# Patent

## Title
Gas and liquid phase catalytic Beckmann rearrangement of oximes to produce lactams

## Abstract

Methods for producing lactams from oximes by performing a Beckmann rearrangement using a silicoaluminophosphate catalyst are provided. These catalysts may be used in gas phase or liquid phase reactions to convert oximes into lactams. High conversion of oxime and high selectivity for the desired lactams are produced using the disclosed methods, including high conversion and selectivity for ε-caprolactam produced from cyclohexanone oxime and high conversion and selectivity for ω-laurolactam produced from cyclododecanone oxime.

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a divisional application of U.S. patent application Ser. No. 13/658,495 Oct. 23, 2012, which claims the benefit under 35 U.S.C. §119(e) of U.S. Provisional Patent Application Ser. No. 61/628,419 filed Oct. 28, 2011, the disclosures of which are hereby incorporated by reference in their entirety.


FIELD
The present invention relates to methods of producing lactams, such as caprolactam, for example. In particular, the present invention relates to a method producing caprolactam utilizing silicoaluminophosphate (SAPO) catalysts.
BACKGROUND
Traditional approaches for producing lactams, used in the production of nylon, include an oxime undergoing a Beckmann rearrangement in the presence of an acid catalyst such as fuming sulfuric acid. Exemplary reactions are shown in FIG. 1. As illustrated in FIG. 1A, cyclohexanone oxime is reacted to form ε-caprolactam, ε-caprolactam in turn is polymerized to form Nylon-8. As illustrated in FIG. 1B, cyclododecanone oxime is reacted to form ω-laurolactam, ω-laurolactam in turn is polymerized to form Nylon-12. Nylon-8 and nylon-12 are extensively used in industry and manufacturing.
One potential reaction mechanism for the reaction of FIG. 1A is illustrated in FIG. 1C. The mechanism generally consists of protonating the hydroxyl group, performing an alkyl migration while expelling the hydroxyl to form a nitirium ion, followed by hydrolysis, tautomerization, and deprotonation to form the lactam.
Typically, Beckmann rearrangement reactions of oximes to form lactams are performed using acids such as fuming sulfuric acid. These reactions are characterized by complete or nearly complete conversion of the oxime and very high selectivity for the desired lactams. However, these reactions also produce byproducts including ammonium sulfate. Although ammonium sulfate is a useful product in itself, minimizing its production may be desirable.
Gas-phase and liquid-phase Beckmann rearrangement of cyclohexanone oximes are known, which employ various natural and synthetic catalysts including solid-acid catalysts. However, the reported results provide low conversion of the oxime and low selectivity of the desired lactam products.
Improvements in the foregoing processes are desired.
SUMMARY
The present disclosure provides methods for producing lactams from oximes by performing a Beckmann rearrangement using a silicoaluminophosphate catalyst. These catalysts are used in gas phase or liquid phase reactions to convert oximes into lactams. High conversion of oxime and high selectivity for the desired lactams are produced using the disclosed methods, including high conversion and selectivity for ε-caprolactam produced from cyclohexanone oxime and high conversion and selectivity for ω-laurolectam produced from cyclododecanone oxime.
In one exemplary embodiment, the present invention provides a method of performing a Beckmann rearrangement reaction. The method comprises reacting an oxime in a liquid phase in the presence of a catalyst to produce a lactam, said catalyst comprising a silicon-containing aluminophosphate with the IZA framework code FAU.
In another exemplary embodiment, the present invention provides another method of performing a Beckmann rearrangement reaction. The method comprises reacting an oxime in a gas phase in the presence of a catalyst to produce a lactam, said catalyst comprising a silicon-containing aluminophosphares with the IZA framework code FAU; wherein said reacting step further comprises the combination of conversion of oxime and selectivity of the lactam is selected from the group consisting of; the conversion of the oxime is at least 50% and the selectivity of the lactam is at least 90%; and the conversion of the oxime is at least 90% and the selectivity of the lactam is at least 80%.
In still another exemplary embodiment, the present invention provides a catalyst. The catalyst comprises, a silicon-containing aluminophosphate framework with the IZA framework code FAU; and a plurality of discrete Brønsted acid sites positioned in an interior of the framework, the acid sites comprising silicon isomorphously substituted for phosphorous in the framework; wherein the catalyst is a SAPO-37 type catalyst, and at least 10% of the total number of acid sites are characterized as weak acid sites.
In still another exemplary embodiment, a method of performing a Beckmann rearrangement reaction is provided. The method comprises reacting an oxime in a liquid or gas phase in the presence of a catalyst to produce a lactam, said catalyst comprising a silicon-containing aluminophosphate with the IZA framework code FAU; wherein where the oxime is in a gas phase said reacting step further comprises the combination of conversion of oxime and selectivity of the lactam is selected from the group consisting of: the conversion of the oxime is at least 50% and the selectivity of the lactam is at least 90%; and the conversion of the oxime is at least 90% and the selectivity of the lactam is at least 80%.
The above mentioned and other features of the invention, and the manner of attaining them, will become more apparent and the invention itself will be better understood by reference to the following description of embodiments of the invention taken in conjunction with the accompanying drawings.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1A illustrates the reaction from cyclohexanone oxime to ε-caprolactam;
FIG. 1B illustrates the reaction from cyclododecanone oxime to ω-laurolactam;
FIG. 1C illustrates the potential steps of a reaction corresponding to a Beckmann rearrangement reaction from cyclohexanone oxime to ε-caprolactam;
FIGS. 2A-2G illustrate a structures of an exemplary SAPO-37 catalyst;
FIG. 3A is a ternary diagram showing the compositional parameters of one embodiment of the silicoaluminophosphates in terms of mole fractions of silicon, aluminum, and phosphorous;
FIG. 3B is a ternary diagram showing the compositional parameters of further embodiments of the silicoaluminophosphates in terms of mole fractions of silicon, aluminum, and phosphorous;
FIGS. 4A-4C correspond to Example 2, and illustrate results from 29Si Solid state NMR characterization of SAPO-37 catalysts;
FIG. 5 corresponds to Example 2, and illustrates, results from NH3-Temperature Programmed Desorption characterization of SAPO-37 catalysts;
FIG. 8 corresponds to Example 2, and illustrates results from X-Ray Diffraction characterization of SAPO catalysts;
FIG. 7 corresponds to Example 2; and illustrates results from BET surface area characterization of SAPO-37 catalysts;
FIGS. 8A-8C correspond to Example 2, and are SEM pictures of SAPO-37 catalysts;
FIGS. 9-15 correspond to Example 3, and illustrate the conversion and selectivity results of gas phase Beckmann rearrangement reactions of cyclohexanone oxime to ε-caprolactam using various catalysts;
FIGS. 16-20 correspond to Example 4, and illustrate the conversion and selectivity results of liquid phase Beckmann rearrangement reactions of cyclohexanone oxime to ε-caprolactam using various catalysts; and
FIGS. 21 and 22 correspond to Example 5, and illustrate the conversion and selectivity results of liquid phase Beckmann rearrangement, reactions of cyclododecanone oxime to ω-laurolactam using various catalysts.



