Integrated method and system for producing amide and nitrile compounds

Abstract

An integrated method and system for the production of acrylamide and acrylonitrile compounds and other compounds from at least beta-lactone and / or beta-hydroxyamide is provided herein.

Description

Technology Field

[0001] The present disclosure generally relates to amide products and / or nitrile products, and more specifically to the production from at least epoxides, beta-lactones and / or beta-hydroxyamides. Background Technology

[0002] Nitrogen-containing compounds, such as amides and nitriles, are valuable compounds that can be used for various commercial and industrial applications. For example, acrylonitrile can be used as a starting material in the production of polymer and monomer precursors.

[0003] Various methods for the industrial production of acrylonitrile are known to the art. For example, acrylonitrile can be produced by the catalytic ammonia oxidation of propylene in which propylene, ammonia, and air are brought into contact with a catalyst at elevated temperature and pressure. However, this process generally requires harsh reaction conditions and the use of expensive reagents. The problem to be solved

[0004] There is still a demand in the industry for the development of an integrated method and system for the industrial production of nitriles and nitrile precursors that utilizes inexpensive and renewable feedstocks, integrates multiple synthesis operations, is designed to avoid the expensive purification of intermediates, and enables the production of nitriles and nitrile precursors under mild reaction conditions. means of solving the problem

[0005] An integrated method and system for the industrial production of nitriles, nitrile precursors, and other compounds desired in the art is disclosed, including a method and system for producing such compounds partially or wholly from renewable sources.

[0006] A method comprising the following is disclosed: combining a hydroxypropanamide stream containing hydroxypropanamide with a dehydrating agent to produce a product stream comprising an unsaturated amide and / or an unsaturated nitrile, or an isomer thereof. A method comprising combining a hydroxypropanamide stream with a dehydrating agent to produce an amide product and / or a nitrile product is disclosed. Hydroxypropanamide may be combined with a dehydrating agent in the presence of a solvent and ammonia. Hydroxypropanamide may be combined with a dehydrating agent in the presence of a solvent and ammonia. A method comprising combining a beta-lactone with ammonia in a solvent is disclosed. Ammonia may be added to the beta-lactone at a temperature of about -100°C to less than 100°C. The combination of the beta-lactone and ammonia is controlled isothermally. The beta-lactone may be prepared by contact with carbon monoxide and an epoxide in the presence of a carbonylation catalyst. Contact between carbon monoxide and an epoxide in the presence of a carbonylation catalyst can produce a carbonylation product stream containing a beta-lactone. The method comprises distilling a product stream containing an unsaturated amide and / or unsaturated nitrile, or its isomer, to isolate the unsaturated amide and / or unsaturated nitrile. The hydroxypropanamide stream may contain molten hydroxypropanamide and optionally a carrier gas. The dehydrating agent may be heterogeneous, and the hydroxypropanamide stream may be contacted with a heterogeneous dehydrating agent to produce a product stream containing an unsaturated amide and / or unsaturated nitrile, or its isomer. Any of the disclosed steps may be carried out in a solvent of a polar aprotic solvent, an alcohol, or a combination thereof. The beta-lactone may be contacted with anhydrous ammonia at a temperature of -100°C to 35°C to produce hydroxypropanamide. Beta-lactone and anhydrous ammonia can be contacted in a solvent. Beta-lactone and anhydrous ammonia can be contacted in the presence of a base. The dehydrating agent may include TiO2 or SiO2, or a combination thereof.The dehydrating agent comprises TiO2 and SiO2. The dehydrating agent is provided to a column, and the column has a zone containing TiO2 and a separate zone containing SiO2. The zone containing TiO2 can operate at a first temperature, and the zone containing SiO2 can operate at a second temperature, and the first temperature and the second temperature are different.

[0007] A hydroxypropanamide stream can be produced by combining a mixed feed stream with ammonia. A beta-lactone can be produced by carbonylating an epoxide with carbon monoxide in the presence of a carbonylation catalyst and a solvent to produce a carbonylation product stream comprising a beta-lactone, a solvent, and a carbonylation catalyst. The beta-lactone and anhydrous ammonia are contacted in the presence of a base. The carbonylation catalyst can be separated from the carbonylation product stream to produce a mixed feed stream. A method for producing a hydroxypropanamide stream by combining a mixed feed stream with ammonia is disclosed. The hydroxypropanamide stream can be produced by combining a beta-lactone with anhydrous ammonia at a temperature of -100°C to less than 100°C, -75°C to 70°C, or -100°C to 35°C. A hydroxypropanamide stream may be prepared by combining a mixed feed stream with anhydrous ammonia at a temperature of -100°C to less than 100°C, or -75°C to 70°C. In another embodiment, a method for producing a hydroxypropanamide stream by combining a mixed feed stream with anhydrous ammonia at a temperature of -100°C to 35°C is provided. A method for producing an amide product and / or a nitrile product by combining a mixed feed stream with ammonia and a dehydrating agent is provided. The hydroxypropanamide stream may comprise hydroxypropanamide, a solvent, and ammonia. The mixed feed stream may comprise a beta-lactone and a solvent. A method for producing an amide product and / or a nitrile product by contacting a hydroxypropanamide stream with a heterogeneous dehydrating agent is provided, wherein the hydroxypropanamide stream comprises molten hydroxypropanamide and a carrier gas. Receiving a mixed feed stream and ammonia; And a system including a reactor that discharges a hydroxypropanamide stream is provided.

[0008] A system is provided comprising a reactor configured to produce a product stream in the presence of a dehydrating agent, wherein the product stream comprises an amide product and / or nitrile product, a solvent, and ammonia. The reactor may receive a hydroxypropanamide stream; and discharge a product stream. The reactor may receive a mixed feed stream and ammonia; and discharge a product stream. The hydroxypropanamide stream may comprise hydroxypropanamide, a solvent, and ammonia. The mixed feed stream may comprise a beta-lactone and a solvent.

[0009] Beta-lactone is the chemical formula (1) It may apply to.

[0010] Hydroxypropanamide is chemical formula (2) It corresponds to.

[0011] Unsaturated nitrile is chemical formula (3) It corresponds to.

[0012] Unsaturated amides have the chemical formula (3-I) It corresponds to.

[0013] Epoxide is the chemical formula (E) It may apply to.

[0014] In these expressions, R 1 silver H, alkyl, alkenyl, cycloalkyl or aryl; H or alkyl.

[0015] A method comprising the following is disclosed: the step of preparing an unsaturated amide or unsaturated nitrile, or its isomer, as disclosed herein, and the step of polymerizing the unsaturated amide or unsaturated nitrile, or its isomer.

[0016] A system comprising a reactor comprising: (i) a mixed feed stream comprising a beta-lactone and a solvent and (ii) at least one inlet configured to receive ammonia; and an outlet configured to discharge a hydroxypropanamide stream comprising hydroxypropanamide, a solvent, and ammonia. The system may comprise an additional reactor configured to receive the hydroxypropanamide stream and produce a product stream in the presence of a dehydrating agent, wherein the product stream comprises an unsaturated amide and / or unsaturated nitrile, or its isomer, a solvent, and ammonia. The additional reactor may comprise a multi-temperature stage column. The system may comprise a distillation unit configured to collect the following: i) an unsaturated amide and / or unsaturated nitrile, or its isomer; ii) a solvent; or iii) ammonia; or iv) any combination of i) to iii).

[0017] A system comprising the following is disclosed: a reactor configured to produce a product stream in the presence of a dehydrating agent, wherein the reactor comprises: an inlet configured to receive a hydroxypropanamide stream comprising hydroxypropanamide, a solvent, and ammonia, and an outlet configured to discharge a product stream comprising an unsaturated amide and / or unsaturated nitrile, or an isomer thereof, a solvent, and ammonia.

[0018] A reactor configured to produce a product stream in the presence of a dehydrating agent is disclosed, and the reactor comprises: (i) a mixed feed stream comprising a mixture of beta-lactone and a solvent, and (ii) ammonia; and at least one inlet configured to receive an outlet configured to discharge a product stream comprising an unsaturated amide and / or unsaturated nitrile, or its isomer, a solvent, and ammonia. The reactor may comprise a multi-temperature stage column. Brief explanation of the drawing

[0019] The present application is best understood by referring to the following description together with the attached drawings, wherein similar parts may be referred to by similar numbers. do 1 and 2 This illustrates an exemplary method for the integrated production of amide products and / or nitrile products of formulas (3) and (3-I). do 3 , 4 and 5 This illustrates an exemplary system for the integrated production of amide products and / or nitrile products of chemical formulas (3) and (3-I). Specific details for implementing the invention

[0020] The following description presents exemplary methods, parameters, etc. However, it should be recognized that such description is not intended to limit the scope of the invention, but rather is provided as an explanation of exemplary embodiments.

[0021] An integrated method and system for the production of an amide product and / or a nitrile product, as well as a precursor of such product, is provided herein. In certain embodiments, the amide product comprises acrylamide, and the nitrile product comprises acrylonitrile. In some variations, the amide product is a compound corresponding to formula (3-I), and the nitrile product is a compound corresponding to formula (3) or an isomer thereof:

[0022]

[0023] During the meal, R 1 It is H or alkyl.

[0024] Integration method

[0025] In some embodiments, an integrated method for producing an amide product and / or a nitrile product and its precursor is provided.

[0026] The integration method is disclosed in the following process flow diagram.

[0027]

[0028] Another process flow diagram is initiated.

[0029]

[0030] In certain embodiments, the amide product and / or nitrile product may be derived from the epoxide and carbon monoxide. For example, in some variations, the epoxide is of formula (E): It is a compound of, and in the formula, R 1 It is as defined above for chemical formulas (3-I) and (3).

[0031] do 1 In relation to this, an exemplary reaction scheme for producing a compound of formula (3-I) and / or a compound of formula (3), or its isomers, from an epoxide and carbon monoxide is shown. The epoxide undergoes carbonylation to produce a beta-lactone, e.g., a compound of formula (1):

[0032] During the meal, R 1 It is as defined above.

[0033] Such a carbonylation reaction occurs in the presence of a carbonylation catalyst and a solvent to produce a carbonylation product stream (1), which includes a compound of formula (1), a solvent, and a carbonylation catalyst. The carbonylation product stream (1) may undergo an additional processing step to remove the carbonylation catalyst. 1As illustrated in the figure, the carbonylation product stream (1) undergoes a separation step to remove the carbonylation catalyst from the stream to produce a mixed feed stream (2), which contains the compound of formula (1) and a solvent. Any suitable technique may be used to separate the carbonylation catalyst from the carbonylation product stream (1). For example, in some variations, a membrane, such as a nanofiltration membrane, may be used. Without requiring further processing of the mixed feed stream (2) to remove the solvent, the mixed feed stream (2) is combined with ammonia to produce a hydroxypropanamide stream (3), which contains the compound of formula (2), a solvent, and ammonia. Ammonia may be provided at any suitable temperature to convert the compound of formula (1) in the mixed feed stream (2) into the compound of formula (2) in the hydroxypropanamide stream (3). In some variations of the foregoing, ammonia is provided at a temperature of -100°C to less than about 100°C, -100°C to about 70°C, -100°C to about 35°C, -100°C to about 0°C, -100°C to about -20°C, -100°C to about -50°C, -100°C to about 10°C, -100°C to about 0°C, -100°C to about -20°C, or -100°C to about -50°C.

[0034] In some variations, the mixed feed stream (2) is added to ammonia to produce a hydroxypropanamide stream (3). In one variation, the mixed feed stream is added to excess ammonia. In certain variations, the mixed feed stream is added to ammonia over a process of 60 minutes to 1 minute, or 30 minutes to 5 minutes, 30 minutes to about 15 minutes, or 15 minutes to 5 minutes; or about 60 minutes, about 30 minutes, about 15 minutes, or about 5 minutes. In some embodiments, the mixed feed stream is added to ammonia at any rate suitable for maintaining a constant temperature. In other variations, the combination of the mixed feed stream (2) and ammonia is controlled isothermally. By controlling the reaction conditions of this step, the reaction can be induced to optionally produce a compound of formula (2). For example, in some variations, the method comprises combining a mixed feed stream (2) with anhydrous ammonia at a temperature of -100°C to 35°C to produce a hydroxypropanamide stream (3). In a specific variation of the foregoing, the compound of formula (2) present in the hydroxypropanamide stream (3) is It is produced with a selectability of over 50%, over 60%, over 70%, over 80%, or over 90%.

[0035] Subsequently, hydroxypropanamide can perform dehydration to produce amide products and / or nitrile products. Again, Figure 1 In relation to this, the hydroxypropanamide stream (3) is combined with a dehydrating agent to produce a product stream (4), which includes a compound of formula (3-I) and / or a compound of formula (3), or its isomer, as well as a solvent and ammonia. Fig. 1In some variations illustrated in Fig. 1, it should be understood that the hydroxypropanamide stream (3) does not require additional treatment to remove solvent and / or ammonia at this stage. Rather, the solvent and / or ammonia can be transported through an integrated process and removed after the production of the product stream (4). Again Fig. 1 1 In this regard, the product stream (4) performs a separation step to isolate the compound of formula (3-I), the compound of formula (3), or its isomer, the solvent, and / or ammonia.

[0036] Accordingly, in some embodiments, an integrated method is provided comprising: carbonylating an epoxide feed stream containing a compound of formula (EI) in the presence of a carbonylation catalyst and a solvent to produce a carbonylation product stream containing a compound of formula (1), a solvent, and a carbonylation catalyst; separating the carbonylation catalyst from the carbonylation product stream to produce a mixed feed stream containing a compound of formula (1) and a solvent; combining the mixed feed stream with ammonia to produce a hydroxypropanamide stream containing a compound of formula (2), a solvent, and ammonia; and combining the hydroxypropanamide stream with a dehydrating agent to produce a product stream containing a compound of formula (3-I) and / or a compound of formula (3), or its isomer, a solvent, and ammonia.

