Caprolactam synthesis method

FIELD: chemistry.

SUBSTANCE: present invention relates to a method for synthesis of caprolactam from alkylcyanovalerate which involves bringing alkylcyanovalerate into contact with hydrogen in gaseous state in the presence of a hydrogenation catalyst and a ring formation catalyst, and treatment after condensation of a gaseous stream containing the formed lactam in order to separate ammonium which may be present, the formed alcohol and/or the caprolactam solvent and extraction of caprolactam, where the hydrogenation catalyst includes a metal element or a mixture of metal elements selected from a group containing an active metal element in form of iron, ruthenium, rhodium, iridium, palladium, cobalt, nickel, chromium, osmium and platinum or several metals from this list, and the ring formation catalyst is porous aluminium oxide.

EFFECT: obtaining caprolactam without intermediate separation of alkylaminocaproate.

10 cl, 5 ex, 1 tbl

 

The present invention relates to a method for producing a lactam.

More specifically, it relates to a method for producing a lactam of alkilirovaniye obtained using as raw materials, in particular mononitriles unsaturated compounds, in particular pentenenitrile, such as 2-, 3-, 4-pentenenitrile, taken individually or in a mixture, and hereinafter referred to as PN mixture and, accordingly, 2PN, 3PN and 4PN.

ε-Caprolactam is a compound used preferably for different polyamides of which the most important are polyamide 6 (PA6) or polycaproamide.

Has been proposed many methods for the synthesis of ε-caprolactam, of which some are used in industry for many years. In the most common method used as the raw material benzene to obtain cyclohexanone oxime as intermediate compounds, and ε-caprolactam obtained by reaction of the Beckmann rearrangement.

Already many years ago was also a method for obtaining ε-caprolactam, which used as the raw material butadiene and as an intermediate connection adiponitrile.

In this way adiponitrile received double hidrotsianova butadiene, partially hydronaut in aminocaproate obtaining simultaneously diamine.

Aminocaproate after separation of the hydrolysis of the t and cyclist obtaining caprolactam or in the gas phase, either in the liquid phase in the presence or in the absence of solvent. This method requires double hydrocyanide butadiene and produces simultaneously hexamethylenediamine were, which must be redesigned for efficiency of the process.

It is also possible on the basis of butadiene to spend alkoxycarbonylmethyl to get alkylphenones, and then hydroformylation followed by reductive amination with obtaining alkylaminocarbonyl. This is the last connection then cyclist in caprolactam.

It was also suggested that the method of synthesis of caprolactam, using as raw material butadiene and as an intermediate connection pentenenitrile (PN)obtained by simple hidrotsianova double bond of butadiene. In this way PN into formalparameter in response hydroformylation in the presence of hydrogen and carbon monoxide.

This formalparameter then the second step is converted into alkilirovanie by oxidation and reaction with alcohol.

After separation, for example, by distillation of alkilirovanie hydronaut to get alkylaminocarbonyl. Caprolactam get to the last step, the cyclization of alkylaminocarbonyl.

This method is described in particular in patent US 6365770, includes many successive stages, requiring between each stage of separation formed promezhutochnogo the connection.

These different stages of separation lead to a decrease in the total yield of the process and, thus, have a strong influence on its economic efficiency.

This combination of reactions and successive stages are described in many patents and articles, as, for example, patent WO 01/96294.

One of the purposes of the present invention is to eliminate these disadvantages by offering a way that will allow you to improve the total yield and reduce the cost required for its industrial use.

For this purpose, the invention proposes a method for the synthesis of caprolactam from allylcarbamate, which differs in that it consists in bringing allylcarbamate in the gaseous state in contact with hydrogen in the presence of catalysts of hydrogenation and cyclization and removing a gas stream containing educated caprolactam, and processing the specified stream after condensation to remove caprolactam.

The method according to the invention allows to obtain caprolactam directly from allylcarbamate without phase separation and collection of the educated alkylaminocarbonyl in-situ.

Therefore, the capital investment required to operate this way, considerably reduced as loss products obtained during separation of alkylaminocarbonyl or during the polymerization.

According to the preferred variationbetween of the invention the method is applicable, in particular, for the synthesis of ε-caprolactam from allylcarbamate, such as medicinealbert.

