxime to Beckmann rearrangement reaction, can be
obtained than using acidic ionic liquid alone and in conversion and selectivity of caprolactam in the liquid
phase of the ZSM-5 molecular sieve higher cyclohexanone oxime.
[0015] wherein the acidic ionic liquid with ZSM-5 Zeolite weight ratio is preferably 1: 0.01 to 1, more
preferably from 1: 5 0.05-0, and most preferably 1: 2 0.08-0. And acidic ionic liquids of ZSM-5 within the
preferred range of ratios is possible to obtain conversion and selectivity higher caprolactam
cyclohexanone oxime.

[0016] In the present invention, the acidic ionic liquid may be present a variety of conventional selection,
preferably, the acidic ionic liquid is a cation selected from Formula I portion shown cation, pyridinium
cation, imidazolium cation, a quaternary ammonium art salt cations and quaternary phosphonium salt is
at least one cation,

[0017]

Gambar CN103288735BD00041

[0018] The acidic ionic liquid anion portion selected bf4_, cr, & _, r, no2_, no3_, so42-, hso4_, CH3C00 \
CF3C00 \ C1CH2C00 \ C6H4C00 \ C6H4CH2C00 \ (CN) 2N \ CF3S03 \ C104 \ AsF6 \ SbF6 \ C4F9S03-, PF6 -,
(CF3S02) 2N- and (CF3S02) at least one of 3C-.

[0019] wherein the pyridinium cation refers to a positively charged pyridine various cation precursor may
be a substituted or unsubstituted pyridinium cation, such as an alkyl substituted pyridinium cation or
other functional groups of the functionalized cationic pyridine ,

Gambar CN103288735BD00042

The alkyl-substituted pyridinium cation, for example of the general formula [C5H5NR] + cation wherein,
R is a carbon atom, an alkyl group having 1 to 20 shown; the other functions of the functional group, for
example a pyridinium cation functionalized sulfonyl chloride pyridine cation.

[0020] The imidazolium cation refers to imidazo various cations having a positive charge of the parent
may be a substituted or unsubstituted imidazolium cation, alkyl-substituted imidazolium cation, or other
functional group of the functionalized imidazolium cation, the said alkyl substituted imidazolium cation,
for example of the general formula [C3HXN2R5_X] + cation represented by (X is an integer of 0 to 4),
wherein, R is an alkyl group of 1 to 20; the other functional groups of the functionalized cations such as
pyridine sulfonyl chloride functionalized pyridinium cation.

[0021] The quaternary ammonium cation may be a cation of the general formula [mRjr shown; the
quaternary phosphonium cation is a cation of FIG. Wherein, Ri, r2, r3 and r4 is a number from 1 to 20
alkyl carbon atoms.

[0022] In the present invention, any combination of the anion portion and cation portion, resulting acidic
ionic liquids include, but are not limited to: l-butyl-3-methylimidazolium tetrafluoroborate ionic liquid, 1-
ethyl-3- methylimidazolium tetrafluoroborate ionic liquid, 1-butyl-3-methylimidazolium chloroaluminate
ionic liquid, 1-ethyl-3-methylimidazolium chloroaluminate ionic liquid, 1-ethyl-3-methyl imidazole nitrate
ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate ionic liquid, 1-ethyl-3-methylimidazolium
hexafluorophosphate ionic liquid, 1-butyl-3-methylimidazolium trifluoromethanesulfonate amine
sulfonate ionic liquid, the ionic liquid-butyl-pyridinium tetrafluoroborate, pyridinium tetrafluoroborate
ionic liquid ethyl, butyl pyridinium chloride aluminate ionic liquid, 1-butyl-3-methylimidazolium ionic
liquids trifluoroacetic acid, 1-butyl-3-methylimidazolium ionic liquids dicarbonitrile amide, butyl amide
ionic liquid dinitrile pyridine, ethyl pyridine carboxamide ionic liquid dinitrile, 3-methyl -l- (4-
chlorosulfonyl-butyl) imidazole trifluoromethanesulfonate ion liquid, methyl -l- (4- chlorosulfonyl-butyl)
imidazole ionic liquid trifluoroacetic acid, 3-methyl -l- (4- chlorosulfonyl-butyl) imidazole P-
toluenesulfonic acid ionic liquid, 1- (4-chlorosulfonyl-butyl) pyridine trifluoromethanesulfonate ionic
liquid, 1- (4-chlorosulfonyl-butyl) pyridine-trifluoroacetic acid ionic liquid, 1_ (4_ chloro sulfonyl butyl)
pyridine p-toluenesulfonic acid ionic liquid, 1_ (4_ chlorosulfonyl-butyl) triphenylphosphonium
trifluoromethanesulfonate ionic liquid, 1- (4_ chlorosulfonyl-butyl) triphenylphosphonium trifluoroacetic
acid ionic liquid, 1_ (4_ chlorosulfonyl-butyl) triphenyl phosphonium ionic liquid p-toluenesulfonic acid,
methyl -L-3- (3- chlorosulfonyl-butyl) imidazole trifluoromethanesulfonate ion liquid, methyl -1_ (3-
chlorosulfonyl-butyl) imidazo trifluoroacetic acid ionic liquids, -L-3-methyl (3-chlorosulfonyl-butyl) p-
toluenesulfonyl imidazole ionic liquid, 1_ ( 3_ chlorosulfonyl-butyl) pyridine trifluoromethanesulfonate
ionic liquid, 1_ (3_ chlorosulfonyl-butyl) pyridine and trifluoroacetic acid ionic liquids 1_ (3_
chlorosulfonyl-butyl) pyridine p-toluenesulfonic acid ion at least one liquid.