[0037] do 1In other variations where this heterogeneous carbonylation catalyst is used, exemplary reaction schemes involving a separation step to isolate the carbonylation catalyst from the carbonylation product stream are illustrated, but such a separation step may not be necessary. For example, in another embodiment, the method comprises: carbonylating an epoxide feed stream containing a compound of formula (EI) in the presence of a heterogeneous carbonylation catalyst and a solvent to produce a mixed feed stream containing a compound of formula (1) and a solvent; combining the mixed feed stream with ammonia to produce a hydroxypropanamide stream containing a compound of formula (2), a solvent, and ammonia; and combining the hydroxypropanamide stream with a dehydrating agent to produce a product stream containing a compound of formula (3-I) and / or a compound of formula (3), or its isomer, a solvent, and ammonia. The produced product stream may undergo further purification to isolate one or more components of the product stream, including isolating the compound of formula (3-I) and / or the compound of formula (3), or its isomers. Again 1 In relation to this, the product stream (4) may undergo distillation to isolate one or more of the following: (a) a compound of formula (3-I) and / or a compound of formula (3), or its isomer; (b) a solvent; and (c) ammonia. Fig. 1 Although exemplary reaction schemes for producing amide products and / or nitrile products from epoxide and carbon monoxide are illustrated, it should be understood that in other variations, the compounds of formula (1) and / or the compounds of formula (2) can be obtained from commercially available sources.

[0038] do 1 Other variations of the exemplary reaction scheme illustrated in are also considered. For example, Fig. 2In this regard, the mixed feed stream (2) may be combined with ammonia and a dehydrating agent in one step to produce a product stream (4). In other variations, a carrier gas may be used to convert hydroxypropanamide into an amide product and / or a nitrile product. Thus, in certain embodiments, a method is provided for producing a compound of formula (3-I) and / or a compound of formula (3), or an isomer thereof, said method comprising: a step of combining a hydroxypropanamide stream with a carrier gas and a dehydrating agent to produce a product stream comprising a compound of formula (3-I) and / or a compound of formula (3), or an isomer thereof. In some variations, the carrier gas comprises ammonia. In other variations, the carrier gas comprises ammonia and nitrogen. In some variations, the product stream further comprises ammonia, water, or a combination thereof.

[0039] Hydroxypropanamide may also exist in different forms in the integration method described herein. For example, in another variation, the method comprises combining a molten compound of formula (2) and a carrier gas with a heterogeneous dehydrating agent to produce a product stream comprising a compound of formula (3-I) and / or a compound of formula (3), or its isomers, as well as a solvent. In some variations of the foregoing, with respect to formulas (1), (2), (3-I) and (3), R 1 is H. Therefore, in one deformation, R 1 In the case where H is present, acrylonitrile is produced from beta-propiolactone via 3-hydroxypropanamide and acrylamide. In other variations, R 1 is a C1-10 alkyl. In another variation, R 1 It is methyl.

[0040] In one example, a mixed feed stream containing beta-propiolactone and a solvent can react with ammonia anhydride to produce a hydroxypropanamide stream containing 3-hydroxypropanamide, a solvent, and excess ammonia. Subsequently, the hydroxypropanamide stream can be fed continuously into a fixed-bed reactor filled with a dehydrating agent. In some variations, the hydroxypropanamide stream can be evaporated and mixed with a carrier gas, then passed through a dehydrating agent (e.g., in a catalyst bed) to produce a product stream containing acrylonitrile, a solvent, and ammonia. The product stream can be processed to isolate the acrylonitrile, a solvent, and ammonia. In another example, beta-propiolactone can react with ammonia anhydride to produce 3-hydroxypropanamide. Subsequently, the pure 3-hydroxypropanamide can be fed continuously into a fixed-bed reactor filled with a dehydrating agent. The 3-hydroxypropanamide solid is heated above its melting point to produce molten 3-hydroxypropanamide, which is then further mixed with a nitrogen carrier gas in a preheating zone / evaporated and then passed through a dehydrator (e.g., in a catalyst bed).

[0041] The amide products and / or nitrile products produced according to the methods and systems described herein may be used in various downstream processes. For example, in one variation, acrylamide may be polymerized to form polyacrylamide; and acrylonitrile may be polymerized to form polyacrylonitrile. The produced polyacrylonitrile may be suitable for various uses, including as carbon fibers. In some embodiments, a method for producing a polymer is provided, said method comprising any of the methods described herein, the step of producing a compound of formula (3-I) and / or a compound of formula (3), or an isomer thereof; and the step of polymerizing the compound of formula (3-I) and / or a compound of formula (3), or an isomer thereof.

[0042] Integrated System

[0043] In another embodiment, a system for the integrated production of an amide product and / or a nitrile product and its precursor is also provided herein. As described above regarding the integrated method, the amide product and / or nitrile product may be derived from an epoxide and carbon monoxide. In some variations, the epoxide is a compound of formula (E), and other products produced therefrom may include a beta-lactone (e.g., a compound of formula (1)), a hydroxypropanamide (e.g., a compound of formula (2), as well as amide and nitrile products (e.g., compounds of formulas (3-I) and (3)).

[0044] do 3 In this regard, the system (100) is an exemplary system for producing a compound of formula (3-I) and / or a compound of formula (3), or its isomers, from an epoxide and carbon monoxide. Carbonylation of the epoxide takes place in a reactor (101). Epoxide (102), carbon monoxide (103), solvent (104) and the carbonylation catalyst (105) are supplied to the reactor (101). The epoxide is carbonylated in the presence of the carbonylation catalyst and the solvent to produce a carbonylation product stream (106), which comprises the compound of formula (1), the solvent, and the carbonylation catalyst. The carbonylation product stream (106) may undergo an additional processing step to remove the carbonylation catalyst. 3As illustrated in [Figure], the carbonylation product stream (106) is directed to a separation unit (107), which separates the carbonylation catalyst (108) and obtains a mixed feed stream (111), which contains a compound of formula (1) and a solvent. For example, in some variations, the separation unit (107) may be a membrane, such as a nanofiltration membrane. The recovered carbonylation catalyst (108) can be reused and recirculated back to the system (100). Without requiring further processing of the mixed feed stream (111) to remove the solvent, the mixed feed stream (111) is fed to a reactor (110). The reactor (110) also contains ammonia (112) and optionally accepts a base (113). The compound of formula (1) in the mixed feed stream (111) is converted to hydroxypropanamide, and the reactor (110) A hydroxypropanamide stream (114) is discharged, which contains a compound of formula (2), a solvent and ammonia, as well as a base if used. The integrated system is configured to provide ammonia (112) to the reactor (110) at any suitable temperature so as to convert the compound of formula (1) in the mixed feed stream (111) into the compound of formula (2) in the hydroxypropanamide stream (114). In some variations of the foregoing, the system may be configured to provide ammonia at a temperature of -100°C to about 35°C, -100°C to about 10°C, -100°C to about 0°C, -100°C to about -20°C, -100°C to about -50°C, -100°C to about 10°C, -100°C to about 0°C, -100°C to about -20°C, or -100°C to about -50°C. In some variations, the system adds a mixed feed stream (111) from a reactor (110) to ammonia (112). It is configured to produce a hydroxypropanamide stream (114). In some variations, the mixed feed stream is added to excess ammonia in the reactor. In certain variations, the system is configured to add the mixed feed stream to the ammonia over a process of 60 minutes to 1 minute, or 30 minutes to 5 minutes, 30 minutes to about 15 minutes, or 15 minutes to 5 minutes; or about 60 minutes, about 30 minutes, about 15 minutes, or about 5 minutes. In some embodiments, the system is configured to add the mixed feed stream to the ammonia at any rate suitable for maintaining a constant temperature. In some variations, the reactor (110) is configured to receive ammonia (112) in liquid form. In other variations, the reactor (110) is configured to receive the mixed feed stream (111) in atomized form. In some variations of the foregoing, the reactor is configured to add the mixed feed stream above the surface of the liquid ammonia, below the surface of the liquid ammonia, or a combination thereof. In another variation, the reactor is configured to stir the liquid ammonia while adding the mixed feed stream. In yet another variation, the reactor is configured to stir the mixed feed stream while adding the mixed feed stream to the liquid ammonia. In some variations, the reactor (110) includes an inert packed bed. In some variations, the gas-liquid reaction takes place through the inert packed bed, and the atomized mixed feed stream and the countercurrent of ammonia flow through the inert packed bed. In some of the above variations, the ammonia is in gaseous form. In other variations, the ammonia is in liquid form. In other variations, the system further includes a controller configured to isothermally control the combination of the mixed feed stream and ammonia. As described above regarding the integration method, by controlling the reaction conditions of this step, the reaction can be induced to optionally produce a compound of formula (2). Again from 3In this regard, the hydroxypropanamide stream (114) is fed to the reactor (120). The reactor (120) additionally receives a dehydrating agent (123). Subsequently, the hydroxypropanamide undergoes dehydration in the reactor (120). Amide products and / or nitrile products can be produced. In some variations, the reactor (120) comprises a continuous packed bed vapor phase reactor. In another variation, the reactor (120) comprises a multi-temperature stage column. In some variations, the reactor (120) is operated at a concentration of about 380°C to about 390°C. Fig. 3 In some variations illustrated in, it should be understood that the hydroxypropanamide stream (114) does not require additional processing to remove solvent and / or ammonia at this stage. Rather, the solvent and / or ammonia can be transported through an integrated system and 3 As illustrated in Fig., it can be removed in the distillation unit (122). 3A distillation unit (122) as illustrated in [Image] is connected to a reactor (120). In some variations, the distillation unit (122) may be part of the reactor (120). In other variations, the distillation unit (122) may be a separate unit from the reactor (120), and a product stream containing an amide product and / or nitrile product, a solvent, ammonia, and other components is fed to the distillation unit (122). The distillation unit (122) is configured to separate the produced products and components in the reactor (120) into four separate streams (124-127) of the compound of formula (3-I) or its isomer, the compound of formula (3) or its isomer, the solvent, and ammonia. However, it should be understood that in other variations, the distillation unit may be configured to separate specific components from the reactor (120). For example, in one variation, the distillation unit focuses on separating the compound of formula (3-I) and / or the compound of formula (3), or its isomers, without separating the solvent and / or ammonia that may be present in the system.

[0045] Accordingly, in a particular embodiment, an integrated system comprising the following is provided: a first reactor configured to receive an epoxide, carbon monoxide, and a solvent and to produce a carbonylation product stream in the presence of a carbonylation catalyst, wherein the carbonylation product stream comprises a beta-lactone, a solvent, and a carbonylation catalyst; a separation unit configured to receive the carbonylation product stream and to remove at least a portion of the carbonylation catalyst to form a mixed feed stream, wherein the mixed feed stream comprises a beta-lactone and a solvent; a second reactor configured to receive the mixed feed stream and ammonia and to produce a hydroxypropanamide stream, wherein the hydroxypropanamide stream comprises hydroxypropanamide, a solvent, and ammonia; and a third reactor configured to receive the hydroxypropanamide stream and a dehydrating agent and to produce a product stream, wherein the product stream comprises an amide and / or nitrile product, a solvent, and ammonia.

[0046] In some variations, the integrated system comprises: an epoxide source configured to discharge an epoxide stream; a carbon monoxide source configured to discharge a carbon monoxide stream; a solvent source configured to discharge a solvent stream; a first reactor comprising at least one inlet configured to receive the epoxide, carbon monoxide, and solvent, and an outlet configured to discharge a carbonylation product stream produced in the presence of a carbonylation catalyst in the first reactor, wherein the carbonylation product stream comprises a beta-lactone, a solvent, and a carbonylation catalyst; a separation unit configured to receive the carbonylation product stream, remove at least a portion of the carbonylation catalyst, and form a mixed feed stream, wherein the mixed feed stream comprises a beta-lactone and a solvent; an ammonia source configured to discharge ammonia; A second reactor comprising at least one inlet configured to receive a mixed feed stream and ammonia, and an outlet configured to discharge a hydroxypropanamide stream, wherein the hydroxypropanamide stream comprises hydroxypropanamide, a solvent, and ammonia; and a third reactor comprising an inlet configured to receive a hydroxypropanamide stream, and an outlet configured to produce a product stream from the body of a dehydrating agent, wherein the product stream comprises an amide and / or nitrile product, a solvent, and ammonia.

[0047] do 3The illustration shows an exemplary system comprising a separation unit (107) for removing the carbonylation catalyst from the carbonylation product stream, but in other variations where a heterogeneous carbonylation catalyst is used, such a separation unit may not be necessary. For example, in other embodiments, the system comprises: a first reactor configured to receive an epoxide, carbon monoxide, and a solvent and to produce a mixed feed stream in the presence of a carbonylation catalyst, wherein the mixed feed stream comprises a beta-lactone, a solvent, and a carbonylation catalyst; a second reactor configured to receive the mixed feed stream and ammonia and to produce a hydroxypropanamide stream, wherein the hydroxypropanamide stream comprises hydroxypropanamide, a solvent, and ammonia; and a third reactor configured to receive the hydroxypropanamide stream and a dehydrating agent and to produce a product stream, wherein the product stream comprises an amide and / or nitrile product, a solvent, and ammonia.

[0048] do 3 Although a reactor (120) containing this dehydrating agent (123) is illustrated, it should be further understood that in other variations, the dehydrating agent (123) may be contained in the reactor (120), for example, in a catalyst bed. 3 Fig. illustrates an exemplary system for producing amide and / or nitrile products from epoxide and carbon monoxide, but it should be understood that in other variations, beta-lactone and / or hydroxypropanamide may be obtained from commercially available sources. Fig. 3 Other variations of the exemplary system illustrated in It is also considered. For example, a mixed feed stream can be combined with ammonia and a dehydrating agent in a single reactor to produce a product stream. 4In this regard, the system (200) is an exemplary system for the integrated production of amide products and / or nitrile products, and the mixed feed stream is combined with ammonia and a dehydrating agent in one reactor to produce a product stream.