According to another characteristic of the invention, the processing gas flow at the outlet of the reactor consists in the condensation of the gas flow and its processing to separate the different components and extraction of caprolactam. For example, the condensed stream can be processed by ion exchange resins. The resulting medium containing caprolactam, after processing the resin is distilled in the presence of a strong base to separate the alcohol and/or solvent and collect caprolactam.

This method of processing environment cyclization to obtain pure caprolactam is described in particular in patent EP 922027.

You can also, without leaving the scope of the invention to use any known ways to extract and purify caprolactam contained in the environment.

So, this extraction and/or purification may include, for example, stages of crystallization, hydrogenation, oxidation.

Alkilirovanie used as raw material in the method according to the invention can be obtained, for example, from pentenenitrile reaction hydroformylation, and then oxidation and reaction with alcohol, such as described, for information, in patents US 6365770, US 5986126 and WO 00/56451.

Alkilirovanie can also be obtained by alkoxycarbonylmethyl of penten is triglow by reaction with carbon monoxide and alcohol, such as methanol. These methods are described in patents WO 01/72697, WO 03/040159 and WO 00/14055.

Other methods of obtaining described, for example, article Reppe, published in Lieb. Ann. Chem. 596 (1995)127, patents BE 850113, EP 576976.

Generally speaking, acceptable for the invention all known methods of synthesis of allylcarbamate as a way of using the enzymatic hydrolysis of adiponitrile described in particular in patent application WO 97/44318.

According to the invention the transformation of allylcarbamate in caprolactam is carried out in a single reactor containing the catalytic system, showing, on the one hand, the catalytic activity for hydrogenation, and on the other hand, the catalytic activity for the reaction of cyclization.

According to one method of carrying out the invention the catalysts of hydrogenation and cyclization are different components that are in the reactor in the form of a mixture of powders or solid granules or in the form catalyst layers, in particular, when the reactor is tubular or columnar type. In this latter case the implementation of a two-layer catalyst favorably located sequentially and next in the reactor, and the catalyst bed of the hydrogenation is in front of the catalyst bed cyclization in the direction of movement of gases or vapors, forming the reaction stream. The reactor may also contain one catalyst layer, with the mixture containing a series of two catalysts.

In another embodiment of the invention a single catalytic system formed caused by the catalyst, and the substrate is preferably a catalyst for cyclization, and metals, catalytic hydrogenation, which precipitated on the specified substrate or impregnate her.

As an example, hydrogenation catalysts that can be used in a mixture or in the form of a catalyst layer, can be called a catalyst containing as the active metal element is iron, ruthenium, rhodium, iridium, palladium, cobalt, Nickel, chromium, osmium and platinum, or several elements from this list. These metals can be used in the form of supported catalysts, or in bulk form. Such catalysts are described in particular in patents US 2003/0153749 and US 6365770.

Generally speaking, to obtain these hydrogenation catalysts may be any substrate catalysts. One or more metals are precipitated on the surface of these substrates, in particular, in the form of oxide. The amount of metal on the substrate is not critical, but it usually ranges from 0.1 to 50 wt.% the weight of deposited catalyst.

As for the cyclization reaction, suitable catalysts are solid heterogeneous catalysts, such as described, for example, in the application for the European patent 1456177.

Of the catalysts described in this document, for the invention are particularly suitable metal oxides, such as oxides of aluminium, silicon oxide, and zeolites, phosphates of metals such as, for example, phosphates of aluminum, titanium phosphates, zirconium phosphate.

As preferred for the invention of the catalysts for the cyclization can be called porous aluminum oxide, in particular, is described in European patent No. 0805801 and 1098875.

According to one variant of the invention, the catalytic system preferably is the only catalyst which is catalytically active in the hydrogenation reactions and catalytically active in the cyclization reaction. The catalysts preferred in the invention having such activity are the catalysts obtained by deposition of one or more metal elements exhibiting catalytic activity in the hydrogenation described above, the solid compound corresponding to the above-described cyclization catalysts. Thus, the preferred catalysts according to the invention are catalysts containing a metal oxide, such as porous alumina, described above, are besieged at least one catalytically active metal element. These catalysts can be obtained by any of the classical methods of making supported catalysts.