[0023] Preferably, the acidic cation of the ionic liquid is selected from cationic moiety shown in formula I,
alkyl pyridinium cation, alkyl imidazolium cation, quaternary ammonium cations and quaternary
phosphonium cations of at least one anionic moiety is selected from BF4
'CF3C00'C1CH2C00'C6H4C00'C6H4CH2C00'Cl'Br'I'PF6'CF3S (V and NO, at least one.
[0024] or, particularly preferably, the cationic acidic cation portion of the ionic liquid is represented by
Formula I, at least one anionic moiety selected BF4'CF3C00'C1CH2C00'C6H4C00'C6H4CH2C0 (T and the
NCV.

[0025] Alternatively again, particularly preferably, the cationic portion of the ionic liquid is selected from
acidic cation alkylpyridinium, alkyl imidazolium cation, quaternary ammonium cations and quaternary
phosphonium cations of at least one anion moiety selected from cr , at least one of r and Bf. Examples of
the ionic liquid include, but are not limited to, alkyl chloride Ionic liquids imidazole, alkyl imidazole
bromo Ionic Liquids, alkylimidazolium iodide Ionic Liquids, quaternary ammonium chloride Ionic liquids,
quaternary ammonium bromo-Ionic liquid, quaternary ammonium iodide ionic liquids, alkylpyridinium
chloride ionic liquids, alkylpyridinium bromo ionic liquids, alkyl pyridinium iodide ionic liquids,
quaternary phosphonium chloride ionic liquids, a quaternary phosphonium salt bromine at least one
liquid and phosphonium iodide ionic liquids season aluminate ions.

[0026] Or, particularly preferably, the acidic ionic liquid cation moiety is a cation of formula II,

[0027]

Gambar CN103288735BD00051

[0028] wherein, R is methyl, at least one, preferably methyl vinyl group and an allyl group; X is a halogen
atom and / or hydroxyl groups, preferably at least one of chlorine, bromine and hydroxyl; n- is an integer
of 2-16, preferably an integer of 3-8, most preferably an integer of 3-5. Anion portion selected
BFpcf3coo'C1CH2C00'c6h4coo'c6h4ch2coo'cr, r, pf6 'cf3so3- no3- and at least one, preferably pf6- and /
or cf3so3-.

[0029] The acidic ionic liquid in the present invention can be prepared by conventional methods, such as
the quaternization reaction, the metathesis reaction and acid neutralization. The tetrafluoroborate ionic
liquid may be in the acid-base and the legal system, chloroaluminate ionic liquid may be prepared by
Lewis acid and reaction with a halide salt, wherein the cation portion of the ionic liquid prepared in
Reference Formula I may be InvestigationofPhysicochemicalPropertiesofLactam-BasedBr0nstedAcidic
IonicLiquids.JournalofPhysicalChemistryB2005,19542-19546. details as follows:
[0030] Take 30ml of benzene was added to a 100ml round bottom flask was added 11. 32g caprolactam
(0.lml) under stirring; the flask in an ice-water bath, then trifluoroacetic acid was added 11. 40g (0 within
30min. lmol). The reaction was continued at room temperature for 4 hours. The reaction product was
isolated and dried for 1 hour at a temperature of 90 ° C, a pressure of l-5mmHg conditions, i.e.,
trifluoroacetic acid ionic liquid to obtain caprolactam.