[0049] The system (200) is It includes a reactor (201) in which carbonylation of the epoxide takes place. Epoxide (202), carbon monoxide (203), solvent (204) and the carbonylation catalyst (205) are supplied to the reactor (201). The epoxide is carbonylated in the presence of the carbonylation catalyst and the solvent to produce a carbonylation product stream (206) comprising the compound of formula (1), the solvent, and the carbonylation catalyst. The carbonylation product stream (206) is The carbonylation catalyst can be removed through an additional processing step. 4 As illustrated in [Image], the carbonylation product stream (206) is It proceeds to a separation unit (207), which separates the carbonylation catalyst (208) and yields a mixed feed stream (211) containing a compound of formula (1) and a solvent. The recovered carbonylation catalyst (208) It can be reused and recycled back into the system (200).

[0050] Without requiring further processing of the mixed feed stream (211) to remove the solvent, the mixed feed stream (211) is fed to the reactor (210). The reactor (210) also contains ammonia (212), It accepts a dehydrating agent (213) and optionally a base (214). Then Hydroxypropanamide may undergo dehydration in a reactor (210) to produce an amide product and / or a nitrile product. A distillation unit (216), which may be incorporated as part of the reactor (210) or as a separate unit from the reactor (210), separates the compound of formula (3-I) or its isomer, the compound of formula (3) or its isomer, the solvent, and ammonia into four separate streams (217-220). However, in other variations, it should be understood that the distillation unit may be configured to separate specific components from the reactor (210). For example, in one variation, the distillation unit focuses on separating the compound of formula (3-I) and / or the compound of formula (3), or its isomer, without separating the solvent and / or ammonia that may be present in the system.

[0051] In other variations, a carrier gas may be used for the conversion of hydroxypropanamide into amide products and / or nitrile products. Thus, in certain embodiments, a system is provided comprising a reactor configured to receive a hydroxypropanamide stream having a carrier gas and a dehydrating agent and to discharge a product stream comprising a compound of formula (3-I) and / or a compound of formula (3), or an isomer thereof. In some variations, the carrier gas comprises ammonia. In other variations, the carrier gas comprises ammonia and nitrogen. In some variations, the product stream further comprises ammonia, water, or a combination thereof.

[0052] do 5 In relation to this, the system (300) is another exemplary system for the integrated production of amide products and / or nitrile products. The system (300) Reactor (310) and includes a reactor (320). The reactor (310) is Mixed feed stream (311) and receives ammonia (312), and discharges a stream (313) that may contain excess ammonia, solvent and / or light material, and a hydroxypropanamide stream (314). The reaction vessel (320) receives the hydroxypropanamide stream (314) and accommodates a carrier gas (323). The reaction vessel (320) contains a dehydrating agent (Figure 5 (Not shown in ). The reaction vessel (320) discharges the product stream (324). In some variations, the product stream (324) Further processing may isolate a compound of formula (3-I) and / or a compound of formula (3) as defined herein, a compound of formula (3-I) and / or a compound of formula (3), ammonia, or water, or any combination thereof.

[0053] The reaction vessel described in the system of the present invention is configured to operate at any suitable temperature and / or pressure. In some variations, the reaction vessel described in the system of the present invention is mounted to maintain the contents of the reaction vessel under positive pressure of an inert gas. In some embodiments, the inert gas comprises nitrogen. The reaction vessel described in the system of the present invention is mounted to discharge gas. In some embodiments, the reaction vessel described in the system of the present invention is mounted to discharge ammonia. The reaction vessel described in the system of the present invention is mounted to remove volatile substances. In some embodiments, the volatile substances comprise ammonia and other gases. The reaction vessel described in the system of the present invention is mounted to deliver any stream described herein. In some variations, the reaction vessel is configured to receive a stream from any other reaction vessel as described in the system of the present invention. In other variations, the reaction vessel is configured to discharge a stream to any other reaction vessel as described in the system of the present invention. In some variations, the reaction vessel is configured to discharge a stream to a downstream plant or storage, or any combination thereof.

[0054] In some variations, any system described herein may be configured to operate as a continuous process. In other variations, any reaction system described herein may be configured to operate as a batch process. In other variations, any reaction system described herein may be configured to operate as a semi-batch process. In other variations, any reaction system described herein may be configured to operate as a semi-continuous process. In some variations, the reactor described in the system described herein may be any vessel suitable for receiving the reagent product involved in the reaction of interest. The reactor may be configured as a receptacle, tank, chamber, pressure vessel, well, or other structure capable of receiving solids or liquids, and may be sealed to contain a gaseous reaction mixture. The reactor includes one or more inlets for providing reagents and / or outlets for removing intermediates and / or products. The reactor may be a standalone unit or one of an array of multiple units. The volume of the reactor may vary within the scope of the invention. The material of the reaction vessel may be any suitable material for accommodating the reagents and products involved in the reaction of interest before, during, or after the reaction of interest. The reactor may include means for providing heat to the reagents and products involved in the reaction of interest. Such means may include the use of a heating jacket, heating coil, heating tube, or heat exchanger, or any combination thereof. The reactor may include means for removing the mixing of the reagents and products involved in the reaction of interest. Such means may include the use of a mechanical shaker. Examples of mechanical shakers include axial flow impellers and radial flow impellers.

[0055] Various aspects of the integration method and system are further explored below, including carbonylation product streams, mixed feed streams, hydroxypropanamide streams, and product streams. Additionally, acrylamide and acrylonitrile compounds and other compounds that can be produced using the integration method, as well as amides, lactones, solvents, dehydrating agents, and various other components that can be used in their production, are explored below.

[0056] Carbonylation product stream

[0057] The carbonylation product stream is a product produced from the carbonylation of an epoxide in the presence of a carbonylation catalyst and a solvent. Any suitable method and condition may be used for the carbonylation reaction. For example, refer to WO 2013 / 063191 and WO 2016 / 130977. In some embodiments, the carbonylation catalyst comprises a metal porphyrin moiety coordinated with a metal carbonyl moiety. In some variations, the metal porphyrin moiety comprises an optionally substituted porphyrin. In other variations, the metal porphyrin moiety comprises an optionally substituted tetraphenylporphyrin. In other embodiments, the carbonylation catalyst comprises a metal salen moiety coordinated with a metal carbonyl moiety. In some variations, the metal salen moiety comprises an optionally substituted salen. In yet another variation, the metal porphyrin moiety comprises aluminum or chromium. In another variation, the metal porphyrin moiety comprises aluminum (III) or chromium (III). In another variation, the metal salen moiety comprises aluminum or chromium. In another variation, the metal salen moiety comprises aluminum (III) or chromium (III). In some embodiments, the metal carbonyl moiety comprises a monovalent anionic carbonyl complex of any metal from Group 5, 7, or 9 of the periodic table. In other embodiments, the metal carbonyl moiety comprises a divalent anionic carbonyl complex of any metal from Group 4 or 8 of the periodic table. It should be understood that when the metal carbonyl moiety is divalent anionic, it may typically be two metal porphyrins or two metal salen moietys coordinated with each divalent anionic metal carbonyl moiety. In some variations, the metal carbonyl moiety comprises cobalt. In another variation, the metal carbonyl moiety includes manganese. In yet another variation, the metal carbonyl moiety includes rhodium. In some embodiments, the metal carbonyl moiety is [Co(CO)4] - , [Ti(CO)6]2- , [V(CO)6] - , [Rh(CO)4] - , [Fe(CO)4] 2- , [Ru(CO)4] 2- , [Os(CO)4] 2- , [Cr2(CO) 10 ] 2- , [Fe2(CO)8] 2- , [Tc(CO)5] - , [Re(CO)5] - , or [Mn(CO)5] - , or any combination thereof. In other variations, the metal carbonyl moiety is [Co(CO)4] - Includes

[0058] In other variations of the foregoing, the carbonylation catalyst may be further coordinated with one or more solvents used in the system and method described herein. In one variation, the carbonylation catalyst further comprises THF. In a specific variation, THF is coordinated to aluminum or chromium in a metal porphyrin moiety. In another variation, THF is coordinated to aluminum in a metal porphyrin moiety. In another variation, at least one THF is coordinated to aluminum in a metal porphyrin moiety. In a specific variation, THF is coordinated to aluminum or chromium in a metal salen moiety. In another variation, THF is coordinated to aluminum in a metal salen moiety. In another variation, at least one THF is coordinated to aluminum in a metal salen moiety.

[0059] Any suitable carbonylation catalyst may also be used. For example, refer to WO 2016 / 015019 and WO 2012 / 158573. The carbonylation catalyst may be homogeneous or heterogeneous. In some embodiments, where the carbonylation catalyst is homogeneous, the produced carbonylation product stream contains the carbonylation catalyst in addition to the compound of formula (1) used and the carbonylation reaction solvent. The method is illustrated in Figure 1As illustrated in [Figure], an additional separation step may be required to remove at least some or all of the carbonylation catalyst from the carbonylation product stream. Any suitable method or technique may be used to remove or isolate the carbonylation catalyst from the carbonylation product stream. For example, a membrane, such as a nanofiltration membrane, may be used. The carbonylation catalyst may be recycled back to the carbonylation reactor for further use in the carbonylation reaction. In other embodiments, if the carbonylation catalyst is heterogeneous (e.g., present in a fixed bed within the carbonylation reactor), the carbonylation catalyst may not be present in the produced carbonylation product, and an additional separation step may not be required to remove the carbonylation catalyst. Any suitable carbonylation reaction solvent may be used. For example, refer to WO 2016 / 130977. In some variations, the solvent comprises a polar solvent. In other variations, the solvent comprises an ether. In one variation, the solvent contains tetrahydrofuran.

[0060] The integrated method and system described herein do not require the removal of a solvent from a feed stream to produce hydroxypropanamide. In fact, the solvent may be carried throughout the integrated process and removed from the final product stream containing the amide product and / or nitrile product (e.g., Fig. 1 and 2 (Refer to producing stream (4) in the exemplary reaction equation).

[0061] Mixed feed stream

[0062] For example, too 1A mixed feed stream as described in is obtained from the treatment of a carbonylation stream to remove the carbonylation catalyst. In some embodiments, the mixed feed stream comprises a beta-lactone, such as a compound of formula (1), and a solvent. In some variations, the compound of formula (1) is And,

[0063] During the meal, R 1 is H, alkyl, alkenyl, cycloalkyl, or aryl. In some embodiments, R 1 It is H or alkyl.

[0064] However, it should be understood that in embodiments of the integration method using a heterogeneous carbonylation catalyst, the treatment step described above for removing the carbonylation catalyst may not be necessary. As previously stated, the solvent may be carried throughout the integration process and removed from the final product stream containing the amide product and / or nitrile product (e.g., e.g., f. 1 and 2 (Refer to producing stream (4) in the exemplary reaction scheme). As a solvent present in the mixed feed stream, in some embodiments, the mixed feed stream is homogeneous. In other embodiments, the compound of formula (1) is at least partially soluble in the mixed feed stream. In other embodiments, the compound of formula (1) is soluble in the mixed feed stream. In some variations, the compound of formula (1) is soluble in the mixed feed stream at all operating temperatures described herein.

[0065] Hydroxypropanamide stream

[0066] For example, too 1 A hydroxypropanamide stream as described in [figure] can be obtained by reacting the mixed feed stream described herein with ammonia to produce hydroxypropanamide. The compound of formula (2) is (2) It can be, among the foods, R 1 is H, alkyl, alkenyl, cycloalkyl, or aryl. In some embodiments, R 1 It is H or alkyl.

[0067] Accordingly, in some embodiments, the hydroxypropanamide stream comprises a compound of formula (2), a solvent, and ammonia. The solvent and ammonia are such that the hydroxypropanamide stream is also 1 As illustrated in the exemplary reaction scheme of, it may be present in the hydroxypropaneamide stream when derived from the carbonylation of an epoxide. In some embodiments, such solvents and ammonia may be carried throughout the entire integration process and removed from the final product stream containing the amide product and / or nitrile product (e.g., Fig. 1 Refer to producing stream (4) in an exemplary reaction scheme of ). In other variations of the integrated system and method, the hydroxypropanamide stream may undergo further processing to remove at least some of the solvent and / or ammonia present in the stream.

[0068] In some embodiments, any of the hydroxypropanamide streams described herein further comprise additional products, such as hydroxypropanamide, such as a compound of formula (2-I) and / or an oligomer. In some variations, the compound of formula (2-I) is and, among the formulas, R 1 is H, alkyl, alkenyl, cycloalkyl, or aryl. In some embodiments, R 1 is H or alkyl. For example, in some variations, R 1 H is H, and the compound of chemical formula (2-I) is beta-alanine.

[0069] In some embodiments, the hydroxypropanamide stream has a molar ratio of the compound of Formula (2) to the additional product of 100:1 to about 1:1, 100:1 to about 10:1, or 100:1 to about 50:1; or about 100:1; about 50:1; or about 10:1. In some variations, the hydroxypropanamide stream contains trace amounts of the additional product. In other variations, the hydroxypropanamide stream has substantially no additional product. In one variation, “substantially no additional product” refers to less than 1% (w / w), less than 5% (w / w), less than 10% (w / w), less than 15% (w / w), or less than 20% of the additional product present in the stream. In another variation, “substantially no additional product” refers to up to 20% (w / w) by weight of the additional product present in the stream. In some variations, the hydroxypropanamide stream has a molar ratio of the compound of formula (2) to beta-alanine of 100:1 to about 1:1, 100:1 to about 10:1, or 100:1 to about 50:1; or about 100:1; about 50:1; or about 10:1. In some embodiments, the hydroxypropanamide stream contains trace amounts of beta-alanine. In other embodiments, the hydroxypropanamide stream is substantially free of beta-alanine. In one variation, “substantially free of beta-alanine” refers to less than 1% (w / w), less than 5% (w / w), less than 10% (w / w), less than 15% (w / w), or less than 20% of the beta-alanine present in the stream. In some variations, the hydroxypropanamide stream has a molar ratio of the compound of formula (2) to the oligomer of 100:1 to about 1:1, 100:1 to about 10:1, or 100:1 to about 50:1; or about 100:1; about 50:1; or about 10:1. In some embodiments, the hydroxypropanamide stream contains a trace amount of the oligomer. In other embodiments, the hydroxypropanamide stream is substantially free of the oligomer.In one variant, “substantially free of oligomers” refers to less than 1% (w / w), less than 5% (w / w), less than 10% (w / w), less than 15% (w / w), or less than 20% of the oligomers present in the stream. In another variant, “substantially free of oligomers” refers to up to 20% (w / w) of the oligomers present in the stream by weight.