According to izaberete the human reactions of hydrogenation and cyclization can be carried out in the presence of ammonia and/or water. Mainly, the weight concentration of ammonia and/or water in the reaction medium ranges from 5 to 40%. These reactions are carried out at a temperature of from 200°C to 450°C, and favorably at a partial pressure of hydrogen of 0.1 to 20 bar.

Getting lactam according to the method according to the invention can be carried out in any reactor, allowing the reaction between the gases, by passing over the catalyst, favorably in the solid state.

Thus, the preferred reactors are tubular reactors or reactor column type, which may contain fixed or fluidized layers of catalysts.

The gas stream at the outlet of the reactor favorably cooled rapidly to avoid the formation of oligomers due to polymerization of the lactam.

Collected lactam then purified and recovered by known purification methods. Thus, in one embodiment of the invention, the gas stream exiting the reactor, condensed and cooled rapidly to a temperature below 150°C. This stage of condensation and cooling is realized at the time of several seconds to several minutes. Ammonia may present, is extracted from the condensed gas stream to the processing stage on the ion-exchange resin or distillation in the presence of acid. The resulting environment containing kaprol ctam, dissolved in the resulting alcohol (methanol in the case of methylcarbamate) or in water-methanol medium, cleaned and then by processing the resin, hydrogenation, oxidation, crystallization and/or distillation. Collected caprolactam has a degree of purity comparable to the get of various known synthesis methods.

Other advantages and details of the invention will become more clear when considering the examples given below solely as illustrations.

Examples 1-5

The experiments were conducted in a cylindrical reactor consisting of a glass tube, equipped with an electric heating device, a sensor for measuring the temperature, inlet and outlet for gas and means for introducing reagent.

The glass pipe in a vertical position sequentially filled, moving from the bottom up, 5 ml quartz beads, 4 ml of catalyst A, 4 ml of catalyst and 5 ml quartz beads.

According to the example, the catalyst And consists of a hydrolysis catalyst, and the catalyst is a hydrogenation catalyst, or catalysts A and B are identical and represent a mixed catalyst formed metal elements deposited on a substrate, typically and preferably aluminum oxide.

The reactor is heated to 300°C in a flow of hydrogen supplied from the top of the reactor at a speed of 5 l/H. After one hour serves a methanol solution of methylcarbamate (reagent) in a stream of hydrogen at the rate of 2 ml/h, This solution contains 60 wt.% methylcarbamate.

Pairs collected at the outlet of the reactor, condensed and analyzed by gas-chromatography, using as internal standard butylbenzoyl.

The degree of transformation (TT) of methylcarbamate and output (RR) of caprolactam are calculated based on the analysis results.

The results obtained are summarized in the table below.

Etc.CatalystTT %RR in %
AB
1Al2O3*Ni/Al2O39837(1)
2Al2O3*Rh/Al2O310045(2)
3Pt/Al2O3 Pt/Al2O39333(2)
4Al2O3*Pd/Al2O310037(2)
5Al2O3*Rh/Al2O38657(2), (3)
*Al2O3is aluminum oxide with a pore volume 117 ml/100 g and a specific surface area of 139 m2/g, manufactured in the sale of the company Axens
(1) the Catalyst produced by Johnson Mattey
(2) the Catalysts manufactured by Engelhard, containing 0.5 wt.% metal
(3) Medicinealbert served neat (without solvent)

1. The method of synthesis of caprolactam from allylcarbamate, characterized in that it consists in bringing into contact of allylcarbamate with hydrogen in a gaseous state in the presence of catalytic hydrogenation and cyclization catalyst and in processing after the condensation of the gas stream containing the resulting lactam, to separate the possible presence of ammonia, obrazovash is gosia alcohol and/or solvent caprolactam and extraction of caprolactam, where the hydrogenation catalyst includes a metal element or a mixture of metal elements selected from the group containing as the active metal element is iron, ruthenium, rhodium, iridium, palladium, cobalt, Nickel, chromium, osmium and platinum, or several metals from this list, as the cyclization catalyst is a porous aluminum oxide.