DETAILED DESCRIPTION
The present disclosure is directed to a method to form lactams from cyclic oxime compounds. Exemplary reactions are shown in FIG. 1. As illustrated in FIG. 1A, cyclohexanone oxime is reacted to form ε-caprolaetam, which in turn can be polymerized to form Nylon-8. As illustrated in FIG. 1B, cyclododecanone oxime is reacted to form ω-laurolactam, which in turn can be polymerized to form Nylon-12. In other exemplary embodiments, additional lactams besides ε-caprolactam and ω-laurolactam are produced from corresponding oximes via this method. The present method is also useful to perform other Beckmann rearrangement reactions.
The methods according to the present disclosure include an oxime reactant undergoing a Beckmann rearrangement reaction in the presence of a catalyst. Exemplary catalysts include mieroporous and roesoporous natural and synthetic molecular sieves, zeolites, aluminophosphate (AiPO) materials, and silicoalumlnophosphafe (SAPO) materials.
Silicoalumlnophosphate (SAPO) catalysts are synthetic molecular sieves known to be useful as catalysts. Exemplary methods of preparing certain SAPO catalysts, are provided in U.S. Pat. No. 4,440,871 to Lok, et al, and N. Jappar, Y. Tanaka, S, Nakats, and T. Tatsumi, “Synthesis and Characterization of a New Titanium Sllicoaluminophospate: TAPSO-37,” Microporous and Mesoporous Materials, Vol. 23, Issues 3-4, August 1998, pp. 189-178, the disclosures of each are hereby incorporated by reference.
An exemplary structure of one SAPO catalyst, SAPO-37, is illustrated in FIGS. 2A-2G. Molecular sieves, such as the SAPO-37 catalyst illustrated in FIG. 2A, are crystalline structures having a three-dimensional framework of geometries. The frameworks of molecular sieves include cages, cavities, channels, and pores, depending on the type of molecular sieve. Acid sites either on the surface or in the interior or both of the molecular sieve provide the ability for some molecular, sieves to act as acid catalysts.
In the exemplary SAPO-37 structure shown in FIGS. 2A-2G, the portion 10 of the catalyst includes a silicon-containing aluminophosphate geometry with a faujasite-type structure. The geometry includes a plurality of pores 12 connecting the interior cavities of the catalyst. FIGS. 2A-2G further illustrate an acid site include a silicon atoms 14. In the interior cavities of the catalyst. The acid sites further include a hydrogen atom, i.e. a proton 16, which is used in catalyzing the Beckmann rearrangement reaction. Silicon atom 14 and proton 18 are enlarged for identification in FIGS. 2A-2G. FIGS. 2A-2F illustrate a variety of perspective views of one interior cavity formed by the catalyst 10. FIG. 2G shows an enlarged view of an acid site including the silicon atom 14 and proton 16 in the interior of the cage formed by the catalyst 10.
As best shown in FIG. 2G, silicon atom 14 is illustratively attached to four oxygen atoms 18A, 18B, 18C, and 18D, indicating it has isomorphousiy been substituted for a phosphorous atom in the framework of the catalyst. Such an isomorphous substitution is referred to as a type-II substitution, in exemplary embodiments, the catalyst contains a plurality of these isomorphousiy substituted silicon atoms forming acid sites, such that the acid sites are discrete and well-isolated from each other. This exemplary arrangement allows each acid site to function as a well isolated single-site Brønsted acid. Catalysts having a greater fraction of type II isomorphous substitution acid sites are typified by higher fractions of weak Brønsted acid sites. Higher silicon loaded catalysts are typified by a greater fraction of strong acid sites, which are attributable to type III substitution of two silicon atoms for adjacent aluminum and phosphorous atoms. Type ill substitution leads to a reduction in available weak Brønsted acid sites.
Proton 16 is illustratively attached to one of the oxygen atoms 18A. The proton 16 can be given up by the acid site to catalyze a reaction in the cavity, such as a Beckmann rearrangement.
Typically, the catalyst is a silicon-containing aluminophosphate with a faujasite-type structure, in an exemplary embodiment, the catalyst is a silicon-containing aluminophosphate or silicoaluminophosphate catalyst with the international Zeolite Association (IZA) framework code FAU as described in the Atlas of Zeolite Framework Types, 6th ed., Christian Baerloeher, Lynne B. McCusker and David H. Olson, Elsevier, Amsterdam (2007), the disclosure of which is hereby incorporated by reference. More particularly, the catalyst is composed of sodalite cages linked together through 6,6 (double-6) secondary building units. Twelve of these sodalite cages are then used to create a super-cage structure of which the pore-aperture is 7.4 Å and the internal diameter of the super-cage is in the region of 12-14 Å. The catalyst further comprises a plurality of discrete Brønsted acid sites positioned in an interior of the framework, the acid sites comprising silicon isomorphousiy substituted for phosphorous in the framework.
In exemplary embodiments, the catalyst is a silicoaluminophosphate having a microporous crystalline framework structure and whose essential empirical chemical composition in the as-synthesized form on an anhydrous basis is:

mR:(SixAlyPz)O2 

wherein:
R represents at least one organic templating agent present in the intracrystaline pore system;
m has a value of from 0.02 to 0.3:
x, y, and z represent, respectively, the mole fraction of silicon, aluminum, and phosphorous present in the oxide moiety;
In one embodiment, the value of x, y, and z being within the compositional area bounded by points A, B, C, D, and E of the ternary diagram which is FIG. 3A representing the values set forth below in Table 1;







TABLE 1







Mole Fractions Corresponding to FIG. 3A









Mole Fraction












Point
x
y
z







A
0.01
0.47
0.52



B
0.94
0.01
0.05



C
0.98
0.01
0.01



D
0.39
0.60
0.01



E
0.01
0.60
0.39










In another embodiment, the value of x, y, and z being within the compositional area bounded by points a, b, c, d, and a of the ternary diagram which is FIG. 3B representing the values set forth below in Table 2;







TABLE 2







Mole Fractions Corresponding to FIG. 3B









Mole Fraction












Point
x
y
z






a
0.02
0.49
0.49



b
0.25
0.37
0.38



c
0.25
0.48
0.27



d
0.13
0.60
0.27



e
0.02
0.60
0.38









said silicoaluminophosphate having a characteristic X-ray powder diffraction pattern which contains at least the d-spacing set forth below in Table 3.







TABLE 3







X-ray Powder Diffraction Pattern d-Spacing











2θ
d
Relative Intensity






6.1-6.3
14.49-14.03
vs



15.5-15.7
5.72-5.64
w-m



18.5-18.8
4.80-4.72
w-m



23.5-23.7
3.79-3.75
w-m



26.9-27.1
3.31-3.29
w-m









One exemplary procedure for preparation of SAPO-37 catalysts is as follows. First, an aluminum source, such as aluminum oxide, is slowly added to a phosphorous source, such as 85% phosphoric acid. A structural template solution is prepared by dissolving tetramethylammonium hydroxide pentahydrate (TMAOH) in tetrapropylammonium hydroxide (TPAOH), to which fumed silica is slowly added. The solution is then added dropwise with vigorous stirring to the aluminum/phosphorous mixture. The resulting gel is heated to synthesize the desired structure. The resulting product is isolated typically by centrifugation, filtering, and washing. The product is then dried, and calcined, prior to storage in an inert atmosphere.
The relative loadings of silicon and aluminum can be adjusted to provide a suitable quantity and distribution of acid sites on the surface of and in the inferior of the catalyst. Exemplary procedures for adjusting the quantity and distribution of acid sites include adjusting the ratio of silicon to phosphorous provided in forming the gel in typical embodiments, the gel ratio of Si:P is from about 0.1:1 to about 0.8:1, in a more particular embodiment, the gel ratio of Si:P is from about 0.11:1 to about 0.63:1. In still other embodiments, the gel ratio of Si:P is as little as 0.1:1, 0.11:1, 0.18:1, 0.17:1, 0.21:1, 0.22:1, or as great as 0.42:1, 0.83:1, 0.75:1, 0.8:1, or within any range defined between any pair of the foregoing values.
The weight percentage of silicon in the formed catalyst can also be determined. An exemplary method for determining the weight percentage of silicon is by inductively coupled plasma. Typically, silicon comprises from about 1 wt % to about 10 wt % of the total weight of the catalyst. In a more particular embodiment, silicon comprises from about 2 wt % to about 9.1 wt % of the total weight of the catalyst. In still other embodiment, silicon comprises a weight percentage of the total weight of the catalyst up from as little as 1 wt %, 1.5 wt %, 2 wt %, 2.1 wt %, 2.6 wt % to as much as 6 wt %, 7 wt %, 8 wt %, 9 wt % 9.1 wt %, 10 wt %, or within any range defined between any pair of the foregoing values.
Oximes are converted to lactams, such as in the examples illustrated in FIGS. 1A and 1B, through contact with the catalysts. The present disclosure is believed to be generally applicable to any oxime generated from a variety of aldehydes and ketones. Exemplary oximes include, but are not limited, to cyclohexanone oxime, cyclododecanone oxime, 4-hydroxy acetophenone oxime and oximes formed from acetophenone, butyraldehyde, cyclopentanone, cycloheptanone, cyclooctanone, benzaldehyde.
In exemplary embodiments, the reaction is performed in the presence of a solvent. Although working examples are provided for reactions performed in a solvent, the present disclosure is believed to also be applicable for Beckmann rearrangement reactions performed in the absence of a solvent, in reactions performed in the absence of a solvent, the product is used to absorb the exothermic beat produced by the reaction. In these embodiments, a large ratio of lactam to oxime is maintained in the reaction area to absorb the energy produced by the reaction.
Exemplary solvents include organic nitriles of the formula:

R1—CN

Wherein R1 represents C1-C8-alkyl, C1-C8alkenyl, C1-C8-alkynyl, C3-C8-cycloalkyl; C3-C8-aralkyl including a C8 aromatic ring. Exemplary nitrites include acetonitrile, benzonitrile and mixtures of any of the foregoing.
Other exemplary solvents include aromatic compounds of the formula:

R2—Ar

Wherein Ar is an aromatic ring and R2 represents H, F, Cl, or Br, Exemplary aromatic solvents include benzene and chlorobenzene.
Still other exemplary solvents include water and alcohols of the formula:

R3—OH

Wherein R3 represents a hydrogen, C1-C8-alkyl, C1-C8-alkenyl, C1-C8-alkynyl, C3-C8-cycloalkyl; C3-C8-arylalkyl. Exemplary alcohols include alcohols of 8 or fewer carbon atoms such as methanol, ethanol, n-propanol, iso-propanol, n-butanol, see-butanol, isobutanol, tert-butanol, n-amyl alcohol, n-hexanol, phenol, and mixtures of any of the foregoing.
In exemplary embodiments, the solvent is rigorously dried prior to contact with the catalyst. As used herein, rigorously dried is understood to mean dried to a level of 100 ppm water or less. Exemplary methods of drying include adsorption of water using molecular sieves, such as Activated 4A molecular sieves. As used herein, a reaction performed in the absence of water means a reaction in which water comprises less than 0.01 wt % of the weight of the reactants.
The reaction is performed as a liquid phase reaction or a gas phase reaction. As used herein, a liquid phase reaction in a reaction in which substantially ail of the oxime is in the liquid phase when reacted to form the lactam. As used herein, a gas phase reaction in a reaction in which substantially all of the oxime is in the gas or vapor phase when reacted to form the lactam.
When performed as a gas phase reaction, the reaction is typically performed at a temperature-beneath 350° C. In a more particular embodiment, the reaction is performed at a temperature from about 130° C. to about 300° C. in still other embodiments, the reaction may be performed at a temperature as low as about 90° C., 100° C., 110° C., 120°, 130°, or as high as about 140° C., 150° C., 170° C., 180° C., 190° C., 200° C., 210° C., 220° C., 230° C., 240° C. 250° C., 275° C., 300° C., 325° C., 350° C., or within any range defined between any pair of the foregoing values.
When performed as a gas phase reaction, the reaction is typically perfored at a pressure from about 0.1 bar to about 1 bar. More particularly, in exemplary embodiments of the reaction performed as a gas phase reaction, the pressure may be as low as 0.01 bar, 0.02 bar, 0.05 bar, 0.1 bar, as high as 0.5 bar, 1 bar, or within a range defined between any pair of the foregoing values.
When performed as a liquid phase reaction, the reaction is typically performed at a temperature beneath 250° C., in a more particular embodiment, the reaction is performed at a temperature from about 130° C. to about 190° C. in still other embodiments, the reaction may be performed at a temperature as low as about 90° C. 100° C., 110° C., 120°, 130°, or as high as about 140° C., 150° C., 170° C., 180° C., 190° C., 200° C., 210° C., 220° C., 230° C., 240° C. 250° C., or within any range defined between any pair of the foregoing values.
When performed as a liquid phase reaction, the reaction is typically performed at a pressure from about 1 bar to about 5 bar. More particularly, in some exemplar) embodiments, the pressure may be as low as 0.5 bar, 1 bar, as high as 1 bar, 2 bar, 5 bar, 10 bar, 15 bar, 20 bar, 25 bar, 30 bar, 35 bar, or within any range defined between any pair of the foregoing values, in some exemplary embodiments of the reaction performed as a liquid phase reaction, the solvent is typically a gas at the reaction temperature, but is maintained in the liquid phase by performing the reaction at an elevated pressure.
When performed as a liquid phase reaction, the reaction is typically performed at a temperature and pressure below the critical point of the solvent, where the pressure may be as low as 1 bar as high as 2 bar, 5 bar, 10 bar, 15 bar 20 bar, 25 bar, 30 bar, 35 bar, or within any range defined between any pair of the foregoing values.
The efficiency of the reaction may be expressed in terms of conversion of oxime, selectivity of the desired product, or yield. Conversion is a measure of the amount of oxime reactant that is consumed by the reaction. Higher conversions are more desirable. The conversion is calculated as:




  
    Conversion
    ⁡
    
      (
      %
      )
    
  
  =
  
    100
    ⁢
    %
    ×
    
      (
      
        1
        -
        
          
            moles
            ⁢
            
              
            
            ⁢
            of
            ⁢
            
              
            
            ⁢
            oxime
            ⁢
            
              
            
            ⁢
            produced
          
          
            moles
            ⁢
            
              
            
            ⁢
            of
            ⁢
            
              
            
            ⁢
            oxime
            ⁢
            
              
            
            ⁢
            supplied
          
        
      
      )
    
  




Selectivity is a measure of the amount of the desired product that is produced relative to all reaction products. Higher selectivities are more desirable. Lower selectivities indicate a higher percentage of reactant being used to form products other than the desired lactam. The selectivity is calculated as:




  
    Selectivity
    ⁡
    
      (
      %
      )
    
  
  =
  
    100
    ⁢
    %
    ×
    
      
        moles
        ⁢
        
          
        
        ⁢
        of
        ⁢
        
          
        
        ⁢
        desire
        ⁢
        
          
        
        ⁢
        lactam
        ⁢
        
          
        
        ⁢
        produced
      
      
        total
        ⁢
        
          
        
        ⁢
        moles
        ⁢
        
          
        
        ⁢
        of
        ⁢
        
          
        
        ⁢
        product
        ⁢
        
          
        
        ⁢
        produced
      
    
  




Yield is a measurement that combines selectivity and conversion. Yield indicates how much of the incoming oxime is reacted to form the desired lactam. The yield is calculated as:

Yield (%)=Selectivity (%)×Conversion (%)/100%

The methods according to the present disclosure result in high conversions and selectivities.
In typical embodiments, the conversion is 50% or higher. In a more particular embodiment, the conversion is from about 50% to about 100%. For example, the conversion may be as low as about 50%, 60%, 70%, 75%, or as high as about 80%, 85%, 90%, 95%, 97.5%, 99%, 99.5%, approaching 100%, or 100%, or may be within any range defined between any pair of the foregoing values.
In typical embodiments, the selectivity is 50% or higher. In a more particular embodiment, the conversion is as low as about 50%, 55%, 60%, 65%, or as high as about 70%, 75%, 80%, 85%, 90%, 95%, 97.5%, 99%, 99.5%, approaching 100%, or may be within any range defined between any pair of the foregoing values.
In typical embodiments, the conversion of cyclohexanone oxime to ε-caprolactam is from about 90% to about 100% and the selectivity is from about 80% to about 100%. In more particular embodiments, the conversion is from about 95% to about 100% and the selectivity is from about 90% to about 98%. In still more particular embodiments, the conversion is from about 98% to approaching 100% and the selectivity is from about 95% to about 98%.
In typical embodiments, the conversion of cyclododecanone oxime to ω-laurolactam is from about 90% to about 100% and the selectivity is from about 80% to about 100%. In more particular embodiments, the conversion is from about 95% to about 100%, and the selectivity is from about 98% to about 99%.
Example 1—Preparation of SAPO-37 Catalyst
A pseudo-boehmite phase of aluminum oxide was slowly added to a diluted solution of phosphoric acid (85 wt %) and left to stir for 7 hours. A second solution of tetramethylammonium hydroxide pentahydrate (TMAOH) dissolved in tetrapropylammonium hydroxide (TPAOH) (40 wt %) was prepared to which fumed silica was slowly added. This was left to stir for 2 hours and was then added dropwise to a stirred aluminum/phosphorous gel. SAPO-37 catalysts were prepared with four different loadings of SiO2. The catalysts were labeled based on the ratio of SiO2 to H3PO4 used in the preparation. Gel loadings for the various samples can be found in Table 4 below.