[0070] In some embodiments, the hydroxypropanamide stream is processed to remove or isolate additional products, such as compounds of formula (2-I) and / or oligomers, from the hydroxypropanamide stream. In some embodiments, the hydroxypropanamide stream is homogeneous. In other embodiments, the compound of formula (2) is at least partially soluble in the hydroxypropanamide stream. In yet another embodiment, the compound of formula (2) is soluble in the hydroxypropanamide stream. In some variations, the compound of formula (2) is soluble in the hydroxypropanamide stream at all operating temperatures described herein. As discussed above, since the hydroxypropanamide stream can be obtained from the mixed feed stream described herein, any additional components present in the reaction to produce the mixed feed stream can be carried into the hydroxypropanamide stream. For example, in some embodiments of the integration method, the mixed feed stream and ammonia (e.g., including ammonia anhydride) may be further combined with a base to produce hydroxypropanamide. In such embodiments, the hydroxypropanamide stream further comprises a base in addition to other components as described above. If a base is present in the hydroxypropanamide stream, the integration method may further include an additional step of removing at least a portion of the base before the dehydration reaction to produce the amide product and / or nitrile product.

[0071] In another variation, a carrier gas may be added to the hydroxypropanamide stream, or the carrier gas may be combined with the hydroxypropanamide stream in a reaction to produce an amide product and / or a nitrile product. For example, in one embodiment, a method is provided comprising: contacting the hydroxypropanamide stream with a heterogeneous dehydrating agent to produce a product stream (as described herein), wherein the hydroxypropanamide stream comprises a molten compound of Formula (2) (as described herein) and a carrier gas. In another embodiment, a method is provided comprising: contacting the hydroxypropanamide stream and the carrier gas with a heterogeneous dehydrating agent to produce a product stream (as described herein), wherein the hydroxypropanamide stream comprises a molten compound of Formula (2). In some variations of the foregoing embodiment, the hydroxypropanamide stream further comprises ammonia and / or evaporated solvent. In another variation, the hydroxypropanamide stream further comprises ammonia and is further combined with the evaporated solvent. In certain embodiments of the integration method, it should be understood that the hydroxypropanamide stream cannot be formed or / or isolated. For example, Fig. 2 Referring again to the, the hydroxypropanamide stream may not be formed or / or isolated when the mixed feed stream reacts with ammonia and dehydration, or reacts in a single reaction vessel to produce an amide product and / or a nitrile product.

[0072] product stream

[0073] The product stream comprises amide products and / or nitrile products produced from hydroxypropanamide. In some variations, the product is an unsaturated nitrile or unsaturated amide compound. The product may correspond to a compound of formula (3-I) and / or a compound of formula (3) or its isomers:

[0074] (3-1) or (3),

[0075] During the meal, R 1 is H, alkyl, alkenyl, cycloalkyl, or aryl. In some embodiments, R 1 is H or alkyl. Accordingly, in some embodiments, the product stream comprises a compound of formula (3-I) or its isomer, a compound of formula (3) or its isomer, a solvent, and ammonia. The solvent and ammonia are such that such a product stream also 1 and 2 As illustrated in the exemplary reaction scheme, it may be present in the product stream if derived from the carbonylation of an epoxide. In some embodiments, such solvent and ammonia may be carried throughout the entire integration process and then removed from the product stream.

[0076] In some variations, the integration method further comprises separating one or more components of the product stream. Any suitable method may be used to separate components from the product stream. For example, in one variation, distillation may be used. For example, in one variation, the integration method further comprises isolating the compound of formula (3-I) and / or the compound of formula (3), or its isomer. In addition to isolating the amide product and / or nitrile product, one or more other components present in the product stream may also be isolated and recovered. For example, in certain variations, the method further comprises isolating ammonia and / or solvent. Such recovered ammonia and / or solvent may be reused in any of the methods or systems described herein. As discussed above, since the product stream may be obtained from the mixed feed stream described herein, any additional components present in the reaction for producing the mixed feed stream may be transported into the product stream. For example, in some embodiments of the integration method, the mixed feed stream and ammonia (e.g., including ammonia anhydride) may be further combined with a base to produce hydroxypropanamide. In such embodiments, the hydroxypropanamide stream further comprises a base in addition to other components as described above. If the base present in the hydroxypropanamide stream is not removed prior to the dehydration reaction, the product stream will also contain the base. Thus, in some variations, if the base is present in the product stream, the product stream may undergo further processing to isolate and recover the base. This recovered base may be reused in any of the methods or systems described herein. Similarly, as discussed above, if a carrier gas is present in the conversion of hydroxypropanamide to an amide product and / or a nitrile product, the carrier gas may also be present in the product stream.If a carrier gas is present in the product stream, the product stream may undergo further processing to recover and isolate the carrier gas. This recovered carrier gas may be reused in any of the methods or systems described herein.

[0077] Acrylonitrile compounds and other nitrile compounds

[0078] In some embodiments, the acrylonitrile compound and other nitrile compound produced according to the method of the present invention are compounds of formula (3) or isomers thereof:

[0079] (3),

[0080] During the meal, R 1 is H, alkyl, alkenyl, cycloalkyl, or aryl. "Alkyl" refers to a monoradical unbranched or branched saturated hydrocarbon chain. In some embodiments, the alkyl has 1 to 10 carbon atoms (i.e., C 1-10 alkyl), 1 to 9 carbon atoms (i.e., C 1-9 alkyl), 1 to 8 carbon atoms (i.e., C 1-8 alkyl), 1 to 7 carbon atoms (i.e., C 1-7 alkyl), 1 to 6 carbon atoms (i.e., C 1-6 alkyl), 1 to 5 carbon atoms (i.e., C 1-5 alkyl), 1 to 4 carbon atoms (i.e., C 1-4 alkyl), 1 to 3 carbon atoms (i.e., C 1-3 alkyl), or 1 to 2 carbon atoms (i.e., C 1-2It has an alkyl group. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, 2-pentyl, isopentyl, neopentyl, hexyl, 2-hexyl, 3-hexyl, 3-methylpentyl, etc. When an alkyl residue having a specific number of carbon atoms is named, all geometric isomers having that number of carbon atoms may be included; thus, for example, "butyl" may include n-butyl, sec-butyl, isobutyl, and t-butyl; and "propyl" may include n-propyl and isopropyl. Additionally, it should be understood that when a range of values ​​is listed, it is intended to encompass each value and sub-range within the range. For example, "C 1-6 alkyl" (this is 1-6 C alkyl, C1-C6 alkyl, or C 1-6 (which may also be referred to as alkyl) is C1, C2, C3, C4, C5, C6, C 1-6 , C 1-5 , C 1-4 , C 1-3 , C 1-2 , C 2-6 , C 2-5 , C 2-4 , C 2-3 , C 3-6 , C 3-5 , C 3-4 , C 4-6 , C4-5, and C 5-6 It is intended to encompass alkyl groups. "Alkenyl" refers to an unsaturated linear or branched monovalent hydrocarbon chain or a combination thereof having at least one site of olefinic unsaturation (i.e., having at least one moiety of the formula C=C). In some embodiments, the alkenyl consists of 2 to 10 carbon atoms (i.e., C 2-10It has an alkenyl group. The alkenyl group may be in a "cis" or "trans" configuration, or alternatively, an "E" or "Z" configuration. Examples of alkenyls include ethenyl, allyl, prop-1-enyl, prop-2-enyl, 2-methylprop-1-enyl, but-1-enyl, but-2-enyl, but-3-enyl, their isomers, etc. "Cycloalkyl" refers to a carbon-circulating non-aromatic group connected through a cyclic carbon atom. Examples of cycloalkyls include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc. "Aryl" refers to a monovalent aromatic carbon-circulating group of 6 to 18 cyclic carbon atoms having a single ring or cyclic system having multiple condensed rings. Examples of aryls include phenyl, naphthyl, etc. In some variations, R 1 The alkyl, alkenyl, cycloalkyl, or aryl group for may be optionally substituted. The term “optionally substituted” means that the specified group is unsubstituted or substituted by one or more substituent groups. In certain variations, the optional substituents include halo, -OSO2R2, -OSiR4, -OR, C=CR2, -R, -OC(O)R, -C(O)OR, and -C(O)NR2, wherein R is independently H, optionally substituted alkyl, optionally substituted alkenyl, or optionally substituted aryl. In some embodiments, R is independently unsubstituted alkyl, unsubstituted alkenyl, or unsubstituted aryl. In some embodiments, R is independently H, methyl (Me), ethyl (Et), propyl (Pr), butyl (Bu), benzyl (Bn), allyl, phenyl (Ph), or haloalkyl. In certain embodiments, the substituents are F, Cl, -OSO2Me, -OTBS (where "TBS" is tert-butyl(dimethyl)silyl), -OMOM (where "MOM" is methoxymethylacetal), -OMe, -OEt, -O i Pr, -OPh, -OCH2CHCH2, -OBn, -OCH2(furyl), -OCF2CHF2, -C=CH2, -OC(O)Me, -OC(O)n Pr, -OC(O)Ph, -OC(O)C(Me)CH2, -C(O)OMe, -C(O)O n It may include Pr, -C(O)NMe2, -CN, -Ph, -C6F5, -C6H4OMe, and -OH. In certain embodiments, R 1 It is H or alkyl. In some variations, R 1 is H, and the compound of chemical formula (3) is chemical formula (also known in the art as acrylonitrile). In other variations, R 1 is an alkyl. In certain variations, R 1 C 1-6 It is an alkyl. In one variation, R 1 It is methyl or ethyl. R 1 In the case of this methyl, the compound of chemical formula (3) is Or its isomer (also known in the art as crotononitrile). R 1 In the case of this ethyl, the compound of chemical formula (3) is Or its isomer (also known in the art as 2-pentenitrile).

[0081] Acrylamide and other amides

[0082] In some embodiments, acrylamide or other amides may be used to produce acrylonitrile compounds and other nitrile compounds. In some variations, such amides are of formula (3-1) It is a compound of, where in the formula, R 1 is H, alkyl, alkenyl, cycloalkyl, or aryl. In certain embodiments, R 1 It is H or alkyl.

[0083] In some variations, R 1 is H, and the compound corresponds to the compound of formula (3-I), and also acrylamide It is also known as. In other variations, R 1 is an alkyl. In certain variations, R1 C 1-6 It is an alkyl. In one variation, R 1 It is methyl or ethyl. R 1 In the case of this methyl, the compound of formula (3-I) is or (Also known in the industry as but-2-enamide) is R 1 In the case of this ethyl, the compound of chemical formula (2) is or (Also known in the art as pent-2-enamide). When a compound of formula (3-I), or its isomer, is used to produce a compound of formula (3), or its isomer, R of formula (3-I). 1 It should be generally understood that it is as defined for formula (3). Acrylamide and other amides, such as compounds of formula (3-I), may be obtained from any commercially available source or produced according to any method known in the art. In certain embodiments, compounds of formula (3-I) produced according to the method of the present invention may be isolated. In some variations, compounds of formula (3-I) produced according to the method of the present invention are isolated and purified. Compounds of formula (3-1) produced according to the method of the present invention may be isolated.

[0084] Beta-hydroxyamides and other hydroxyamides

[0085] In some embodiments, the beta-hydroxyamide and other hydroxyamides that can be used to produce acrylonitrile compounds and other nitrile compounds according to the method of the present invention are of formula (2) It is a compound of, and in the formula, R 1 is H, alkyl, alkenyl, cycloalkyl, or aryl. In certain embodiments, R 1 It is H or alkyl. In some variations, R 1 is H, and the compound of chemical formula (2) is (or 3-hydroxypropanamide). In other variations, R 1 is an alkyl. In certain variations, R 1 C 1-6 It is an alkyl. In one variation, R 1 It is methyl or ethyl. R 1 In the case of this methyl, the compound of chemical formula (2) is (or 3-hydroxybutanamide). R 1 In the case of this ethyl, the compound of chemical formula (2) is (or 3-hydroxypentanamide).

[0086] If the compound of formula (2) is used to produce the compound of formula (3) or its isomer, R of formula (2) 1 It should be generally understood that it is as defined for formula (3). Beta-hydroxyamides and other amides, such as compounds of formula (2), may be obtained from any commercially available source or produced according to any method known in the art. In certain embodiments, compounds of formula (2) produced according to the method of the present invention may be isolated. In some variations, compounds of formula (2) produced according to the method of the present invention are isolated and purified. Compounds of formula (2) produced according to the method of the present invention may be isolated.

[0087] Beta-lactones and other lactones

[0088] In some embodiments, beta-lactone may be used to produce beta-hydroxyamide, acrylamide, acrylonitrile, and other compounds according to the method of the present invention. In certain embodiments, beta-lactone is of formula (1): (1) is a compound, and in the formula, R 1 is H, alkyl, alkenyl, cycloalkyl, or aryl. In certain embodiments, R 1 It is H or alkyl. In some variations, R1 is H, and the compound of chemical formula (1) is known in the art as (also known as beta-propiolactone) is. In other variations, R 1 is an alkyl. In certain variations, R 1 C 1-6 It is an alkyl. In one variation, R 1 It is methyl or ethyl. R 1 In the case of this methyl, the compound of chemical formula (1) is (Also known in the industry as beta-butyrolactone) is. R 1 In the case of this ethyl, the compound of chemical formula (1) is (It is also known in the industry as beta-valerolactone.)