2. The method according to claim 1, characterized in that the catalysts of hydrogenation and cyclization mix.

3. The method according to one of claims 1 and 2, characterized in that the hydrogenation catalyst and the catalyst for the cyclization are placed separately in the reactor to form two consecutive catalytic layer.

4. The method according to one of claims 1 and 2, characterized in that the reaction is carried out in the presence of a mixed catalyst of hydrogenation and cyclization containing compound constituting the catalyst for cyclization, and metal elements, catalytically active for hydrogenation reactions, which are precipitated on the specified connection or impregnate it.

5. The method according to claim 4, characterized in that the mixed catalyst contains a substrate consisting of aluminum oxide and forming a cyclization catalyst that precipitated or impregnated with a metal element or elements selected from the group comprising iron, ruthenium, rhodium, iridium, palladium, cobalt, Nike is ü, chromium, osmium and platinum, or several elements from this list.

6. The method according to one of claims 1 and 2, characterized in that alkilirovanie is medicinewhere.

7. The method according to one of claims 1 and 2, characterized in that the reaction is carried out at a temperature of from 200 to 450°C.

8. The method according to one of claims 1 and 2, characterized in that the reaction is carried out at a hydrogen pressure of 0.1 to 20 bar.

9. The method according to one of claims 1 and 2, characterized in that the processing of the gas stream exiting the reactor after condensation, includes the processing stage on the ion-exchange resin or distillation in the presence of a strong acid and the stage of distillation of the caprolactam in the presence of a strong base.

10. The method according to claim 9, characterized in that the ammonia, if present, is extracted from the condensed gas stream to the processing stage on the ion-exchange resin or distillation in the presence of acid.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: invention relates to derivatives of 3-aminocaprolactam of formula (I): , where X represents -CO-R1 or -SO2-R2, R1 represents alkyl (with the exception of 5-methylheptanyl and 6-methylheptanyl, where radical R1 is bonded to carbonyl in position 1), halogenalkyl, alkoxy (with the exception of tret-butyloxy), alkenyl, alkinyl or alkylamino radical from 4-20 carbon atoms (for example, from 5-20 carbon atoms, 8-20 carbon atoms, 9-20 carbon atoms, 10-18 carbon atoms, 12-18 carbon atoms, 13-18 carbon atoms, 14-18 carbon atoms, 13-17 carbon atoms) and R2 is alkyl radical from 4-20 carbon atoms (for example, from 5-20 carbon atoms, 8-20 carbon atoms, 9-20 carbon atoms, 10-18 carbon atoms, 12-18 carbon atoms, 13-18 carbon atoms, 14-18 carbon atoms, 13-17 carbon atoms); or to its pharmacologically acceptable salt. Invention also relates to application and pharmacological composition, which has anti-inflammatory activity, based on said compounds.

EFFECT: obtaining new compounds and based on them pharmacological composition, which can be applied for obtaining medications for treatment, relief or prevention of inflammatory disease symptoms.

57 cl, 62 ex

FIELD: chemistry.

SUBSTANCE: invention refers to bengamide derivatives produced by fermented microorganism Myxococcus virescens ST200611 (DSM 15898), to application in cancer therapy and/or prevention, to medical products containing bengamide derivatives, making process of bengamide of formula . In addition, the invention refers to compound of formula .

EFFECT: new bengamide derivatives are characterised with useful biological properties.

15 cl, 7 tbl, 18 ex

FIELD: organic chemistry, medicine, biochemistry, pharmacy.