TABLE 4







Gel loadings for SAPO-37 materials








Sample
Gel composition





SAPO-37
1.00H3PO4:0.67Al2O3:0.97TPAOH:0.025TMAOH:0.11SiO2


(0.11)



SAPO-37
1.00H3PO4:0.67Al2O3:0.97TPAOH:0.025TMAOH:0.21SiO2


(0.21)



SAPO-37
1.00H3PO4:0.67Al2O3:0.97TPAOH:0.025TMAOH:0.42SiO2


(0.42)



SAPO-37
1.00H3PO4:0.67Al2O3:0.97TPAOH:0.025TMAOH:0.63SiO2


(0.63)









The mixture stirred for 68 hours and was then transferred to an autoclave. The solution was heated under autogenous pressure at 200° C. for 24 hours. On removal the gel was centrifuged, filtered and washed. The material was then dried overnight at room temperature. The white solid was then calcined at 550° C. for 16 hours and kept in an inert atmosphere.
Example 2—Characterization of Catalysts
29Si Solid State NMR
All NMR measurements were performed on a Chemagnetics infinity 400 spectrometer on a 4 mm magic angle spinning (MAS) double-resonance probe. The sample was packed in a thin wall zirconium oxide rotor and spun at 8 kHz using compressed nitrogen to prevent sample degradation in air. 27Al NMR: all experiments were performed using direct acquisition. 31P NMR data were acquired both with direct acquisition (120 s delay between scans) and with cross-polarization. 29Si HMR data for all 1D experiments were performed using ramped cross-polarization with SPINAL64 decoupling during acquisition. Two dimensional experiments were performed using proton driven spin diffusion (PDSD) with a mixing time of 5 ms.
The results of the HMR measurements can be seen in FIG. 4. FIG. 4A shows the results of 2D MAS 29Si HMR of SAPO-37 (0.21). FIG. 4B shows the results of 2D MAS 29Si HMR of SAPO-37(0.63). FIG. 4C shows the results of MAS 29Si HMR of SAPO-37 systems of different gel-ratios, FIG. 4C shows the presence of isolated Si(OAl)4 sites at −93 ppm and Si(OAl)3(OSi) sites at −98 ppm.
FIGS. 4A-4C illustrate that silicon begins to cluster at higher loadings. FIG. 4A shows low to no peaks at −103 ppm corresponding to a cluster of two sites, and at −108 ppm, corresponding to a cluster of three sites. As illustrated in FIGS. 4B and 4C, at higher levels of silicon loading, the silicon begins to cluster, forming peaks at −103 ppm-Si(OAl)2(OSi)2 and −108 ppm, Si(OAl)(OSi)3. Lower silicon loadings, such as using SAPO-37 (0.21) as shown in FIGS. 3A and 3C, reduces the peak at −98 ppm, indicating a higher prevalence of isolated single sites with weak Brønsted acidity over clusters of multiple sites.
NH3—Temperature Programmed Desorption (TPD)
The quantity and strength of acid sites was investigated using temperature programmed desorption (TPD) of ammonia. As-synthesized materials were pretreated in a 20% O2 in He mixture and heated at 10° C./min to 550° C. and held at 550° C. for 2 hours. Desorption was performed at 10° C./min to 600° C. for 40 minutes.
In this experiment, ammonia is adsorbed onto the surface of the catalyst, binding to the acid sites, giving a defined peak. The area of this peak corresponds to the quantity of ammonia in the system. The system is then heated and the ammonia desorbs with the temperature. The stronger the acid site, the higher the temperature required to desorb the ammonia.
The total acidity values for SAPO-37(0.21) and SAPO-37(0.42) obtained by NH3-TPP were within experimental error. As shown in FIG. 5, the total number of acid sites, as measured by total mmol/g of desorbed NH3, showed that SAPO-37(0.21) and SAPO-37(0.42) had similar amounts of acid sites, while with SAPO-37(0.83) showed far fewer acid sites than either SAPO-37(0.21) or SAPO-37(0.42). Analyzing the temperature regions indicates the relative strength of the acid sites present, with stronger sites requiring higher temperatures for desorption. As shown in FIG. 5, the lower loading materials SAPO-37(0.21) and SAPO-37(0.42) had more weak acid sites as shown by the higher values at lower temperatures, but increased silicon loading lead to a decrease in weak acid sites and an increase in strong acid sites. These results are consistent with the silicon clustering results suggested by the NMR data in FIGS. 4A-4C.
FT-IR, CO Probe
The number and strength of acid sites were further investigated using FT-IR spectra from a carbon monoxide (CO) probe. Samples of each tested catalyst were ground and pressed into self-supporting pellets. The pellets were then heated at 10° C./min to 550° C. in flowing gas comprising 20% O2/80% N2, then held at temperature for 1 hour. Gas flow was then switched to helium and held for additional 1 hr. The samples were cooled to 30° C. and the spectrum recorded. Nine 0.02 cc infections of CO were added to the samples, followed by 1 final 0.2 cc injection. Following each injection, the system was equilibrated for 3 min before the spectrum was recorded. All spectra were recorded on a Nicolet Nexus 870 IR spectrometer, with 128 scans using a cooled MCT detector. All spectra were processed using the GRAMS/Al 9 software available from Thermo Scientific.
The results, of FT-IR, CO probe testing are presented in Table 5.







TABLE 5







FT-IR, CO probe results











System
CO area/au
Peak shift/cm−1






SAPO-37 (0.21)
0.854
305



SAPO-37 (0.42)
0.856
311



SAPO-37 (0.63)
0.582
321









Table 5 shows that the total acidity, as indicated by the CO area/arbitrary unit (au) is:

SAPO-37(0.21) ̃SAPO-37(0.42)>SAPO-37(0.63)

The peak shift gives an insight into the acid strength, where a higher shift corresponds to stronger acid sites. Table 5 shows that in terms of acid strength:

SAPO-37(0.63)>SAPO-37(0.42)>SAPO-37(0.21)

Both the NH3-TPD and FT-IR CO probe data suggest that SAPO-37(0.21) has the same quantity of acid sites as SAPO-37(0.42), and that SAPO-37(0.63) has fewer acid sites than either SAPO-37(0.21) or SAPO-37(0.42). Similarly, both the NH3-TPD and FT-IR CO probe data suggest that SAPO-37(0.63) has the strongest acid sites and SAPO-37(0.21) has the weakest. The NH3-TPD suggested that SAPO-37(0.21) and SAPO-37(0.42) had more weak sites (desorption at 200-300° C. and 300-400° C.) than SAPO-37(0.63), but SAPO-37(0.63) had more strong acid sites (400-500° C.) than either SAPO-37(0.21) or SAPO-37(0.42).
FT-IT, Collidene Probe
The number and strength of acid sites were further investigated using FT-IR spectra from a collidene probe. Samples were ground and pressed into self-supporting pellets. The pellets were then heated at 10° C./min to 550° C. in flowing 20% O2/N2, then held at temperature for 2 hours. The samples were cooled to 30° C. and the spectrum recorded. Collidene was adsorbed at 150° C. for 1 hr. Collidene was then desorbed at 150/300/450° C. for 1 hr each step. All spectra were recorded on a Nicolet Nexus 870 IR spectrometer, with 128 scans using a cooled MCT detector. All spectra were processed using the GRAMS/Al 9 software available from Thermo Scientific.
In this experiment, collidene is adsorbed onto the surface of the catalyst, binding to the acid sites, giving a defined peak. The area of this peak corresponds to the quantity of collidene in the system. The system is then heated and the collidene desorbs with the temperature. The stronger the acid site, the higher the temperature required to desorb the collidene. Weak sites are characterized as collidene desorbs between 150° and 300° C., medium sites are characterized as collidene desorbs between 300° and 450° C., and strong sites are characterized as still having collidene adsorbed at 450° C.
The results of FT-IR collidene probe testing are presented in Table 6.







TABLE 6







FT-IR, collidene probe results











System
Weak sites
Medium sites
Strong sites
Total sites





SAPO-37 (0.21)
0.913
2.845
1.609
5.367


SAPO-37 (0.42)
0.389
2.722
1.593
4.704


SAPO-37 (0.63)
0.382
2.420
1.501
4.303









Table 6 shows that the total acidity as measured by the total number of acid sites is:

SAPO-37(0.83)>SAPO-37(0.42)>SAPO-37(0.21)

Regarding the strength of the acid sites, the weak and medium sites both showed higher numbers for the SAPO-37(0.21) than SAPO-37(0.63). The large number of weak sites for SAPO-37(0.21), 0.913 out of 5.367 total sites, accounted for more than 15% of the total. This was much higher than for SAPO-37(0.42), which had 0.389 out of 4.704 or 8.3% of the total and SAPO-37(0.83), which had 0.382 out of 4.303 or 8.9% of the total, and suggests a large proportion of Brønsted acid sites that are discrete and of a single-site nature. The strength of the SAPO-37(0.42) weak acid sites and the SAPO-37(0.83) for strong acid sites does not perfectly align with the other acid investigations, but the medium site data is nearly equivalent for SAPO-37(0.21) and SAPO-37(0.42).
The greater fraction of weak Brønsted acid sites is attributable to a greater proportion of type II isomorphous substitutions of silicon for phosphorous in the catalyst framework. Catalysts with higher silicon loadings are typified by greater proportion of strong acid sites that are attributable to type III substitutions, which lead to a reduction in the proportion of weak Brønsted acid sites.
The SAPO-37 unit cell was optimized using CRYSTAL09 package to perform ab initio calculations of crystal system, R. Dovesi, R. Orlando, B. Civalleri, C. Roetti, V. R. Saunders, and C. M. Zicovich-Wilson, Z. Kristallogr. 220, 571 (2005). The SAPO-37 unit cell contained 577 atoms with the formula H1Si1Al96P95O384. This corresponds, to a 1 mol % loading of silicon. A unit cell was modeled with NH3 present such that it could interact with the acid site (H4N1Si1Al96O384). Using the following equation the binding energy of NH3 with SAPO-37 was estimated to be 117 kJ mol−1:

Ebind=E(SAPO-37+NH3)−E(SAPO-37)−E(NH3)

The above calculation may be used as a measure of acidity. The results are in the expected range for these calculations.
Powder X-Ray Diffraction and BET Surface Area
Powder X-Ray diffraction patterns were obtained using a Siemens D5000 diffractometer where λ=1.54058 angstrom (Å) with Cu Kα1 radiation, in addition, an X-ray diffraction pattern of the catalyst SAPO-5 (AFI) was obtained. The three higher loading samples were found to be phase-pure, but SAPO-37(0.11) showed a significant AFI impurity phase. The SAPO-37(0.11) showed peaks corresponding to both FAU-type framework at 111 and 331, as well as IZA AFI-type framework at 100 and 200. The results of powder X-ray diffraction can be found in FIG. 6.
BET surface area measurements to investigate the total surface area of the catalysts were performed using a Gemini 2375 surface area analyzer and prepared using flow gas preparation. The results of BET surface area measurements and estimated silicon content in wt % can be found in FIG. 7. The unit cell determinations provided similar unit cell sizes for the three measured SAPO-37 catalysts, although the larger loadings of SiO2 resulted in slightly larger unit, cells, providing additional evidence for increased silicon substitution in the molecular sieve framework.
The XRD and BET results were typical for this system.
Inductively Coupled Plasma (ICP)
ICP measurements were taken to quantify the actual weight percentage of silicon in each of the prepared catalyst. A Perkin-Elmer Optimum 3000 DV was used to provide ICP results. Calcined samples were prepared and fully digested in 10 ml of deionized water and 10 ml of ACS Plus Certified sulfuric acid available from Fisher Scientific. Solutions of standard concentrations were used for calibration.
The ICP results and ratio of silicon to phosphorous loadings in the gel formed in Example 1 can be found in Table 7 below:







TABLE 7







ICP results












Si/P Gel ratio
Si/wt %



System
from synthesis gel
From ICP measurements














SAPO-5 (AFI)
0.21
1.33



SAPO-34 (CHA)
0.23
0.73



SAPO-BER
0.21
0.73



SAPO-37 (0.21)
0.21
2



SAPO-37 (0.63)
0.63
9.1









The ratio of silicon to phosphorous in the gel used to form the catalysts for SAPO-37(0.83) and SAPO-37(0.21) was 0.63:0.21, or 3:1. The silicon weight percentage of SAPO-37(0.63) was higher than the silicon weight percentage of SAPO-37(0.21). The ratio of silicon weight percentage between SAPO-37(0.63) and SAPO-37(0.21) was 9.1:2, or 4.55:1. This was higher than the gel loading ratio of 3:1.
Scanning Electron Microscopy Images
Scanning Electron Microscopy images of the catalysts were obtained using a JOEL-JSM5910 microscope with accelerating voltage of 0.3-30 kV. The samples were prepared by gold costing, SEM revealed that all 3 systems consisted, of regular octahedral crystals of roughly 1 μm in length. An SEM image of SAPO-37(0.21) is provided as FIG. 8A, an SEM image of SAPO-37(0.42) is provided as FIG. 8B, and an SEM image of SAPO-37(0.83) is provided as FIG. 5C.
Example 3—Gas Phase Catalysis
Preparation of Catalysis
The gel loadings for the catalysts used in the gas phase examples is given in Table 8.







TABLE 8







Gel loadings for SAPO materials








Sample
Gel composition





SAPO-5
2.0 H3PO4:1.0 Al2O3:0.4 SiO2:



2.0 Triethylamine:50.0 H2O


HSAPO-37 (0.42)
1.00H3PO4:0.67Al2O3:0.97TPAOH:



0.025TMAOH:0.42SiO2


MSAPO-37 (0.22)
1.00H3PO4:0.69Al2O3:2.40 TPAOH:



0.026TMAOH:0.22SiO2:6.96 H2O


LSAPO-37 (0.17)
1.00H3PO4:0.68Al2O3:2.40 TPAOH:



0.026TMAOH:0.17SiO2:7.12 H2O


SAPO-11
2.0 H3PO4:1.0 Al2O3:0.4 SiO2:2.0 Pr2NH:50.0 H2O


SAPO-41
2.0 H3PO4:1.0 Al2O3:0.4 SiO2:2.0 Pr2NH:50.0 H2O









The SAPO-37 catalysts were made as in Example 1.
SAPO-5 was prepared by diluting 4.7 g of H3PO4 (85% in H2O) in a Teflon beaker with 10 ml of H2O and stirred until homogeneous (5 minutes). 4.3 g of Al(OH)3 was slowly added to the acid, followed by a further 10 ml of H2O. The mixture was stirred for 10 minutes. 0.76 g of fumed silica was slowly added, followed by 10 ml of H2O. The mixture was stirred for 30 minutes. Finally the templating agent (N-Methyl-dicyclohexyl-amine) was added dropwise and a further 10 ml of H2O was added. The mixture was stirred for 1 hour. The white gel was then transferred to an autoclave and heated to 200° C. for 2 hours. On removal, the gel was filtered and washed with H2O and left to dry at 70° C. overnight. The white solid produced was calcined at 550° C. for 10 hours before use.
SAPO-TRY was prepared in the same manner as the SAPO-5 above, except that no templating agent was used.
The SAPO-34 catalyst was prepared according to the method provided by D. Dubois, et al., Fuel Process. Technol. 2003, 83, 203, the disclosures of which are hereby incorporated by reference.
TS-1, a titanium silicalite zeolite-based catalyst was obtained from the National Chemical laboratory, Pune India. The sample has a Ti loading of 2 wt %. The TS-1 catalyst is disclosed in U.S. Pat. No. 4,859,785, the disclosure of which is hereby incorporated by reference.
Analysis and Conversion and Selectivity
The conversion and selectivity of the system was analyzed using a Clarus 400 gas chromatogram with FID and using an Elite 5 column, the peak areas were calibrated using known response factors. The method was: start at 120° C., hold for 2 minutes, then ramp at 15° C./min up to 220° C., and hold for 5 minutes at 220° C. The method was 13 minutes and 40 seconds long in total. The cyclohexanone oxime has a peak corresponding to a retention time of 4.0 minutes, ε-caprolactam peak has a peak corresponding to a retention time of 5.8 minutes, the by-product has a peak corresponding to a retention time of 6.6 minutes. The injector port was set to 220° C. and the detector was set to 250° C. The carrier pressure (Helium) was 14 psig. The method was given 1 minute to equilibrate before injection. A centrifuged sample of 5 μl was injected.
The samples were calibrated using a relative response factor of ε-caprolactam relative to cyclohexanone oxime, which was found to be 1.119. The samples were calibrated to an internal standard of chlorobenzene for the mass balance. Cyclohexanone oxime was found to have a relative response factor of 1.2972 relative to chlorobenzene, and ε-caprolactam was found to have a response factor of 1.4518 relative to chlorobenzene. The mass balance at 130° C. was found to be 106% after 6 hours. Using the following formula, the response factors were used to calculate the moles of cyclohexanone oxime, ε-caprolactam, and by-products (response factor assumed to be 1.00):




  
    
      Moles
      ⁡
      
        [
        A
        ]
      
    
    
      Moles
      ⁡
      
        [
        B
        ]
      
    
  
  =
  
    Relative
    ⁢
    
      
    
    ⁢
    Response
    ⁢
    
      
    
    ⁢
    Factor
    ×
    
      
        Area
        ⁡
        
          [
          A
          ]
        
      
      
        Area
        ⁡
        
          [
          B
          ]
        
      
    
  




Experimental Procedure

A cylindrical glass tube (4 mm in diameter) with a glass frit was packed with a 5 mm layer of glass beads, a layer of pelletized catalyst ( ̃0.25 g, 40 mm) and a further 60 mm layer of glass beads, was placed inside a flow reactor heated by a jacket to 673 K. The sample was then treated under a flow of Helium gas for 1 hour. The temperature was dropped to the test temperature as set forth below and a liquid feed of 10 wt % cyclohexanone oxime in ethanol was fed into the reactor, maintaining the experimental weight hour space velocity (WHSV) as set forth below.
Comparison of Catalysts of WHSV 0.3 hr−1 and 300° C.
Gas phase runs were made for various catalysts under similar conditions. The conditions selected were a WHSV of 0.3 hr−1, a liquid feed of 10 wt % oxime in ethanol, a temperature of 300° C., helium flow of 33.3 mL/min, and 0.25 g of catalyst. Each catalyst was pre-activated at 400° C. for 1 hour in a 33.3 mL/min flow of helium. Samples were taken for conversion and selectivity analysts after an hour.
The results can be found in Table 9 and FIG. 9.