[0089] Beta-lactones, such as compounds of formula (1), can be obtained from any commercially available source or produced according to any method known in the art. For example, beta-propiolactones can be obtained by reacting ethylene oxide and carbon monoxide under suitable conditions. In some variations, amide products and / or nitrile products can be produced from any beta-lactone provided in column B of Table A below. As indicated in Table A, such beta-lactones in column B can be produced from the corresponding epoxides in column A of the table.

[0090] Table A.

[0091]

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101] Beta-lactones, such as compounds of formula (1), can be obtained from renewable feedstocks. For example, if beta-propiolactones are produced from ethylene oxide and carbon monoxide, either or both of the ethylene oxide and carbon monoxide can be obtained from renewable feedstocks using methods known in the art. If beta-lactones, such as compounds of formula (1), are obtained partially or wholly from renewable feedstocks, polyamides produced from such beta-lactones according to the methods described herein have a biocontent greater than 0%. Various techniques are known in the art to determine the biocontent of a material. For example, in some variations, the biocontent of a material can be measured using the ASTM D6866 method, which enables the determination of the biocontent of a material using accelerator mass spectrometry, liquid scintillation counting, and radiocarbon analysis by isotope mass spectrometry. Biocontent results can be derived by assigning 100% to 107.5 pMC (modern carbon percentage) and 0% to 0 pMC. For example, a sample measuring 99 pMC will provide an equivalent biocontent result of 93%. In one variation, biocontent can be determined according to ASTM D6866 Modification 12 (i.e., ASTM D6866-12). In another variation, biocontent can be determined according to the procedure of Method B of ASTM-D6866-12. Other techniques for evaluating the biocontent of a material are described in US Patent Nos. 3,885,155, 4,427,884, 4,973,841, 5,438,194, and 5,661,299, as well as WO2009 / 155086.

[0102] ammonia

[0103] The ammonia described herein may be obtained from any commercially available source or produced according to any method known in the art. In some embodiments, the ammonia comprises anhydrous ammonia. In other embodiments, the ammonia comprises liquid ammonia. In yet another embodiment, the ammonia comprises liquid anhydrous ammonia. In some variations, the ammonia is anhydrous ammonia. In other variations, the ammonia is liquid ammonia. In yet another variation, the ammonia is liquid anhydrous ammonia. In some variations of the foregoing, the ammonia may further comprise water. In such variations, the ammonia comprises at least 0.1%, at least 1%, at least 5%, at least 10%, at least 15%, or at least 30% by weight of water. In other variations, ammonia comprises at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, or at least 90% by weight of water. In yet another variation, ammonia comprises about 0.1 wt% to about 15 wt% of water, 0.1 wt% to about 10 wt% of water, or 0.1 wt% to about 1 wt% of water. In some embodiments, ammonia is a carrier gas in any of the systems and methods described herein. In other embodiments, ammonia is a component of the carrier gas in any of the systems and methods described herein. In such cases, other components of the carrier gas may comprise nitrogen, evaporated solvent, or a combination thereof. In some embodiments, ammonia is present in excess in any of the methods or systems described herein. In some embodiments, ammonia is volatile. In another embodiment, ammonia is volatile and is removed from any of the systems or methods described herein by distillation. In some variations, distillation includes vacuum distillation. In other variations, ammonia is removed from any of the systems or methods described herein by vacuum.In another variation, ammonia is removed from any of the systems or methods described herein by off-gas generation of ammonia. In some variations, ammonia is removed from the hydroxypropanamide stream. In some variations, ammonia is removed from the hydroxypropanamide stream by off-gas generation of ammonia. In other variations, ammonia is removed from the product stream. In other variations, ammonia is removed from the product stream by off-gas generation of ammonia. In another embodiment, at least a portion of the ammonia is allowed off-gas, but a portion of the ammonia remains with the hydroxypropanamide stream to dissolve the compound of formula (2). In some variations, the compound of formula (2) is 3-hydroxypropanamide (3-HPA). In such a variation, partially allowing 3-HPA dissolved in ammonia to go off-gas can provide a spurious liquid that can be used as a substitute for molten 3-HPA. In any of the embodiments described above, the removed ammonia can be recovered to storage and / or reused in any of the methods or systems described herein.

[0104] menstruum

[0105] The solvents described herein may be obtained from any commercially available source or produced according to any method known in the art. 1 and 2 Referring to, the solvent present throughout the entire integration method may be a carbonylation solvent, and this also 1 and 2It should be understood that it can be used in the first step of an exemplary reaction to produce a carbonylation product stream. Accordingly, in some variations, the solvent may also be referred to as the carbonylation solvent. In some embodiments, the solvent comprises a polar solvent. In other embodiments, the solvent comprises a polar aprotic solvent. In some variations, the solvent comprises an ether. In other variations, the solvent comprises tetrahydrofuran. In some embodiments, the solvent comprises a polar protic solvent. In some variations, the solvent comprises an alcoholic solvent. In other variations, the solvent comprises an alcohol. In yet another variation, the alcohol is C1-C 10 It includes alcohol. In some embodiments, the alcohol includes ethanol. In some embodiments, the solvent includes ethanol. In some embodiments, the solvent includes a polar aprotic solvent and an alcohol. In some variations, the solvent includes an ether and an alcohol. In one variation, the ether is tetrahydrofuran. In another variation, the alcohol is ethanol. In some embodiments, the solvent is used as a carrier gas in any of the systems and methods described herein. In other embodiments, the solvent is used as a component of the carrier gas in any of the systems and methods described herein. In the aforementioned embodiments, the solvent is evaporated. In such cases, other components of the carrier gas may include nitrogen, ammonia, or a combination thereof. In some embodiments, the solvent is removed from any of the systems or methods described herein by distillation. In some variations, the distillation includes vacuum distillation. In other variations, the solvent is removed from any of the systems or methods described herein by vacuum. In some variations, the solvent is removed from the hydroxypropanamide stream. In other variations, the solvent is removed from the product stream. In any of the embodiments described above, the removed solvent may be recovered for storage and / or reused in any of the methods or systems described herein.

[0106] Carrier gas

[0107] The carrier gas described herein may be obtained from any commercially available source or may be produced according to any method known in the art. In some embodiments, the carrier gas described herein facilitates the passage of any beta-hydroxyamide described herein through any of the dehydrating agents described herein. In other variations, the carrier gas described herein facilitates the passage of any of the hydroxypropanamide streams described herein through any of the dehydrating agents described herein. In yet another variation, the carrier gas described herein facilitates the passage of any mixed feed stream described herein through any of the dehydrating agents described herein. In some variations of the foregoing, the dehydrating agent is heterogeneous. In some variations of the foregoing, the dehydrating agent is a heterogeneous dehydrating agent. In other variations, any beta-hydroxyamide, hydroxypropanamide stream, or mixed feed stream described herein is mixed / evaporated with the carrier gas and fed continuously to a fixed-bed reactor filled with a dehydrating agent. In another variation, any beta-hydroxyamide, hydroxypropanamide stream, or mixed feed stream described herein is evaporated in the absence of an additional carrier gas and fed continuously to a fixed-bed reactor filled with a dehydrating agent. In such cases, various components of the beta-hydroxyamide, hydroxypropanamide stream, or mixed feed stream may contain a carrier gas. For example, in the case of a hydroxypropanamide stream containing a compound of formula (2), a solvent, and ammonia, the evaporated solvent and / or ammonia may contain a carrier gas. In some embodiments, the carrier gas contains nitrogen. In other embodiments, the carrier gas contains ammonia. In some variations, the carrier gas contains nitrogen and ammonia. In other variations, the carrier gas contains nitrogen, ammonia, and the evaporated solvent. In yet another variation, the carrier gas contains nitrogen and the evaporated solvent.In another variation, the carrier gas comprises ammonia and evaporated solvent. In some variations, the carrier gas comprises nitrogen and ammonia, and the relative volume of the ammonia gas is in the range of about 1% to about 99%, about 30% to about 99%, about 60% to about 99%, about 90% to about 99%, about 1% to about 60%, about 1% to about 30%, or about 1% to about 10% with respect to the nitrogen gas.

[0108] base

[0109] The bases described herein may be obtained from any commercially available source or produced according to any method known in the art. In some embodiments, the bases described herein facilitate the ring opening of any beta-lactone described herein. In some embodiments, the bases described herein facilitate the conversion of any beta-lactone described herein to produce any of the beta-hydroxyamide, acrylamide, acrylonitrile, and other compounds described herein according to any of the methods or systems described herein. In some embodiments, the base comprises an amine. In some variations, the base comprises an aliphatic amine. In other variations, the base comprises an aromatic amine. The base may be a tertiary amine, a secondary amine, or a primary amine. In some variations, the base comprises triethylamine. In other variations, the base comprises trimethylamine. In other variations, the base comprises pyridine. In some embodiments, the base comprises a metal amide, a metal oxide, a mixed metal oxide, or a metal hydroxide, or any combination thereof. In some embodiments, the base comprises a metal amide. In some variations, the base comprises a sodium amide. In other embodiments, the base comprises a metal oxide. In some variations, the base comprises calcium oxide. In yet another embodiment, the base comprises a metal hydroxide. In some variations, the base comprises tetramethylammonium hydroxide. In yet another embodiment, the base is heterogeneous. In some variations, the base comprises a zeolite or clay mineral, or a combination thereof. In some embodiments, the base is volatile. In other embodiments, the base is volatile and is removed from any of the systems or methods described herein by distillation. In some variations, the distillation comprises vacuum distillation. In other variations, the base is removed from any of the systems or methods described herein by vacuum.In some variations, the base is removed from the hydroxypropanamide stream. In other variations, the base is removed from the product stream. In any of the embodiments described above, the removed base may be recovered to storage and / or reused in any of the methods or systems described herein.

[0110] Dehydration agent

[0111] Dehydration generally involves converting carbon-carbon single bonds into carbon-carbon double bonds and producing water molecules. The dehydration reaction described herein may occur in the presence of a suitable homogeneous or heterogeneous catalyst. In some embodiments, a suitable dehydration catalyst may include an acid, a base, and an oxide. Examples of suitable acids may include H2SO4, HCl, titanic acid, metal oxide hydrates, metal sulfates (MSO4, where M may be Zn, Sn, Ca, Ba, Ni, Co, or other transition metals), metal oxide sulfates, metal phosphates (e.g., M3(PO4)2, where M may be Ca or Ba), metal phosphates, metal oxide phosphates, carbon (e.g., transition metals on a carbon support), inorganic acids, carboxylic acids, their salts, acidic resins, acidic zeolites, clays, SiO2 / H3PO4, fluorinated Al2O3, phosphotungstic acid, phosphomolybdic acid, silicomolybdic acid, silicotungstic acid, and carbon dioxide. Examples of suitable bases may include NaOH, ammonia, polyvinylpyridine, metal hydroxides, Zr(OH)4, and substituted amines. Examples of suitable oxides may include Nb2O5, TiO2, ZrO2, Al2O3, SiO2, ZnO2, SnO2, WO3, MnO2, Fe2O3, and V2O5. In some embodiments, the dehydrating agent used in the method described herein comprises phosphorus pentoxide, organoin compounds, carbodiimide compounds, triazine compounds, organosilicon compounds, mixed oxides, transition metal complexes, or aluminum complexes. In certain embodiments, the dehydrating agent used in the method described herein may further comprise a solid support. Suitable solid support may include, for example, hydrotalcite. The dehydrating agent may be obtained from any commercially available source or may be prepared according to any method known in the art.

[0112] Phosphorus compound

[0113] The dehydrating agent used in the method described herein may include a phosphorus compound. In one variation, the dehydrating agent includes a phosphorus pentoxide. In some variations, the dehydrating agent includes an organoin compound. In certain variations, the organoin compound is an organophosphate. In certain variations, the organoin compound is an alkyl halophosphate or a cycloalkyl halophosphate. In one variation, the alkyl halophosphate is an alkyl dihalophosphate or a dialkyl halophosphate. In another variation, the cycloalkyl halophosphate is a cycloalkyl dihalophosphate or a dicycloalkyl halophosphate. In some variations of the aforementioned organoin compound, the alkyl is C1-C 10 It is an alkyl. In other variations of the aforementioned organoin compound, the cycloalkyl is C3-C 10 It is a cycloalkyl. In some variations, the cycloalkyl contains only C and H when unsubstituted. In other variations, the cycloalkyl may have one or multiple rings. In other variations, cycloalkyls having more than one ring may be linked together by CC bonds, fused, spiro or bridging, or a combination thereof. In some embodiments, the cycloalkyl is C3-C 10 It is a cycloalkyl. In another variation of the aforementioned organoin compound, the halophosphate is a chlorophosphate. In another variation of the aforementioned organoin compound, the halophosphate is a fluorophosphate. Suitable organoin compounds used in the method described herein may include, for example, ethyl dichlorophosphate, diethyl chlorophosphate, methyl dichlorophosphate, dimethyl chlorophosphate, ethyl difluorophosphate, diethyl fluorophosphate, methyl difluorophosphate, or dimethyl fluorophosphate, or any combination thereof.

[0114] Carbodiimide compounds

[0115] In certain embodiments, the dehydrating agent includes carbodiimide. The carbodiimide compound has the chemical formula It can correspond to, where each R 4 and R 5 is independently an alkyl or cycloalkyl. In a specific variation of the foregoing, R 4 and R 5 is different. In another variation of the aforementioned, R 4 and R 5 is identical. In other variations, each R 4 and R 5 is independently cycloalkyl. In certain variations, each R 4 and R 5 is independently alkyl. In certain variations, each R 4 and R 5 is independently independently C 1-6 It is an alkyl. In one variation, each R 4 and R 5 is independently methyl, ethyl, or propyl. In another variation, R 4 and R 5 Both are methyl, ethyl, or propyl. In another variation, R 4 and R 5 Both are cyclohexyl. In another variant, R 4 is alkyl, and R 5 is a cycloalkyl.