SUBSTANCE: invention relates to novel azaheterocycles of the general formula (I): possessing inhibitory effect on activity of tyrosine kinase and can be used in treatment of different diseases mediated by these receptors. In compound of the general formula (1) W represents azaheterocycle comprising 6-13 atoms that can be optionally annelated with at least one (C5-C7)-carbocycle and/or possibly annelated with heterocycle comprising 4-10 atoms in ring and comprising at least one heteroatom chosen from oxygen (O), sulfur (S) or nitrogen (N) atom; Ra1 represents a substitute of amino group but not hydrogen atom, such as substituted (C1-C6)-alkyl, possibly substituted aryl and possibly substituted 5-10-membered heterocyclyl comprising at least one heteroatom chosen from O, S or N; Rb represents carbamoyl group -C(O)NHRa wherein Ra represents a substitute of amino group but not hydrogen atom, such as possibly substituted alkyl, possibly substituted aryl, possibly substituted 5-10-membered heterocyclyc comprising at least one heteroatom chosen from O, S or N; Rc represents a substitute of cyclic system, such as possibly substituted (C1-C6)-alkyl, possibly substituted aryl and possibly substituted 5-6-membered heterocyclyl comprising at least one heteroatom chosen from O, S or N; or Rb and Rc form in common aminocyanomethylene group [(=C(NH2)CN], or their pharmaceutically acceptable salts. Also, invention relates to methods for synthesis of these compounds (variants), a pharmaceutical composition, combinatory and focused libraries.

EFFECT: valuable medicinal properties of compounds and pharmaceutical composition, improved methods for synthesis and preparing.

35 cl, 16 sch, 13 tbl, 43 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to technology for preparing caprolactam by the cyclization reaction of derivatives of aminocaproic acid. Method is carried out by cyclizing hydrolysis of compound chosen from the group comprising aminocaproic acid esters or amides, or their mixtures. The process is carried out in the presence of water, in vapor phase at temperature 200-450°C in the presence of a solid catalyst comprising of aluminum oxide that comprises at least one macroporosity with pores volume corresponding to pores with diameter above 500 Å taken in the concentration 5 ml/100 g of above. Preferably, the specific square of catalyst particles is above 10 m2/g and the total volume of pores is 10 ml/100 g or above wherein pores volume corresponds to pores with diameter above 500 Å is 10 ml/100 g or above. Invention provides improving the process indices due to the improved properties of the solid catalyst.

EFFECT: improved preparing method.

5 cl, 2 ex

FIELD: chemistry of lactams' derivatives.

SUBSTANCE: the present innovation deals with obtaining N-(2-chloroalkyl)- and N-alkyl-aromatic derivatives of lactams of the following general formula: , where R=H, Cl, R'=(CH2)3, (CH2)5 which could be modifiers of unsaturated carbon-chain caoutchoucs and rubber mixtures based upon them. The suggested method for obtaining the mentioned N-substituted lactams deals with combining N-chlorolactams and allyl benzene, moreover, as N-lactams one should apply either N-chlorobutyrolactam or N-chlorocaprolactam. The process should be carried out at molar ratio of N-chlorolactam to allyl benzene being equal to 1-1.15:1, at availability of a catalyzer as mono-tertiary-butylperoxy-α-methylmethoxyethoxyethyl ether of ethylene glycol taken at the quantity of 0.4-4.0% weight, in the medium of inert solvent, for example, chlorobenzene at 100-125° C for about 15-20 min. The innovation enables to shorten terms of reaction by 20-30 times, simplify the way for obtaining target products and widen the assortment of the obtained compounds, as well.

EFFECT: higher efficiency.

The invention relates to a method of evaporation aminonitriles and water in the synthesis of lactam by the reaction between aminonitriles and water in the vapor phase in the presence of a catalyst of aluminum hydroxide

The invention relates to the protection of building materials and structures from the biodegradation of microscopic mushrooms

The invention relates to acylaminocinnamic derivative of the formula (I), where R denotes phenyl which is not substituted or may be substituted with halogen, alkyl, trifluoromethyl, hydroxy and alkoxygroup, R1is hydrogen, alkyl, R2is hydrogen, alkyl or phenyl which is not substituted or may be substituted with halogen, alkyl, trifluoromethyl, hydroxy and alkoxygroup, R3is phenyl which is not substituted or may be substituted with halogen, alkyl, trifluoromethyl, hydroxy and alkoxygroup, or represents naphthyl, lH-indol-3-yl or 1-alcheringa-3-yl, R4' and R4"is hydrogen, alkyl, and one of the radicals R4' and R4"is hydrogen, and R5- cycloalkyl, D-azacycloheptan-2-he-3-yl or L-azacycloheptan-2-he-3-yl, or its salt

The invention relates to the production of aliphatic lactams from dinitriles
The invention relates to the production of caprolactam, which is used to produce polymeric products