TABLE 9







Gas phase results













ε-caprolactam



System
Conversion/mol %
selectivity/mol %






SAPO-37 (0.42)
99.7
86.2



SAPO-5
66.0
53.8



SAPO-34
78.2
75.2



SAPO-TRY
74.9
79.0









The SAPO-37 (0.42) catalyst produced much higher conversion and selectivity results than any of the other SAPO catalysts tested.
Comparison of SAPO-37 Catalysts with SAPO-41 and TS-1 at Various Temperatures
As a comparison, gas phase runs were made for SAPO-37, SAPO-41, and TS-1 catalysts under similar conditions. The conditions selected were a WHSV of 0.3 hr−1, a liquid feed of 10 wt % oxime in ethanol, a helium flow of 33.3 ml/min, and 0.25 g of catalyst. Each catalyst was pre-activated at 400° C. for 1 hour in a 33.3 mL/min flow of helium. Samples were taken for conversion and selectivity analysts after an hour. The results for various temperatures are provided in FIGS. 10-13.
The results for SAPO-37(0.22) are shown in FIG. 10, SAPO-37(0.22) resulted in high conversions and selectivity. Conversion increased as temperature increased from 300° to 350°. Selectivity also increased, but was above 80% in at all three measured temperatures.
The results for SAPO-37(0.42) are shown in FIG. 11, SAPO-37(0.22) resulted in high conversions and selectivity. Conversion and selectivity decreased as temperature increased from 300° to 325°. However, conversion remained high at 94.6% and selectivity remained above 80%.
As shown in FIG. 12, the SAPO-41 provided high conversion, but much lower selectivity to the ε-caprolactam than the SAPO-37 catalysts.
The results for TS-1 are shown in FIG. 13. Conversion and selectivity were high for TS-1 at 300° C.
FIGS. 14 and 15 compare the results from the various catalysts at the same temperatures.
As can be seen in FIG. 14, at 300° C., high selectivity and conversion were obtained for SAPO-37 (0.42) compared to the SAPO-41 catalyst.
As shown in FIG. 15, all three SAPO catalysts gave good conversion at 325° C. However, only the SAPO-37 catalysts gave high selectivities.
Example 4—Liquid Phase Catalysis
Preparation of Catalysis
The gel loadings for the catalysts used in the gas phase examples is given in Table 10.







TABLE 10







Gel loadings for SAPO materials








Sample
Gel composition





SAPO-5
2.0 H3PO4:1.0 Al2O3:0.40 SiO2:2.0 TEA:50 H2O


SAPO-34
2.0 H3PO4:1.0 Al2O3:0.30 SiO2:2.0 TEAOH:50 H2O


(CHA)



SAPO-37
1.00H3PO4:0.67Al2O3:0.97TPAOH:0.025TMAOH:0.21SiO2


(0.21)



SAPO-37
1.00H3PO4:0.67Al2O3:0.97TPAOH:0.025TMAOH:0.42SiO2


(0.42)



SAPO-41
2.0 H3PO4:1.0 Al2O3:0.4 SiO2:2.0 Pr2NH:50.0 H2O









The SAPO-37 catalysts were made as in Example 1.
The SAPO-5 and SAPO-34 catalysts were made as in Example 3.
The SAPO-11 catalyst was made according to P. Meriaudeau, V. A. Tuan, V. T. Nghiem, S, Y. Lai, L. N. Hung and C. Naccache, Journal of catalysis, 1997, 169, 55-66, the disclosure of which is hereby incorporated by reference.
The SAPO-41 catalyst was made according to P. Meriaudeau, V. A. Tuan, V. T. Nghiem, S. Y. Lai, L. N. Hung and C. Naccache, Journal of catalysis, 1997, 169, 56-66, the disclosure of which is hereby incorporated by reference.
Experimental Procedure
100 mg of cyclohexanone oxime, 100 mg of catalyst and 20 ml of benzonitrile as solvent (Aldrich) were added to a glass reactor and stirred at 500 rpm at the selected temperature under reflux. Samples were taken at predetermined intervals based on the selected temperature: 30 minutes for 130° C., 15 minutes for 150° C., 5 minutes for 170° C., and 5 minutes for 190° C. All samples were analysed on a Varian Star 3400CX gas chromatogram with flame ionization detector (FID). Samples were injected into a Perkin Elmer a HP1 cross linked methylsiloxane (30 m×0.32 mm×1 μm film thickness) column. The samples were mass balanced using chlorobenzene as an internal standard.
Analysis of Conversion and Selectivity
The samples were analyzed as in Example 3, with benzonitrile solvent peak having a large peak corresponding to a retention time of 3.5 minutes.
Comparison of Catalysis at 130° C.
Liquid phase runs were made for various catalysts under similar conditions. The conditions selected were 130° C., with a catalyst:cyclohexanone oxime:benzonitrile ratio of 1:1:200, and 0.1 g of cyclohexanone oxime. The samples were analyzed after 7 hours.
The results can be found in Table 11 and FIG. 16.







TABLE 11







Liquid phase results












IZA






framework
Pore
Conversion/
ε-caprolactam


System
code
diameter
mol %
selectivity/mol %





SAPO-5
AFI
7.3 Å × 7.3 Å
33.2
65.9


SAPO-34
CHA
3.8 Å × 3.8 Å
18.6
87.3


SAPO-37
FAU
7.4 Å × 7.4 Å
98.8
90.3


(0.42)






SAPO-41
AFO
7.0 Å × 4.3 Å
23.5
68.1









The SAPO-37 and SAPO-5 frameworks have similar pore diameters, the former 7.4 Å, the latter 7.3 Å, yet they showed very different levels of activity, therefore the environments were probed using 29Si MAS NMR techniques. The SAPO-37 spectrum showed a dominant peak at −93 ppm, with a smaller secondary peak at −98 ppm, corresponding to Si(OAl)4 and Si(OSi)(OAl)3 environments respectively. The Si(OAl)4 environment shows that the silicon has substituted a single phosphorus atom, therefore generating a Brønsted acid site (a type II substitution mechanism), the Si(OSi)(OAl)3 environment shows that two silicons have substituted a phosphorus and aluminium pair, therefore not generating an acidify (type III substitution mechanism). In contrast the SAPO-5 spectrum showed a dominant peak at −110 ppm, corresponding to a Si(OSi)4 environment, suggesting the silicon was present mostly in siliceous zones. This showed that the isolated silicon sites are the active site for this reaction. The silicon content of the SAPO-37 species was varied (denoted SAPO-37(X) where X is the assynthesised gel ratio), giving three different samples, which showed subtle differences in catalytic performance.
Both SAPO-37 catalysts showed very high conversion and selectivity, especially when compared to the other SAPO catalysts.
Liquid Beckmann Rearrangement Using Chlorobenzene Solvent
The same experimental procedure as for the liquid reactions with benzonitrile were performed with chlorobenzene as a solvent. The reaction was performed at 130° C., with 100 mg of cyclohexanone oxime, 10.0 mg of SAPO-37(0.21) catalyst, and 20 ml of chlorobenzene. After 7 hours, 14.6% conversion of oxime and 95.0% selectivity for ε-caprolactam were observed.
Progression of Reaction Over Time for Various Catalysts at 130° C.,
The conversion, selectivity, and yield over time of a reaction with a SAPO-37 (0.16) catalyst, a SAPO-11 catalyst, and a SAPO-41 catalyst at 130° C. are illustrated in FIGS. 17-20. The SAPO-37 catalyst showed very high conversion and selectivity compared to the other SAPO catalysts.
FIG. 17 illustrates the high conversion and selectivity using the SAPO-37 (0.16) catalyst in a liquid phase reaction using benzonitrile as solvent. The reaction was performed at 130° C., with a catalyst:cyclohexanone oxime:benzonitrile ratio of 1:1:200, with 0.1 g of cyclohexanone oxime used, and performed for 7 hours.
FIG. 13 illustrates the same reaction using anhydrous benzonitrile as solvent. The reaction was performed at 130° C., with a catalyst:cyclohexanone oxine:anhydrous benzonitrile ratio of 1:1:200, with 0.125 g of cyclohexanone oxime used, and performed for 7 hours.
The anhydrous benzonitrile shown in FIG. 18 resulted in greater selectivity but lower conversion than the (wet) benzonitrile shown in FIG. 17. Both FIGS. 17 and 18 show high conversion and selectivity in a liquid phase reaction.
FIG. 19 illustrates a lower conversion and selectivity for a liquid phase reaction with SAPO-11 as the catalyst. The reaction was performed at 130° C. with a catalyst:cyclohexanone oxime:benzonitrile ratio of 1:1:200, with 0.1 g of cyclohexanone oxine used, and run for 7 hours.
FIG. 20 illustrates an even lower conversion and selectivity for a liquid phase reaction with SAPO-41 as the catalyst. The reaction was performed at 130° C., with a catalyst:cyclohexanone oxime:benzonitrile ratio of 1:1:200, with 0.1 g of cyclohexnone oxime used, and run for 7 hours.
Further liquid test results are provided in Tables 12 and 13. Table 12 presents the conversion, selectivity, and yield for SAPO-37 catalysts with various gel loadings at time intervals during the reaction. Table 13 presents the final conversion and selectivity values taken for each catalyst at the indicated temperature. Benzonitrile was used as the solvent in each of the runs in Tables 12 and 13, SAPO-37(0.21)AN designates the use of anhydrous benzonitrile as the solvent.