[0116] Suitable carbodiimide compounds used in the methods described herein are, for example, (also N,N ' - May include (known in the art as dicyclohexylcarbodiimide), and in the formula, R 4 and R 5 Both are cyclohexyl.

[0117] triazine compounds

[0118] In a specific embodiment, the dehydrating agent comprises a triazine compound. In one variation, the triazine compound is 1,3,5-triazine, which has the following structure:

[0119] .

[0120] The triazine compounds described herein may be optionally substituted with one or more substituents. In some variations, the triazine compounds are substituted with one, two, or three substituents. In certain variations, the substituents may be halo groups. For example, in certain variations, the triazine compound is a halo-substituted triazine compound. In certain variations, the triazine compound is a 1,3,5-triazine substituted with one, two, or three halo groups. In one variation, the triazine compound is a halo-substituted 1,3,5-triazine. An exemplary triazine compound used in the method described herein is, for example, cyanuric acid chloride It may include.

[0121] organosilicon compounds

[0122] In certain embodiments, the dehydrating agent comprises an organosilicon compound. In some variations, the organosilicon compound is a silazane. The silazane may be unsubstituted or substituted.

[0123] In one variant, the silazane is substituted with an aryl, halo, alkyl, alkoxy, or amino group.

[0124] In certain embodiments, the organosilicon compound is and, among the expressions, each R 6 , R 7 , R 8 and R 9(In each case) is independently H, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl, heteroaryl, halo, amino, or alkoxy. In other variations, the organosilicon compound is a silane. The silane may be unsubstituted (e.g., hydrosilane) or substituted. In some variations, the silane is substituted with 1, 2, 3, or 4 substituents. In one variation, the silane is substituted with an aryl, halo, alkyl, alkoxy, or amino group.

[0125] In certain embodiments, the organosilicon compound is and, where each R 6 , R 7 , R 8 and R 9 is independently H, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl, heteroaryl, halo, amino, or alkoxy. In one embodiment, the organosilicon compound is an arylsilane. In some variations, the arylsilane comprises one, two, or three aryl groups. In a variation of the foregoing, the aryl group is phenyl. Suitable arylsilanes may include, for example, diphenylsilane and phenylsilane. In one variation, the organosilicon compound is Ph2SiH2. In another variation, the organosilicon compound is PhSiH3. In another embodiment, the organosilicon compound is a halosilane, alkoxysilane, or aminosilane. In one embodiment, the organosilicon compound is halosyl, and in some variations, the halosilane comprises one, two, or three halo groups. In certain variations, the halosilane may be further substituted with one or more substituents (non-halo). In one variation, the halosilane is further substituted with one, two, or three substituents (non-halo). In variations of the foregoing, the substituents of the halosilane are independently alkyl or aryl. In one variation of the foregoing, the alkyl substituents of the halosilane are C 1-6It is alkyl. In another variation, the substituent of the halosilane is independently methyl or phenyl. Suitable halosilanes may include, for example, dialkyldihalosilane, aryltrihalosilane, arylalkyldihalosilane, or aryltrihalosilane. In a specific variation, the halosilane is chlorosilane. Suitable chlorosilanes may include, for example, dimethyldichlorosilane, phenyltrichlorosilane, or phenylmethyldichlorosilane. In another embodiment, the organosilicon compound is an alkoxysilane. In a specific variation, the alkoxysilane includes an alkylsilicate. In one variation, the alkoxysilane is C 1-6 It includes alkyl silicates. Suitable alkyl silicates are, for example, n - It includes butylsilicate. In other variations, the alkoxysilane includes one, two, or three alkoxy groups. In certain variations of the foregoing, the alkoxysilane may be further substituted with one, two, or three substituents (other than alkoxy). In one variation, the substituents of the alkoxysilane are independently alkyl or aryl. In one variation of the foregoing, the alkyl substituents of the alkoxysilane are C 1-6 It is alkyl. In another variation, the substituent of the alkoxysilane is independently methyl or phenyl. Suitable alkoxysilanes may include, for example, dimethoxy(methyl)phenylsilane. In another embodiment, the organosilicon compound is aminosilane. In a specific variation, the aminosilane is alkylaminosilane. In a specific variation of the foregoing, the aminosilane may be further substituted with one, two, or three substituents (for example, in addition to amino groups containing alkylamino groups). In one variation, the substituent of the aminosilane is an alkoxy group. In one variation of the foregoing, the alkoxy substituent of the aminosilane is C 1-6It is an alkoxy. In another variation, the substituent of the aminosilane is independently a methoxy or ethoxy. Suitable aminosilanes may include, for example, (3-aminopropyl)triethoxysilane. In another embodiment, the organosilicon compound is bis(trialkylsilyl)amine; in one variation, the organosilicon compound is bis(trimethylsilyl)amine. In some variations of the foregoing, the silanes described herein may be used in combination with an alkylhalogenated ammonium as a dehydrating agent. In one variation, the alkylhalogenated ammonium is a tetrabutylhalogenated ammonium, such as tetrabutylammonium chloride or tetrabutylammonium fluoride. In certain variations, the organosilicon compound and the alkylhalogenated ammonium are provided as a mixture (e.g., in a solvent) or combined separately.

[0126] Transition metals complex

[0127] In certain embodiments, the dehydrating agent comprises a transition metal complex. In some variations, the transition metal complex comprises at least one halide or oxide ligand. The halide or oxide ligand is associated or complexed with the transition metal. In certain variations of the foregoing, the transition metal complex is provided in a solvent. In other variations, the transition metal complex is provided in water or acetonitrile, or a mixture thereof. In one embodiment, the transition metal complex is a metal halide. In some variations, the metal halide comprises a Group 10 metal or a Group 12 metal. In certain variations, the metal halide comprises palladium or zinc. In certain variations, the metal halide comprises chloro. Suitable metal halides may include, for example, palladium chloride or zinc chloride. In some variations of the foregoing, the metal halide is provided in a solvent. In one variation, the metal halide is provided in water, acetonitrile, or a mixture thereof. For example, the transition metal complex used in the method described herein may be palladium chloride or zinc chloride provided in water, acetonitrile, or a mixture thereof. In another embodiment, the transition metal complex comprises a Group 5 metal. In some variations, the transition metal complex comprises vanadium oxide. In one variation, the vanadium oxide is monomeric vanadium oxide. In certain variations, the dehydrating agent comprises vanadium oxide and hydrotalcite. In one variation, the dehydrating agent comprises monomeric vanadium oxide and hydrotalcite. Vanadium oxide (e.g., including monomeric vanadium oxide) may be incorporated onto the surface of the hydrotalcite.

[0128] aluminum complex

[0129] In certain embodiments, the dehydrating agent comprises an aluminum complex. In some variations, the aluminum complex comprises an aluminum halide. In certain variations, the aluminum complex is complexed with water, acetonitrile, or an alkali metal salt, or a mixture thereof. In some variations, the alkali metal salt is a sodium salt or a potassium salt. In some variations, the alkali metal salt is an alkali metal halide salt. In some variations, the alkali metal halide salt is an alkali metal iodide salt. In some variations, the alkali metal halide salt is sodium iodide or potassium iodide. In some variations, the aluminum complex is AlCl3·H2O / KI / H2O / CH3CN. In some variations, the aluminum complex is AlCl3·NaI.

[0130] Other heterogeneous dehydrators

[0131] In some variations, the dehydrating agent is heterogeneous. For example, in certain variations, the dehydrating agent comprises a solid metal oxide, a solid acid, an acid, a weak acid, a strong acid, an ion exchange resin, an aluminosilicate, or any combination thereof. In certain variations, the dehydrating agent comprises a solid metal oxide. In one variation, the dehydrating agent comprises TiO2, ZrO2, Al2O3, SiO2, ZnO2, SnO2, WO3, MnO2, Fe2O3, SiO2 / Al2O3, ZrO2 / WO3, ZrO2 / Fe2O3, or ZrO2 / MnO2, or any combination thereof. In certain variations, the dehydrating agent comprises titanic acid, a metal oxide hydrate, a metal sulfate, a metal oxide sulfate, a metal phosphate, a metal oxide phosphate, an inorganic acid, a carboxylic acid or its salt, an acidic resin, an acidic zeolite, a clay, or any combination thereof. In certain variations, the dehydrating agent is H3PO4 / SiO2, fluorinated Al2O3, or Nb2O3 / PO4 -3 , Nb2O3 / SO4 -2It includes Nb2O5, H3PO4, phosphate salts, phosphotungstic acid, phosphomolybdic acid, silicomolybdic acid, silicotungstic acid, Mg2P2O7 or MgHPO4, or any combination thereof. In some variations, the dehydrating agent comprises a zeolite. In certain variations, the zeolite is in the form of hydrogen or ammonia, or is a metal-exchanged zeolite. In one variation, the metal-exchanged zeolite comprises Li, Na, K, Ca, Mg, or Cu. In another variation, the zeolite has a pore size with a diameter ranging from 1 to 10 angstroms. In one variation, the zeolite is an intermediate-pore zeolite. In some variations, the zeolite has a pore size of about 5 to 6 Angstroms, or about 5.6 x 6.0 Angstroms, or about 5.1 x 5.5 to 5.3 x 5.6 Angstroms. In another variation, the zeolite is a large-pore zeolite. Suitable zeolites may include, for example, ZSM-12, ZSM-5, mordenite, fauzacite, or zeolite Y. In variations where heterogeneous dehydrating agents, such as those described above, are used, the compound of formula (2) undergoes dehydration to produce the compound of formula (3-I) or the compound of formula (3), or a combination thereof, by passing the compound of formula (2) in the vapor phase through a heated reactor receiving the dehydrating agent. In one variation, the reactor is a packed bed reactor, a fluidized bed reactor, or a moving bed reactor.

[0132] Combination of dehydrating agents

[0133] It should be understood that in some variations, the term "dehydrating agent" may include a combination of formulations. In some variations of the method described herein, the combination of dehydrating agents described herein may be used. In some embodiments, the dehydrating agent comprises a combination of an organosilicon compound and a transition metal complex. In certain variations of the aforementioned combination, the organosilicon compound is N -methyl- N- It is (trimethylsilyl)trifluoroacetamide. In some variations of the aforementioned combination, the transition metal complex is a metal trilate or a metal halide. In one variation, the metal trilate is zinc trilate. In another variation, the metal halide is copper chloride. In another embodiment, the dehydrating agent comprises a combination of a silane and a transition metal complex. In a specific variation of the aforementioned combination, the transition metal complex is an iron complex. In one variation, the dehydrating agent comprises a combination of a silane and an iron complex. In another variation of the combination of a silane and a transition metal complex, the transition metal complex is a metal carbonate. In a specific variation, the metal carbonate is iron. In a specific variation, the metal carbonate is iron carbonate. Suitable metal carbonates include, for example, Fe2(CO)9. In some variations of the aforementioned combination, the organosilicon compound is an alkoxyalkylsilane. In a specific variation, the alkoxyalkylsilane is diethoxymethylsilane. In one variation, the dehydrating agent comprises a combination of iron carbonate and alkoxyalkylsilane. Exemplary combinations of dehydrating agents that can be used in the method described herein include zinc trilate and N -methyl- N -(trimethylsilyl)trifluoroacetamide; copper chloride and N -methyl- N -(trimethylsilyl)trifluoroacetamide; iron complex and silane; and includes iron carbonate and diethoxymethylsilane.

[0134] Specific dehydrating agent

[0135] In certain variations, the dehydrating agent comprises TiO2 and / or SiO2. These variations of the dehydrating agent are explored in more detail below. It should be understood that the TiO2 described herein may be provided in any suitable mineral form, including rutile or zeolite forms. In certain variations, the use of TiO2 as a dehydrating agent in any of the methods and systems described herein unexpectedly resulted in the formation of the compound of formula (3) in exchange for the exclusion of the compound of formula (3-I) in whole or at least in part. For example, in some embodiments, a hydroxypropanamide stream comprising the compound of formula (2), a solvent, and ammonia is combined with TiO2 to produce a product stream comprising the compound of formula (3), or its isomer, a solvent, and ammonia. In some variations of the foregoing, the hydroxypropanamide stream is combined with TiO2 at a temperature of about 300°C to about 450°C. In another variation, the hydroxypropanamide stream is combined with TiO2 at a temperature of 350°C to about 400°C. In yet another variation, the hydroxypropanamide stream is combined with TiO2 at a temperature of about 400°C. In yet another variation, the hydroxypropanamide stream is combined with TiO2 at a temperature of 350°C to 400°C. In some variations of the foregoing, the compound of formula (3) is acrylonitrile, and the compound of formula (2) is 3-hydroxypropanamide. In another variation of the foregoing, the solvent comprises tetrahydrofuran. In yet another variation of the foregoing, the solvent comprises ethanol. In yet another variation of the foregoing, the solvent comprises tetrahydrofuran and ethanol. In some variations of the foregoing, the product stream further comprises the compound of formula (3-I). In some variations, the product stream comprises a trace amount of the compound of formula (3-I).

[0136] In certain variations, the use of SiO2 as a dehydrating agent in any of the methods and systems described herein unexpectedly resulted in the formation of the compound of Formula (3-I) with respect to the wholly or at least partially excluded compound of Formula (3). For example, in some embodiments, a hydroxypropanamide stream comprising the compound of Formula (2), a solvent, and ammonia is combined with SiO2 to produce a product stream comprising the compound of Formula (3-I), or its isomer, a solvent, and ammonia. In some variations of the foregoing, the hydroxypropanamide stream is combined with SiO2 at a temperature of about 250°C to about 350°C. In another variation, the hydroxypropanamide stream is combined with SiO2 at a temperature of 250°C to about 300°C. In yet another variation, the hydroxypropanamide stream is combined with SiO2 at a temperature of about 300°C. In another variation, the hydroxypropanamide stream is combined with SiO2 at a temperature of 300°C. In some variations of the foregoing, the compound of formula (3-I) is acrylamide, and the compound of formula (2) is 3-hydroxypropanamide. In another variation of the foregoing, the solvent comprises tetrahydrofuran. In another variation of the foregoing, the solvent comprises ethanol. In another variation of the foregoing, the solvent comprises tetrahydrofuran and ethanol. In some variations of the foregoing, the product stream further comprises the compound of formula (3). In some variations, the product stream comprises a trace amount of the compound of formula (3).