[0031] In the present invention, the use of ZSM-5 may be conventional in the zeolite ZSM-5, preferably,
ZSM-5 zeolite silica-alumina molar ratio of the field from 15 to 100, more preferably 25 to 60; primary
particle diameter to 0. 01-0 5iim, further preferably square • 1-0 3iim;. a specific surface area of 380-
550m2 / g, more preferably 390-500m2 / g. Above zeolite ZSM-5 may be a silicon source, an aluminum
source with an inorganic acid as raw materials, with or without the presence of seed crystals, the
pretreatment ultrasound, hydrothermal crystallization, filtration, exchanged, filtered and washed and
dried to obtain. More specifically, methods of preparation can be found in Chinese patent
CN101041442B.

[0032] The present invention provides a method for the preparation of caprolactam, characterized in
that the method comprises contacting cyclohexanone oxime with a catalyst system described above, the
contacting conditions comprise: a temperature of 50-200 ° C, preferably 80 -150 ° C, more preferably
100-120 ° C; time 0.l_24h, preferably l-10h, and most preferably 2-5h. Under the above preferred
conditions, the selectivity and conversion of caprolactam to obtain a higher cyclohexanone oxime.

[0033] For the present invention, ZSM-5 zeolite and the contact order of the acidic ionic liquid
cyclohexanone oxime and the catalyst system is not particularly limited, for example, cyclohexanone
oxime first mixed with an acidic ionic liquid, and then added ZSM- 5 zeolite, zeolite ZSM- may be first
mixed and acidic ionic liquid, and then cyclohexanone oxime, or in addition to other order of addition.

[0034] The contacting is preferably carried out under stirring.

[0035] In the present invention, when the molar ratio of the two feed molar ratio of cyclohexanone
oxime to the catalyst system in the ring for the acidic ionic liquid may be converted to conventional
oxime acidic ionic liquid catalyzed quite cyclohexyl. In particular molar addition, cyclohexanone oxime
with the catalyst system of the acidic ionic liquid ring may be 1: 01-20 billion, preferably from 1: 0.1 to
10, more preferably 1: 0.5-5.
[0036] will be described in detail by way of examples of the present invention. In the following examples,
conversion and selectivity of caprolactam cyclohexanone oxime were analyzed by gas chromatography
(an Agilent 7890A USA) to obtain; the X-ray diffractometer is DMAX2500; Chemicals used were of
analytical grade.

Preparation [0037] Example 1

[0038] This Example was prepared for the preparation of ZSM-5 Z-1

[0039] was added to the kettle 22g sodium silicate (Si02:. 28 7 wt%, Na20:. 6 5 wt%) and 22g of
deionized water, was added lg of aluminum sulfate under stirring, 35g of deionized water and 0. 14g a
mixed solution of sulfuric acid, sonicated lh (40KHz), the treatment temperature is 50 ° C. A closed
reaction vessel, reacted at 180 ° C 15 hours reaction mixture was cooled, the reaction mixture was
cooled and washed, filtered (ceramic filter) and concentrated, then at 30 ° C under a lmol / L of nitric
acid for 6 hours ion exchange. After the last solution was washed well to neutral, dried to constant
weight, to obtain the molecular sieve product Z-1.

[0040] X ray diffraction analysis by Z-1, it can be seen that the product of ZSM-5 zeolite, its parameters as
shown in Table 1.

[0041] Preparation Example 2

[0042] This Example was prepared zeolite ZSM-5 for the preparation of Z-2

[0043] was added to the kettle 22g sodium silicate (Si02:. 28 7 wt%, Na20:. 6 5 wt%) and 28g of
deionized water, 2. 3g of aluminum sulfate was added under stirring, 35g of deionized water and 2 . 6g of
phosphoric acid mixed solution, sonicated 5h (40KHz), the treatment temperature is 40 ° C. A closed
reaction vessel, reacted at 170 ° C 20 hours reaction mixture was cooled, the reaction mixture was
cooled and washed, filtered (ceramic filter) and concentrated, then at 40 ° C under a lmol / L
hydrochloric acid for four hours ion exchange. After the last solution was washed well to neutral, dried to
constant weight, to obtain the molecular sieve product Z-2.
[0044] By X-ray diffraction analysis of Z-2, the product can be seen that a ZSM-5 zeolite, its parameters as
shown in Table 1.