TABLE 12







Conversion and selectivity of SAPO-37 catalysts at various temperatures













Tem-







perature
Time
Conversion
Selectivity
Yield


System
° C.
mins
mol %
mol %
mol %















SAPO-37(0.21)
130
30
33.7
97.1
32.7


SAPO-37(0.21)
130
60
55.3
95.3
52.8


SAPO-37(0.21)
130
90
69.5
95.0
66.0


SAPO-37(0.21)
130
120
78.1
96.1
75.1


SAPO-37(0.21)
130
150
84.6
95.5
80.8


SAPO-37(0.21)
130
180
89.3
96.0
85.7


SAPO-37(0.21)
130
210
92.2
95.4
88.0


SAPO-37(0.21)
130
240
94.2
95.7
90.2


SAPO-37(0.21)
130
270
95.6
96.7
92.4


SAPO-37(0.21)
130
300
96.5
96.7
93.4


SAPO-37(0.21)
130
330
97.8
96.1
94.0


SAPO-37(0.21)
130
360
98.2
94.6
92.9


SAPO-37(0.21)
130
390
98.7
94.0
92.8


SAPO-37(0.21)
130
420
98.9
93.5
92.4


SAPO-37(0.21)AN
130
30
30.2
100.0
30.2


SAPO-37(0.21)AN
130
60
54.1
99.1
53.6


SAPO-37(0.21)AN
130
90
71.0
98.6
70.0


SAPO-37(0.21)AN
130
120
82.5
99.0
81.6


SAPO-37(0.21)AN
130
150
88.4
98.3
86.9


SAPO-37(0.21)AN
130
180
93.4
97.8
91.3


SAPO-37(0.21)AN
130
210
96.5
97.9
94.4


SAPO-37(0.21)AN
130
240
97.9
97.8
95.7


SAPO-37(0.21)AN
130
270
98.4
98.1
96.5


SAPO-37(0.21)AN
130
300
99.0
98.4
97.4


SAPO-37(0.21)AN
130
330
99.3
97.7
97.0


SAPO-37(0.21)AN
130
360
99.5
97.8
97.3


SAPO-37(0.21)AN
130
390
99.7
97.9
97.6


SAPO-37(0.21)AN
130
420
99.8
97.8
97.6


SAPO-37(0.42)
130
30
33.5
96.4
32.3


SAPO-37(0.42)
130
60
53.0
98.4
52.1


SAPO-37(0.42)
130
90
69.0
94.9
65.5


SAPO-37(0.42)
130
120
78.3
95.7
74.9


SAPO-37(0.42)
130
150
85.0
93.5
79.5


SAPO-37(0.42)
130
180
89.8
93.3
83.8


SAPO-37(0.42)
130
210
92.3
92.7
85.5


SAPO-37(0.42)
130
240
94.3
91.3
86.1


SAPO-37(0.42)
130
270
96.0
90.5
86.8


SAPO-37(0.42)
130
300
97.1
91.1
88.5


SAPO-37(0.42)
130
330
97.6
90.7
88.5


SAPO-37(0.42)
130
360
98.1
91.0
89.2


SAPO-37(0.42)
130
390
98.5
90.7
89.3


SAPO-37(0.42)
130
420
98.8
90.3
89.1


SAPO-37(0.63)
130
30
38.2
91.6
35.0


SAPO-37(0.63)
130
60
58.4
91.5
53.4


SAPO-37(0.63)
130
90
73.1
90.3
66.1


SAPO-37(0.63)
130
120
80.8
90.4
73.0


SAPO-37(0.63)
130
150
87.0
90.9
79.1


SAPO-37(0.63)
130
180
91.4
90.9
83.0


SAPO-37(0.63)
130
210
94.3
90.9
85.7


SAPO-37(0.63)
130
240
96.5
89.3
86.2


SAPO-37(0.63)
130
270
97.8
89.3
87.3


SAPO-37(0.63)
130
300
98.6
88.9
87.7


SAPO-37(0.63)
130
330
99.3
89.9
89.2


SAPO-37(0.63)
130
360
99.5
88.1
87.7


SAPO-37(0.63)
130
390
99.7
88.8
88.5


SAPO-37(0.63)
130
420
99.8
88.4
88.2


SAPO-37(0.21)
150
15
44.5
94.5
42.1


SAPO-37(0.21)
150
30
75.4
95.7
72.1


SAPO-37(0.21)
150
45
87.3
94.7
82.7


SAPO-37(0.21)
150
60
95.0
92.8
88.2


SAPO-37(0.21)
150
75
97.2
92.5
89.9


SAPO-37(0.21)
150
90
98.7
93.7
92.4


SAPO-37(0.21)
150
105
99.4
92.7
92.2


SAPO-37(0.21)
150
120
99.7
91.1
90.8


SAPO-37(0.21)
150
135
99.8
92.5
92.3


SAPO-37(0.21)
150
150
99.9
92.7
92.6


SAPO-37(0.21)
150
165
99.9
91.6
91.6


SAPO-37(0.21)
150
180
99.9
91.4
91.4


SAPO-37(0.21)
150
195
100.0
91.3
91.3


SAPO-37(0.21)
150
210
100.0
91.3
91.3


SAPO-37(0.21)
150
225
100.0
91.0
91.0


SAPO-37(0.21)
150
240
100.0
90.8
90.8


SAPO-37(0.42)
150
15
44.6
94.6
42.2


SAPO-37(0.42)
150
30
69.8
90.2
62.9


SAPO-37(0.42)
150
45
80.8
88.9
71.8


SAPO-37(0.42)
150
60
87.3
89.5
78.1


SAPO-37(0.42)
150
75
93.2
90.4
84.2


SAPO-37(0.42)
150
90
95.2
91.1
86.7


SAPO-37(0.42)
150
105
96.6
90.1
87.1


SAPO-37(0.42)
150
120
97.9
88.0
86.1


SAPO-37(0.42)
150
135
98.5
89.4
88.1


SAPO-37(0.42)
150
150
99.0
89.5
88.7


SAPO-37(0.42)
150
165
99.3
90.6
90.0


SAPO-37(0.42)
150
180
99.5
90.9
90.5


SAPO-37(0.42)
150
195
99.7
91.1
90.8


SAPO-37(0.42)
150
210
99.8
91.0
90.8


SAPO-37(0.42)
150
225
99.9
88.5
88.4


SAPO-37(0.42)
150
240
99.9
88.7
88.7


SAPO-37(0.63)
150
15
45.5
84.3
38.3


SAPO-37(0.63)
150
30
66.7
82.1
54.8


SAPO-37(0.63)
150
45
79.5
84.4
67.1


SAPO-37(0.63)
150
60
86.7
83.3
72.2


SAPO-37(0.63)
150
75
90.4
84.1
76.0


SAPO-37(0.63)
150
90
92.1
85.0
78.3


SAPO-37(0.63)
150
105
94.7
84.1
79.6


SAPO-37(0.63)
150
120
96.2
84.2
81.0


SAPO-37(0.63)
150
135
97.2
84.2
81.8


SAPO-37(0.63)
150
150
98.0
85.2
83.5


SAPO-37(0.63)
150
165
98.6
85.0
83.8


SAPO-37(0.63)
150
180
98.9
85.2
84.2


SAPO-37(0.63)
150
195
99.2
84.3
83.6


SAPO-37(0.63)
150
210
99.4
83.8
83.4


SAPO-37(0.63)
150
225
99.6
83.7
83.3


SAPO-37(0.63)
150
240
99.7
84.1
83.8


SAPO-37(0.21)
170
5
27.2
97.1
26.4


SAPO-37(0.21)
170
10
57.9
92.7
53.7


SAPO-37(0.21)
170
15
77.5
91.1
70.6


SAPO-37(0.21)
170
20
88.2
91.3
80.5


SAPO-37(0.21)
170
25
93.9
91.2
85.6


SAPO-37(0.21)
170
30
96.3
90.3
87.0


SAPO-37(0.21)
170
35
97.9
91.0
89.1


SAPO-37(0.21)
170
40
98.6
90.4
89.2


SAPO-37(0.21)
170
45
99.1
89.7
88.9


SAPO-37(0.21)
170
50
99.5
91.1
90.6


SAPO-37(0.21)
170
55
99.7
89.9
89.6


SAPO-37(0.21)
170
60
99.8
90.1
89.9


SAPO-37(0.42)
170
5
18.2
96.7
17.6


SAPO-37(0.42)
170
10
46.5
93.4
43.4


SAPO-37(0.42)
170
15
63.5
94.3
59.9


SAPO-37(0.42)
170
20
75.0
94.9
71.2


SAPO-37(0.42)
170
25
83.4
92.0
76.7


SAPO-37(0.42)
170
30
89.8
92.2
82.8


SAPO-37(0.42)
170
35
93.2
90.2
84.1


SAPO-37(0.42)
170
40
95.5
88.8
84.8


SAPO-37(0.42)
170
45
97.0
89.0
86.3


SAPO-37(0.42)
170
50
98.4
90.1
88.7


SAPO-37(0.42)
170
55
98.8
89.3
88.2


SAPO-37(0.42)
170
60
98.9
89.9
88.9


SAPO-37(0.63)
170
5
27.8
79.2
22.0


SAPO-37(0.63)
170
10
50.9
82.9
42.2


SAPO-37(0.63)
170
15
68.1
83.2
56.7


SAPO-37(0.63)
170
20
76.6
83.7
64.2


SAPO-37(0.63)
170
25
83.3
84.9
70.7