[0137] In some embodiments, the dehydrating agent comprises TiO2 and SiO2. It has been found, as expected, that in any of the methods and systems described herein, the use of a combination of TiO2 and SiO2 as a dehydrating agent results in the formation of the compound of Formula (3) for the exclusion of all or at least part of the compound of Formula (3-I). For example, in some embodiments, a hydroxypropanamide stream comprising the compound of Formula (2), a solvent, and ammonia is combined with a dehydrating agent comprising TiO2 and SiO2 to produce a product stream comprising the compound of Formula (3), or its isomer, a solvent, and ammonia. In some variations of the foregoing, the hydroxypropanamide stream is combined with TiO2 and SiO2 at a temperature of about 250°C to about 450°C. In some variations of the foregoing, the hydroxypropanamide stream is combined with TiO2 and SiO2 in a column, and the column has a zone containing TiO2 and, separately, a zone containing SiO2. In some variations, the hydroxypropanamide stream first passes through a zone containing SiO2 and then through a zone containing TiO2. In other variations, the hydroxypropanamide stream first passes through a zone containing TiO2 and then through a zone containing SiO2. In some variations, the column is a multi-temperature stage column. In some variations, the zone containing TiO2 operates at a first temperature, and the zone containing SiO2 operates at a second temperature, and the first temperature and the second temperature are different. In some variations, the first temperature is higher than the second temperature. In other variations, the first temperature is 390°C to 400°C, and the second temperature is about 250°C to 300°C. In some variations of the foregoing, the compound of formula (3) is acrylonitrile, and the compound of formula (2) is 3-hydroxypropanamide. In other variations of the foregoing, the solvent comprises tetrahydrofuran. In another variation of the above, the solvent includes ethanol.In another variation of the foregoing, the solvent comprises tetrahydrofuran and ethanol. In another variation of the foregoing, the solvent was absent. In such a variation, the compound of formula (2) can be dissolved in ammonia. In some variations of the foregoing, the product stream further comprises the compound of formula (3-I). In some variations, the product stream comprises a trace amount of the compound of formula (3-I).

[0138] hard material

[0139] Various streams in the integrated method and system described herein, including a carbonylated product stream, a mixed feed stream, a hydroxypropanamide stream and / or a product stream, may further comprise a light material. In some variations, the light material is a low-boiling point component from any upstream process that is not isolated by distillation. In some variations, the light material comprises a solvent or reactant from any upstream process. In other variations, the light material comprises ethylene oxide, acetaldehyde, or carbon monoxide, or any combination thereof. The light material from a given stream may be removed at any point during the process, or may be carried through the process and removed from the final product stream. Thus, in some variations of the integrated method and system described herein, at least a portion of the light material may be removed, and a given stream may have less than 10%, less than 5%, less than 1%, or less than 0.1% by weight of light material. For example, in one variation, the mixed feed stream has less than 10%, less than 5%, less than 1%, or less than 0.1% by weight of light material.

[0140] Downstream use

[0141] Acrylamide, acrylonitrile, and other compounds produced according to the integrated method described herein and using the integrated system described herein may, in some variations, be used as monomers for the industrial production of polymers. The produced compounds of Formula (3-I) may be used to produce one or more downstream products. For example, acrylamide produced according to the method described herein may be used for the production of polyacrylamide. Accordingly, in certain embodiments, a method is provided comprising: producing a compound of Formula (3-I) according to any method of the present invention; and polymerizing the compound of Formula (3-I). In one variation, a method for producing polyacrylamide is provided comprising: producing acrylamide according to any method of the present invention; and polymerizing the acrylamide to produce polyacrylamide.

[0142] The compound of formula (3) produced may be used to produce one or more downstream products. For example, acrylonitrile produced by the method described herein may be used to produce polyacrylonitrile. Accordingly, in a specific embodiment, a method is provided comprising: producing a compound of formula (3) according to any method of the present invention; and polymerizing the compound of formula (3). In one variation, a method for producing polyacrylonitrile is provided comprising: producing acrylonitrile according to any method of the present invention; and polymerizing the acrylonitrile to produce polyacrylonitrile. Polyacrylonitrile may be suitable for various uses, including carbon fibers. In another embodiment, acrylonitrile produced by the method described herein or produced by the system described herein may be used to produce acrylic acid and / or acrylamide.

[0143] Examples

[0144] The following examples are merely illustrative and do not imply that any aspect of the present disclosure is limited in any way.

[0145] Examples 1 3- of hydroxypropanamide (3-HPA) synthesis

[0146] This example demonstrates a process for the synthesis of 3-hydroxypropanamide (3-HPA) by combining a mixed feed stream containing beta-propiolactone (BPL) and tetrahydrofuran (THF) with anhydrous ammonia.

[0147] method 30 mL of anhydrous ammonia supplied from a 1 L anhydrous ammonia bottle was filled into a 100 mL pressure vessel in a -78 °C acetone / dry ice bath via a stainless steel line and a magnetic stirring rod. A solution of BPL in THF (20 wt% as determined by GC analysis) was introduced over 15 minutes. The pressure tube was sealed. The solution was stirred at -78 °C for 10 minutes, then heated to 0 to 3 °C over the next 10 minutes and stirred at that temperature for 2 hours. Afterward, the solution was cooled to -78 °C, the pressure valve was opened, the vessel was heated, and the ammonia was allowed to be discharged at -30 to 3 °C. After 50 minutes, no ammonia gas generation was observed, along with insoluble white 3-HPA on the side of the vessel. The purple THF phase was separated by gradient separation and sent for GC analysis. After GC analysis confirmed the complete conversion of BPL, the byproduct was dissolved in ethanol and concentrated under vacuum to obtain a solid product.

[0148] result: The results are provided in Table 1 below with reference to Experiment 2. Table 1 also provides the results for experiments involving the use of BPL and aqueous ammonia under the conditions mentioned for Experiment 1 in the table. The final composition was determined by 1H NMR.

[0149]

[0150] When 3-HPA was synthesized using the conditions described above (Experiment 2), only trace amounts of beta-alanine were unexpectedly observed in the product mixture. In other words, there was improved regioselectivity favorable to the 3-HPA ring-opening product. For comparison, when 3-HPA was synthesized using NH3H2O ​​(Experiment 1), 8% of beta-alanine was observed in the product mixture.

[0151] Examples 2 3- Hydroxypropanamide ( Synthesis of acrylonitrile using a solution of 3-HPA

[0152] This example demonstrates the synthesis process of acrylonitrile by passing evaporated 3-HPA and a solvent (in the presence of a nitrogen carrier gas) over a dehydrating agent. method: 7 g of 3-HPA was packed into a 50 mL stainless steel shot tank and dissolved in 8 mL of EtOH and 20 mL of THF. This was then passed through a TiO2 column at 380 to 390 °C. A 17:1 molar ratio of N2 to 3-HPA was used at a rate of 19 mmol N2 per minute.

[0153] result: The results are provided in Table 2 below.

[0154]

[0155] Examples 3 3- Hydroxypropanamide ( Anti- for synthesizing 3-HPA Raw fish meal process

[0156] This example investigates the yield and selectivity of 3-HPA when a BPL feed stream is reacted with excess ammonia in the liquid phase. The BPL feed stream is added above and below the surface of the liquid ammonia in the following two scenarios: (A) controlled addition of carbonylation reaction permeate; permeate stripped of light; and distilled BPL without shaking in a glass pressure tube. (B) liquid NH3 with shaking using a magnetic needle and controlled shaking in a glass pressure tube: carbonylation reaction permeate; permeate stripped of light; and distilled BPL. The yield and selectivity of 3-HPA are measured.

[0157] Example 4 Continuous process for synthesizing acrylonitrile (ACN)

[0158] This example investigates the yield and selectivity of ACN when the crude feed from Example 3 is dehydrated through a continuous packed-bed vapor-phase reactor at 380-390°C using pure TiO2 or a mixed TiO2 and SiO2 catalyst and NH3 or a mixed NH3 and N2 carrier gas. The feed is the product of reactions Ai, A-ii, A-iii, Bi, B-ii, ​​and B-iii in Example 3. The temperature is 380 to 390°C. The carrier gas is NH3 or NH3+N2.

[0159] Several baseline experiments are conducted using streams of NH3 and H2O (10 wt% water), a stream of NH3, a stream of THF and H2O (10 wt% water), and a stream of THF through a packed-bed reactor to verify the effects of catalysts and operating conditions on the carrier fluid. The yield and selectivity of ACN, as well as the weighted hourly space velocity (WHSV), are measured.

[0160] Example 5 Continuous process for the synthesis of 3-HPA followed by continuous conversion to ACN

[0161] This example investigates the yield and selectivity of 3-HPA and ACN when a BPL feed stream is reacted with excess ammonia in the vapor phase. An exemplary setup for this example is shown in Figure5 The BPL feed stream can be atomized and fed into a reactor having a counter-current flow of NH3 gas. The gas-liquid reaction can take place on an inert packed bed. Unreacted NH3 and volatile substances from the BPL feed stream can be removed from the top, but the product can be recovered from the bottom of the reactor. Phase change and volumetric flow are determined by the reactor operating temperature and pressure. The product of liquid 3-HPA is then fed continuously into a second reactor, which is converted to acrylonitrile. The yield and selectivity of 3-HPA and ACN are measured.

[0162] Example 6 Process synthesis of 3-hydroxypropanamide (3-HPA)

[0163] This example demonstrates a process for the synthesis of 3-hydroxypropanamide (3-HPA) by combining a mixed feed stream containing beta-propiolactone (BPL) and tetrahydrofuran (THF) and a carbonylation catalyst with water ammonia. method : A 100 mL pressure vessel was filled with ammonia solution at room temperature and a magnetic stirring rod. A bPL solution in THF containing a carbonylation catalyst (22 wt%, directly from the carbonylation process, as determined by GC analysis) was slowly introduced over 8 minutes. The solution was stirred at that temperature for 2 hours. Afterward, stirring was stopped to allow the two layers to separate. The THF phase was separated by gradient separation and sent for GC analysis to confirm the complete conversion of bPL. The aqueous layer was evaporated under heat and reduced pressure to yield a solid product. The feed consisted of bPL (22% w / w in tetrahydrofuran with carbonylation catalyst), ammonia, and water. The composition was analyzed by 1H NMR to have 79 percent HPA, 11 percent β-alanine, and 10 percent oligomers.

[0164] Examples 7 3- Hydroxypropanamide ( Synthesis of acrylamide using 3-HPA

[0165] This example demonstrates a process for the synthesis of acrylonitrile by passing 3-HPA evaporated (in the presence of a nitrogen carrier gas) and a solvent through a dehydrating agent. method: 16.7 g of 3-HPA was packed into a 50 mL stainless steel shot tank. This was then passed through a SiO2 column at 300 °C. A 15:1 molar ratio of N2 to 3-HPA was used at a rate of 19 mmol N2 per minute. The conversion rate was 100 wt percent. The product was analyzed by 1H NMR to contain 99 percent acrylamide and 1 percent oligomer.

[0166] Implementation example

[0167] 1. A method for producing a compound of formula (3-I) and / or a compound of formula (3) or its isomer:

[0168] or ,

[0169] During the meal, R 1 is H or alkyl, and the method comprises the step of combining a hydroxypropanamide stream comprising a compound of formula (2), a solvent, and ammonia with a dehydrating agent to produce a product stream comprising a compound of formula (3-I) and / or a compound of formula (3), or its isomer, a solvent, and ammonia, and

[0170] The compound of chemical formula (2) is and, among the formulas, R 1 It is as defined above for chemical formulas (3-I) and (3).

[0171] 2. As a method of Embodiment 1, the method further comprises combining a mixed feed stream containing a compound of formula (1) and a solvent with ammonia to produce a hydroxypropanamide stream, and

[0172] The compound of chemical formula (1) is and, among the formulas, R 1It is as defined above for chemical formulas (3-I) and (3).

[0173] 3. As a method of Embodiment 2, the combination includes the following:

[0174] A step of providing ammonia at a temperature of -100℃ to about 35℃; and a step of adding a mixed feed stream to the ammonia to produce a hydroxypropanamide stream.

[0175] 4. As a method of Embodiment 2 or 3, the combination of the mixed feed stream and ammonia is controlled isothermally.

[0176] 5. As a method of any one of embodiments 2 to 4, the method further comprises the step of carbonylating an epoxide with carbon monoxide in the presence of a carbonylation catalyst and a solvent to produce a mixed feed stream.

[0177] 6. A method of any one of embodiments 2 to 4 further comprises the step of carbonylating an epoxide with carbon monoxide in the presence of a carbonylating catalyst and a solvent to produce a carbonylated product stream comprising a compound of formula (1), a solvent, and a carbonylated catalyst; and the step of separating the carbonylated catalyst from the carbonylated product stream to produce a mixed feed stream.

[0178] 7. Any one of embodiments 1 to 6 further comprises the step of distilling a product stream to isolate one or more of a compound of formula (3-I) and / or a compound of formula (3), or its isomer; a solvent; and ammonia.

[0179] 8. As a method of any one of embodiments 1 to 7, the hydroxypropanamide stream comprises a molten compound of formula (2).

[0180] 9. As a method of any one of embodiments 1 to 7, the hydroxypropanamide stream comprises a molten compound of formula (2) and a carrier gas.

[0181] 10. As a method of Embodiment 9, the dehydrating agent is heterogeneous, and the hydroxypropanamide stream is contacted over the heterogeneous dehydrating agent to produce a product stream.