Preparation [0045] Example 3

[0046] This Example was prepared for the preparation of ZSM-5 Z-3

[0047] 22g of water glass was added to the kettle (Si02:. 28 7 wt%, Na20:. 6 5 wt%) and 30g of deionized
water was added 1. 6g aluminum sulfate under stirring, 30g of deionized water and 0 . 22g of sulfuric
acid mixed solution, sonicated 3h (40KHz), the treatment temperature is 40 ° C. A closed reaction vessel,
reacted at 175 ° C 15 hours reaction mixture was cooled, the reaction mixture was cooled and washed,
filtered (ceramic filter) and concentrated, then at 40 ° C under a lmol / L hydrochloric acid for four hours
ion exchange. After the last solution was washed well to neutral, dried to constant weight, to obtain the
molecular sieve product Z-3.

[0048] X ray diffraction analysis by Z-3, we can see the product as ZSM-5 zeolite, its parameters as shown
in Table 1.

[0049] TABLE 1

Gambar CN103288735BD00071

[0051] Example 1

[0052] The acidic ionic liquid, ZSM-5 zeolite and cyclohexanone 5mmol | losses added to a 100ml round
bottom flask and gradually heated under stirring, the reaction temperature was raised after the reaction,
after the reaction product was cooled to room temperature.

[0053] wherein the reaction temperature, reaction time, amount of the acidic ionic liquid was added and
the zeolite ZSM-5, and the type of ionic liquid and acidic zeolite ZSM-5 are shown in Table 2.
[0054] The product was analyzed to calculate conversion and selectivity to caprolactam, cyclohexanone
oxime, and the results are shown in Table 2.

[0055] The conversion of cyclohexanone oxime (%) = (moles of cyclohexanone oxime number V
(cyclohexanone oxime was added to the reaction molar number) X100%.

[0056] caprolactam selectivity (%) = (number of moles of caprolactam obtained V (reaction of

cyclohexanone oxime number of moles) X100%.

[0057] Example 2-12

[0058] The method for preparing caprolactam in Example 1, except that the reaction temperature,
reaction time, amount of acidic ionic liquids, and ZSM-5 zeolite, as well as the type of zeolite acidic ionic
liquid and ZSM-5 used are shown in Table 2.

[0059] The calculated conversion and selectivity of cyclohexanone oxime to caprolactam, the results
shown in Table 2.

[0060] Example 13-16

[0061] The method of preparation of caprolactam according to Example 1, except that the reaction
temperatures of 90 ° C, 130 ° C, 7 (rC and 160 ° C. The reaction conditions and results are shown in Table
2.

[0062] Examples 17-20

[0063] was prepared according to the method of Example 12, caprolactam, except that the acidic ionic
liquid and the weight of ZSM-5 molecular sieve are added in ratio of 1: 0. 〇 6,1: 0. 3, 1: 0.02 and 1: 0.6.
The reaction conditions and results are shown in Table 2 / _J, i 〇
[0064] Comparative Example 1

[0065] The preparation of caprolactam The method of Example 3, except that, without the addition of
ZSM-5. The reaction conditions and results are shown in Table 2.

[0066] Comparative Example 2

[0067] The method of preparing caprolactam Example 3, except that, instead of an acidic ionic liquid
with an equal volume of DMSO after drying. The reaction conditions and results are shown in Table 2.

[0068] Comparative Example 3

[0069] The method of preparation of caprolactam according to Example 6, except that, without the
addition of ZSM-5. The reaction conditions and results are shown in Table 2.

[0070] Comparative Example 4

[0071] was prepared according to the method of Example 8 caprolactam, except that, without the
addition of ZSM-5. The reaction conditions and results are shown in Table 2.

[0072] Comparative Example 5

[0073] was prepared according to the method of Example 12, caprolactam, except that, without the
addition of ZSM-5. The reaction conditions and results are shown in Table 2 are not.

[0074] TABLE 2
[0075]

Gambar CN103288735BD00091

Gambar CN103288735BD00101

[0077] In Table 1, the reaction temperatures are in ° C, with the reaction time is in units of hours.

[0078] Example 1-12 and Comparative Examples 1-5 As can be seen, the acidic ionic liquid is used alone
and separately in the use of ZSM-5 as compared to the liquid phase system, can obtain a higher
cyclohexanone oxime conversion and selectivity to caprolactam, and, according to the most preferred
embodiment of the invention, the conversion and selectivity can be obtained more than 95% of
caprolactam cyclohexanone oxime.

[0079] Comparative Example 1 and the results of Examples 13-16 shows that the reaction temperature is
80-150 ° C is the preferred embodiment of the present invention, the reaction temperature is 100-120 °
C is a more preferred embodiment.

[0080] Comparative Example 12 and Example 17-20 shows that the reaction system of the present
invention, the acidic ionic liquid of ZSM-5 with a weight ratio of 1: 5 0.05-0 preferred embodiments, the
acidic ionic liquid weight ratio of ZSM-5 zeolite is 1: 0.05-0 2 is a more preferred embodiment.