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to technology for preparing caprolactam by the cyclization reaction of derivatives of aminocaproic acid. Method is carried out by cyclizing hydrolysis of compound chosen from the group comprising aminocaproic acid esters or amides, or their mixtures. The process is carried out in the presence of water, in vapor phase at temperature 200-450°C in the presence of a solid catalyst comprising of aluminum oxide that comprises at least one macroporosity with pores volume corresponding to pores with diameter above 500 Å taken in the concentration 5 ml/100 g of above. Preferably, the specific square of catalyst particles is above 10 m2/g and the total volume of pores is 10 ml/100 g or above wherein pores volume corresponds to pores with diameter above 500 Å is 10 ml/100 g or above. Invention provides improving the process indices due to the improved properties of the solid catalyst.

EFFECT: improved preparing method.

5 cl, 2 ex

The invention relates to a method of evaporation aminonitriles and water in the synthesis of lactam by the reaction between aminonitriles and water in the vapor phase in the presence of a catalyst of aluminum hydroxide

The invention relates to the processing of lactams

The invention relates to a method for regenerating catalyst tsiklitiria hydrolysis of aminonitriles order to obtain lactam

The invention relates to a method tsiklitiria hydrolysis aminonitriles compounds in the lactam by the interaction of aminonitriles General formula I NC-R-NH2(I) in which R denotes a substituted or unsubstituted aliphatic, cycloaliphatic or arylaliphatic radical containing from 3 to 12 carbon atoms, with water in the presence of a solid catalyst, wherein the catalyst is granulated catalyst obtained by deposition and/or adsorption of at least one oxygen-containing compounds, at least one element selected from the group comprising elements of groups 1 to 16 of the universal classification of the elements (new classification), and rare-earth metals on a carrier of simple or mixed inorganic oxide or mixture of oxides, at least one element selected from the group comprising silicon, aluminum, titanium, zirconium, vanadium, niobium, tantalum, tungsten, molybdenum, iron and rare earth metals, and the catalyst has at least one macroporous structure with a pore volume corresponding to pores with a diameter
The invention relates to the separation of water from an aqueous solution of lactam

The invention relates to a method of purification of lactams by liquid-liquid extraction and/or processing using ion exchange resin
The invention relates to the processing of lactams directly after their synthesis in the reaction stream resulting from the hydrolysis and cyclization of aminonitriles, for example, containing caprolactam

FIELD: chemistry.

SUBSTANCE: in accordance with the method A) at least two propane-containing gas supply streams are fed into the first reaction zone A, where at least one of the said streams contains fresh propane, and propane fed into this reaction zone undergoes heterogeneous catalytic dehydrogenation with a fixed bed catalyst, obtaining a propane- and propylene-containing gaseous mixture of products A, B) which is extracted from reaction zone A, in the first separation zone, A is separated from at least a portion of components contained in it, which are different from propane and propylene, and the remaining gaseous mixture of products A' which contains propane and propylene C) is used in the second reaction zone B for supplying at least one oxidation reactor, and propylene contained in the gaseous mixture of products A' in at least one oxidation reactor undergoes heterogeneous catalytic two-step gas-phase partial oxidation with molecular oxygen to acrylic acid or a mixture of acrolein and acrylic acid as an end product, as well as to an excess molecular oxygen-containing gaseous mixture of products B, D) which is extracted from the reaction zone B, in the second separation zone B, the end product contained in it is extracted through absorption or fractional condensation, and at least a portion of the remaining residual gas which contains unconverted propane, molecular oxygen, and also if necessary, unconverted propylene are recycled into the reaction zone A as at least one of two propane-containing supply streams, where the said recycling into the reaction zone A is done along the path of the heterogeneous catalysed dehydrogation of propane in that reaction zone such that, at the point for feeding the recycled gas into reaction zone A at least 5 mol % of propane has already undergone dehydrogenation, where the said propane is fed into this reaction zone with other supply streams, where molar ratio of the propylene contained in the reaction gaseous mixture to molecular hydrogen contained in the said mixture within the reaction zone A does not exceed 10.

EFFECT: design of an improved method of obtaining acrolein, acrylic acid or their mixture from propane.

41 cl, 3 ex

Up!