[0182] 11. As a method of any one of embodiments 1 to 10, the solvent comprises a polar aprotic solvent, an alcohol, or a combination thereof.

[0183] 12. In any one of the methods of Embodiments 1 to 11, the solvent is evaporated.

[0184] 13. A method for producing a polymer, wherein the method comprises the step of producing a compound of formula (3-I) and / or a compound of formula (3), or an isomer thereof, according to any one of embodiments 1 to 12; and the step of polymerizing the compound of formula (3-I) and / or a compound of formula (3), or an isomer thereof.

[0185] 14. A method for producing a hydroxypropanamide stream comprising a compound of formula (2), a solvent, and ammonia, wherein the compound of formula (2) (during food, R 1 is H or alkyl; and the method comprises the step of producing a hydroxypropanamide stream by combining a mixed feed stream containing a compound of formula (1) and a solvent with ammonia, and

[0186] The compound of chemical formula (1) is and, among the formulas, R 1 It is as defined above for chemical formula (2).

[0187] 15. Chemical formula (2): Method for producing the compound of (2):

[0188] During the meal, R 1 The compound is H or alkyl, and the method comprises the step of producing a compound of formula (2) by combining a compound of formula (1) with anhydrous ammonia at a temperature of -100°C to 35°C, and

[0189] The compound of chemical formula (1) is and, among the formulas, R 1 It is as defined above for chemical formula (2).

[0190] 16. Chemical formula (2): Method for producing the compound of (2):

[0191] During the meal, R 1 is H or alkyl, and the above method,

[0192] The method comprises the step of producing a hydroxypropanamide stream containing a compound of formula (2) by combining a mixed feed stream containing a compound of formula (1) and a solvent at a temperature of -100℃ to 35℃ with anhydrous ammonia, and

[0193] The compound of chemical formula (1) is and R 1 It is as defined above for chemical formula (2).

[0194] 17. As a method of Embodiment 16,

[0195] Compound of chemical formula (1) in a solvent.

[0196] The mixed feed stream contains a 20 wt% solution.

[0197] 18. By the method of Embodiment 16 or 17, the compound of Formula (2) is produced with a selectivity of more than 50%.

[0198] 19. As a method of any one of embodiments 16 to 18, the hydroxypropanamide stream further comprises an additional product selected from the group consisting of a compound of formula (2-I), an oligomer, and combinations thereof, and the compound of formula (2-I) (2-I) and, among the formulas, R 1 is as defined above for chemical formula (3), and

[0199] The hydroxypropanamide stream has a molar ratio of compound of formula (2) to additional product of 10:1.

[0200] 20. As a method of any one of embodiments 16 to 19, the mixed feed stream and anhydrous ammonia are further combined with a base.

[0201] 21. As a method of Embodiment 20, the hydroxypropanamide stream further comprises a base, and the method further comprises the step of recovering the base from the hydroxypropanamide stream.

[0202] 22. Method for producing a compound of formula (3-I) and / or a compound of formula (3) or its isomer:

[0203] (3-1) or (3),

[0204] During the meal, R 1 is H or alkyl, and the method comprises the step of contacting a hydroxypropanamide stream comprising a molten compound of formula (2) and a carrier gas over a heterogeneous dehydrating agent to produce a product stream comprising a compound of formula (3-I) and / or a compound of formula (3), or its isomer, and optionally a solvent, and

[0205] The compound of chemical formula (2) is and, among the formulas, R 1 It is as defined above for chemical formulas (3-I) and (3).

[0206] 23. As a method of Embodiment 22, the hydroxypropanamide stream further comprises ammonia.

[0207] 24. As a method of Embodiment 23, the carrier gas comprises nitrogen and ammonia, and the relative volume of the ammonia gas is in the range of about 1% to about 99% with respect to the nitrogen gas.

[0208] 25. As a method of any one of embodiments 22 to 24, the hydroxypropanamide stream further comprises an evaporated solvent.

[0209] 26. In any one of embodiments 22 to 24, the hydroxypropanamide stream is further combined with an evaporated solvent.

[0210] 27. As a method of Embodiment 25 or 26, the solvent comprises a polar solvent.

[0211] 28. As a method of Embodiment 25 or 26, the solvent comprises ether.

[0212] 29. As a method of Embodiment 25 or 26, the solvent comprises tetrahydrofuran.

[0213] 30. As a method of Embodiment 25 or 26, the solvent comprises alcohol.

[0214] 31. As a method of any one of embodiments 25 to 29, the solvent further comprises alcohol.

[0215] 32. As a method of Embodiment 30 or 31, the alcohol is C1-C 10 It is alcohol.

[0216] 33. As a method of any one of embodiments 22 to 32, the dehydrating agent comprises TiO2 or SiO2, or a combination thereof.

[0217] 34. As a method of Embodiment 33, the dehydrating agent comprises TiO2 and SiO2.

[0218] 35. As a method of Embodiment 34, a dehydrating agent is provided to a column, and the column has a zone containing TiO2 and, separately, a zone containing SiO2.

[0219] 36. As a method of Embodiment 35, the zone containing TiO2 operates at a first temperature, and the zone containing SiO2 operates at a second temperature, and the first temperature and the second temperature are different.

[0220] 37. As a method of Embodiment 36, the first temperature is higher than the second temperature.

[0221] 38. Method for producing a compound of formula (3-I) and / or a compound of formula (3) or its isomer:

[0222] or ,

[0223] During the meal, R 1 is H or alkyl, and the method comprises the step of combining a mixed feed stream containing a compound of formula (1) and a solvent with ammonia and a dehydrating agent to produce a product stream containing a compound of formula (3-I) and / or a compound of formula (3), or its isomer, a solvent, and ammonia, and

[0224] The compound of chemical formula (1) is and, among the formulas, R 1 It is as defined above for chemical formulas (3-I) and (3).

[0225] 39. A system including the following

[0226] reactor,

[0227] (i) a mixed feed stream containing a compound of formula (1) and a solvent (wherein the compound of formula (1) and, among the formulas, R 1 is H or alkyl);

[0228] and (ii) ammonia

[0229] At least one inlet configured to accommodate; and

[0230] An outlet configured to discharge a hydroxypropanamide stream containing a compound of formula (2), a solvent, and ammonia (wherein the compound of formula (2) and, among the formulas, R 1 is as defined above for chemical formula (1).

[0231] 40. As a system of Embodiment 39, the reactor is configured to add a mixed feed stream to the excess ammonia.

[0232] 41. As a system of either Embodiment 39 or 40, the reactor is configured to add a mixed feed stream to ammonia at a rate suitable for maintaining the temperature.

[0233] 42. As a system of any one of embodiments 39 to 41, the reactor is configured to receive ammonia and a mixed feed stream in liquid form.

[0234] 43. As a system of any one of embodiments 39 to 42, the hydroxypropanamide stream is homogeneous.

[0235] 44. As a system of any one of embodiments 39 to 43, at least one inlet is configured to receive a base.

[0236] 45. A system of any one of embodiments 39 to 44 further comprises an additional reactor configured to receive a hydroxypropanamide stream and produce a product stream in the presence of a dehydrating agent, wherein the product stream comprises a compound of formula (3-I) and / or a compound of formula (3), or an isomer thereof, a solvent, and ammonia, wherein the compound of formula (3-I) and / or the compound of formula (3) (3-1) or (3) and, among the formulas, R 1 It is as defined above for chemical formula (1).

[0237] 46. ​​As a system of Embodiment 45, the additional reactor further comprises a multi-temperature stage column.

[0238] 47. As a system of embodiment 45 or 46, an additional reactor is further configured to receive a carrier gas.

[0239] 48. A system of any one of embodiments 45 to 47 further comprises a distillation unit configured to collect the following:

[0240] i) Compound of formula (3-I) and / or compound of formula (3) (compound of formula (3-I) and / or compound of formula (3) or and, among the formulas, R 1 (as defined above for the equation)

[0241] ii) solvent; or ammonia; or any combination of i) to iii).

[0242] 49. As a system of Embodiment 48, a distillation unit is additionally configured to collect a base, a carrier gas, or a combination thereof.

[0243] 50. Any one of embodiments 39 to 49 further comprises: a carbonylation reactor configured to receive an epoxide and carbon monoxide and to produce a carbonylation product stream in the presence of a carbonylation catalyst and a solvent, wherein the carbonylation product stream comprises a compound of formula (1), a solvent and a carbonylation catalyst; and a separation unit configured to receive the carbonylation product stream and to separate at least a portion of the carbonylation catalyst to produce a mixed feed stream.

[0244] 51. As a system of any one of embodiments 39 to 49, a carbonylation reactor configured to receive an epoxide and carbon monoxide and to produce a mixed feed stream in the presence of a heterogeneous carbonylation catalyst and a solvent, wherein the mixed feed stream further comprises a carbonylation reactor comprising a compound of formula (1) and a solvent.

[0245] 52. A system comprising a reactor configured to produce a product stream in the presence of a dehydrating agent, wherein the reactor comprises a hydroxypropanamide stream comprising a compound of formula (2), a solvent, and ammonia (wherein the compound of formula (2) and, among the formulas, R 1 An inlet configured to receive (which is H or an alkyl); and an outlet configured to discharge a product stream, wherein the product stream comprises a compound of formula (3-I) and / or a compound of formula (3), or its isomer, a solvent, and ammonia (wherein the formula, the compound of formula (3-I) and / or the compound of formula (3) (3-1) or (3) and, among the formulas, R 1 It includes the chemical formula (2) as defined above.

[0246] 53. A system comprising a reactor configured to produce a product stream in the presence of a dehydrating agent, wherein the reactor comprises (i) a mixed feed stream comprising a compound of formula (1) and a solvent (wherein the compound of formula (1) and, among the formulas, R 1 (i) at least one inlet configured to receive (where is H or alkyl); and (ii) ammonia; and an outlet configured to discharge a product stream, wherein the product stream comprises a compound of formula (3-I) and / or a compound of formula (3), or its isomer, a solvent, and ammonia (wherein the formula, the compound of formula (3-I) and / or the compound of formula (3) or and, among the formulas, R 1 It includes an outlet containing a chemical formula (1) as defined above.

[0247] 54. As a system of Embodiment 53, the reactor is configured to add a mixed feed stream to the excess ammonia.

[0248] 55. As a system of Embodiment 53 or 54, the reactor is configured to add a mixed feed stream to ammonia at a rate suitable for maintaining the temperature.

[0249] 56. As a system of any one of embodiments 53 to 55, the reactor is configured to receive ammonia and a mixed feed stream in liquid form.

[0250] 57. As a system of any one of embodiments 53 to 56, at least one inlet is configured to receive a base.

[0251] 58. As a system of any one of embodiments 53 to 57, the reactor further comprises a multi-temperature stage column.

[0252] 59. As a system of any one of embodiments 53 to 58, the reactor is further configured to receive a carrier gas.

[0253] 60. A system of any one of embodiments 53 to 59 further comprises a distillation unit configured to collect the following:

[0254] i) a compound of formula (3-I) and / or a compound of formula (3) (wherein, the compound of formula (3-I) and / or the compound of formula (3) (3-1) or (3) and, among the formulas, R 1 is as defined above for equation (3-I) or (3);

[0255] ii) solvent; or iii) ammonia; or any combination of i) to iii).

[0256] 61. As a system of Embodiment 60, the distillation unit is additionally configured to collect a base, a carrier gas, or a combination thereof.

Claims

Claim 1 A step of preparing a hydroxypropanamide stream by combining a beta-lactone and a solvent with ammonia, wherein the combination of the beta-lactone and ammonia is controlled isothermally; and a step of producing a product stream containing an unsaturated amide and / or unsaturated nitrile by combining the hydroxypropanamide stream containing the hydroxypropanamide with a dehydrating agent, wherein the dehydrating agent is a heterogeneous dehydrating agent, and the hydroxypropanamide is of formula (2) A method for producing a nitrogen-containing compound, wherein R1 is H, alkyl, alkenyl, cycloalkyl, or aryl, and R1 is H or alkyl, and the hydroxypropanamide is combined with a dehydrating agent in the presence of a solvent and ammonia. Claim 2 A method according to claim 1, comprising producing the beta-lactone by contacting carbon monoxide with an epoxide in the presence of a carbonylation catalyst. Claim 3 A method according to claim 1, comprising distilling a product stream containing the unsaturated amide and / or unsaturated nitrile to isolate the unsaturated amide and / or unsaturated nitrile. Claim 4 In paragraph 2, the beta-lactone is chemical formula (1) It corresponds to, and the above unsaturated nitrile is chemical formula (3) Corresponds to, and the above unsaturated amide is of chemical formula (3-I) It corresponds to, and the above epoxide is chemical formula (E) Corresponding to, wherein R1 is H, alkyl, alkenyl, cycloalkyl, or aryl; and R1 is H or alkyl, method. Claim 5 A method according to claim 1, wherein the beta-lactone and ammonia are contacted in the presence of a base. Claim 6 A method according to claim 1, wherein the dehydrating agent comprises TiO2 or SiO2, or a combination thereof. Claim 7 A method according to claim 1, wherein the dehydrating agent comprises TiO2 and SiO2. Claim 8 In claim 7, the dehydrating agent is provided to a column, the column has a zone containing TiO2 and a separate zone containing SiO2, the zone containing TiO2 operates at a first temperature and the zone containing SiO2 operates at a second temperature, and the first temperature and the second temperature are different, method. Claim 9 A method for producing a polymer, comprising the step of preparing an unsaturated amide and / or unsaturated nitrile according to any one of claims 1 to 8 and polymerizing the unsaturated amide and / or unsaturated nitrile. Claim 10 delete Claim 11 delete Claim 12 delete Claim 13 delete Claim 14 delete Claim 15 delete Claim 16 delete Claim 17 delete Claim 18 delete Claim 19 delete Claim 20 delete Claim 21 delete Claim 22 delete Claim 23 delete Claim 24 delete Claim 25 delete Claim 26 delete Claim 27 delete Claim 28 delete Claim 29 delete Claim 30 delete

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