[0081] Further, among various embodiments of the present invention may be arbitrarily combined as
long as it does not violate the spirit of the invention, which should also be considered as the disclosure
of the present invention.

Klaim (11)

Sembunyikan Tanggungan

diterjemahkan dari bahasa Cina

A method for preparing caprolactam, characterized in that the method comprises contacting
cyclohexanone oxime with a catalyst system comprising an ionic liquid and an acidic ZSM-5 molecular
sieve, said contacting conditions comprise: a temperature of 50-200 ° C, time is 0 · l-24h.

Condition 2. The method according to claim 1, wherein said contacting comprises: a temperature of 80-
150 ° C, time is I-IOh0

3. The method of claim 1 or claim 2, wherein the acidic ionic liquid feeding cyclohexanone oxime to the
catalyst system of the ring molar ratio of 1: 01-20 billion.

4. The method according to claim 3, wherein the acidic ionic liquid feeding cyclohexanone oxime to the
catalyst system of the ring molar ratio of 1: 1-10 billion.

The method according to claim 1, wherein said acidic ionic liquid weight ratio of ZSM-5 zeolite was 1:
001-1.

6. The method according to claim 5, wherein the weight ratio of the acidic ionic liquid with the zeolite is
ZSM-5 1: 005-0 5 〇

1, 5 and 7. The method according to any one of claim 6, wherein the cation of Formula I, as the acidic
ionic liquid is selected from the cationic moiety, a pyridinium cation, imidazolium cation, quaternary
ammonium cations and quaternary at least one cationic phosphonium salt,

Gambar CN103288735BC00021

The anionic portion of the acidic ionic liquid is selected from BF4 'Cl-, Br' Γ, NO2 'NO3' SO42 'HSO4'
CH3COO 'CF3COO' ClCH2COO 'C6H4COO' C6H4CH2COO '(CN) 2N' CF3SO3 'ClO4' AsF6 'SbF6' C4F9SO3
'PF6' (CF3SO2) 2N_ and in 3C_ (CF3SO2) at least one.

8. The method according to claim 7, wherein the acidic cation of the cation portion of the ionic liquid of
formula I as the anion moiety selected from at least one BF4'CF 3COO'ClCH2COO'C6H4COO'C6H
4CH2COCT and the NCV species.

9. The method of claim 7, wherein the acidic ionic liquid cation moiety selected from alkyl pyridinium
cation, imidazolium cation alkyl, at least one anionic moiety and quaternary ammonium cations of the
quaternary phosphonium cations is selected from cr, and at least one of Γ.

10. The method according to claim 7, wherein the cation portion of the acidic ionic liquid is a cation of
formula II,

Gambar CN103288735BC00022

Wherein, R is methyl, at least one allyl group and vinyl group, X is a halogen atom and / or a hydroxyl
group, [eta] is an integer of 2-16, anionic moiety is selected from BF4 'CF3COO' ClCH2COO 'C6H4COO'
C6H4CH2COO ' cl 'Γ, PF6' CF3SCV and at least one of the NCV.
Alumina molar ratio of 1, 5 and 11. A method according to any one of claim 6, wherein the zeolite ZSM-5
of 15 to 100, primary particle diameter 0. 01-0. 5 μ m specific surface area of 380-550m2 / g.

Kutipan paten (6)

Nomor publikasi Tanggal prioritas Tanggal publikasiJudul Penugasan

CN1566089A * 2003-06-30 2005-01-19 中国 石油 化工 股份有限公司 Proses persiapan

kaprolaktam

CN1781908A * 2004-12-02 2006-06-07 中国科学院 兰州 化学 物理 研究所 Proses untuk

menyiapkan epsilon-heksanolaktam dengan mengkatalisasi pengaturan ulang sikloheksanon-oksim

CN1852898A * 2003-09-18 2006-10-25 住友 化学 株式会社 Cairan ionik dan metode reaksi

menggunakan hal yang sama

CN1919833A * 2005-08-26 2007-02-28 中国科学院兰州化学物理研究所 Method of

preparing amide from ketoximes by Beckmann rearrangement

CN101117327A * 2006-07-31 2008-02-06 中国石油化工股份有限公司;中国石油化工股

份有限公司石油化工科学研究院 Preparation method of aminocaprolactam

Family To Family Citations

ITMI20012470A1 * 2001-11-23 2003-05-23 Enichem Spa Procediemnto for the

preparation of zeolite-type revitalisers mfi

* Cited by examiner, † Cited by third party

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