SAPO-37(0.63)
170
30
88.5
82.7
73.2


SAPO-37(0.63)
170
35
91.8
82.7
75.9


SAPO-37(0.63)
170
40
93.5
82.3
77.0


SAPO-37(0.63)
170
45
94.9
82.9
78.7


SAPO-37(0.63)
170
50
96.1
82.5
79.3


SAPO-37(0.63)
170
55
96.9
83.9
81.3


SAPO-37(0.63)
170
60
97.6
83.9
81.9


SAPO-37(0.21)
190
5
41.3
98.1
40.6


SAPO-37(0.21)
190
10
72.0
98.0
70.5


SAPO-37(0.21)
190
15
86.3
96.1
82.9


SAPO-37(0.21)
190
20
92.9
92.4
85.9


SAPO-37(0.21)
190
25
97.3
90.6
88.1


SAPO-37(0.21)
190
30
98.3
91.2
89.6


SAPO-37(0.21)
190
35
99.1
91.7
90.9


SAPO-37(0.21)
190
40
99.5
91.1
90.6


SAPO-37(0.21)
190
45
99.7
92.4
92.1


SAPO-37(0.21)
190
50
99.8
89.6
89.4


SAPO-37(0.21)
190
55
99.9
88.7
88.6


SAPO-37(0.21)
190
60
99.9
89.8
89.7


SAPO-37(0.42)
190
5
29.5
100.0
29.5


SAPO-37(0.42)
190
10
66.4
100.0
66.4


SAPO-37(0.42)
190
15
87.1
95.6
83.2


SAPO-37(0.42)
190
20
93.7
95.2
89.2


SAPO-37(0.42)
190
25
97.0
96.3
93.4


SAPO-37(0.42)
190
30
98.6
96.0
94.6


SAPO-37(0.42)
190
35
99.3
96.6
96.0


SAPO-37(0.42)
190
40
99.7
93.2
93.0


SAPO-37(0.42)
190
45
99.8
93.3
93.1


SAPO-37(0.42)
190
50
99.9
91.8
91.8


SAPO-37(0.42)
190
55
99.9
92.3
92.2


SAPO-37(0.42)
190
60
100.0
90.6
90.6


SAPO-37(0.63)
190
5
35.9
85.5
30.7


SAPO-37(0.63)
190
10
70.8
84.3
59.6


SAPO-37(0.63)
190
15
87.7
80.9
70.9


SAPO-37(0.63)
190
20
92.2
80.8
74.5


SAPO-37(0.63)
190
25
95.8
80.0
76.7


SAPO-37(0.63)
190
30
97.1
81.2
78.8


SAPO-37(0.63)
190
35
98.0
79.7
78.2


SAPO-37(0.63)
190
40
98.7
78.9
77.9


SAPO-37(0.63)
190
45
99.0
78.4
77.6


SAPO-37(0.63)
190
50
99.3
79.2
78.7


SAPO-37(0.63)
190
55
99.5
79.0
78.5


SAPO-37(0.63)
190
60
99.7
79.5
79.3
















TABLE 13







Final conversion and selectivity of SAPO-37 catalysts at various


temperatures















ε-






caprolactam




Time
Conversion
selectivity



System
mins
mol %
mol %














130° C.
SAPO-37(0.21)
420
98.9
93.5



SAPO-37(0.21)
420
99.8
97.8



AN






SAPO-37(0.42)
420
98.8
90.3



SAPO-37(0.63)
420
99.8
88.4


150° C.
SAPO-37(0.21)
240
100.0
90.8



SAPO-37(0.42)
240
99.9
88.7



SAPO-37(0.63)
240
99.7
84.1


170° C.
SAPO-37(0.21)
60
99.8
90.1



SAPO-37(0.42)
60
98.9
89.9



SAPO-37(0.63)
60
97.6
83.9


190° C.
SAPO-37(0.21)
60
99.9
89.8



SAPO-37(0.42)
60
100.0
85.4



SAPO-37(0.63)
60
99.7
79.5









The results in Tables 12 and 13 indicate high levels of conversion and selectivity using SAPO-37 as the catalyst and benzonitrile as the solvent in a liquid phase reaction. The data in Tables 12 and 13 show conversion greater than 97.5% within the measured times, while selectivity for ε-caprolactam ranged from about 80% for SAPO-37(0.63) at 190° C. to about 98% for SAPO-37(0.21) at 130° C. in anhydrous benzonitrile.
Generally, the SAPO-37(0.21) provided higher selectivity than the SAPO-37(0.42), which in turn provided higher selectivity than the SAPO-37(0.63), although high selectivity and conversion were seen for ail three catalysts. These results are consistent with the higher quantity of acid site suggested by the characterization data in Example 2.
Liquid Beckmann Rearrangement of Cyclododecanone to ω-Laurolactam
The Beckmann rearrangement is also known to be useful in producing ω-laurolactam from cyclododecanone (see FIG. 1B).
The same experimental procedure as for the liquid reactions with cyclohexanone oxime were performed with cyclododecanone oxime using SAPO-37(0.21) and SAPO-11 catalysts. The reaction was performed at 130° C., with 175 mg of cyclododecanone oxime, 100 mg of catalyst, and 20 ml of benzonitrile. The gas chromatogram retention times were 8.4 minutes for cyclododecanone, 10.8 minutes for cyclododecanone oxime, and 11.8 minutes for ω-laurolactam. The results using SAPO-37(0.21) are provided in FIG. 19 and Table 14. The results using SAPO-11 are provided in FIG. 20.







TABLE 14







Results of liquid cyclododecanone oxime reaction


SAPO-37(0.21), 190° C.










Time/minutes
Conversion/mol %
Selectivity/mol %
Yield/mol %













5
83.9
99.9
83.9


10
99.3
99.4
98.8


60
100.0
99.8
99.8









FIG. 21 illustrates very high conversion and selectivity using SAPO-37 as the catalyst, while FIG. 22 illustrates much lower conversion and selectivity using SAPO-37 as the catalyst. The only notably by-product found using SAPO-37 was cyclododecanone.
While the present disclosure is primarily directed to production of ε-caprolactam and ω-laurolactam, it should be understood that the features disclosed herein have application to the production of other lactams and other monomers.
While this invention has been described as relative to exemplary designs, the present invention may be further modified within the spirit and scope of this disclosure. Further, this application is intended to cover such departures from the present disclosure as come within known or customary practice in the art to which this invention pertains.

## Claims

1. A catalyst comprising:
a silicon-containing aluminophosphate framework with the IZA framework code FAU; and
a plurality of discrete Brønsted acid sites positioned in an interior of the framework, the acid sites comprising silicon isomorphously substituted for phosphorous in the framework;
wherein the catalyst is a SAPO-37 type catalyst, and the catalyst is formed from a gel having a molar ratio of silicon to phosphorous from 0.21:1 to 0.42:1.

2. The catalyst of claim 1, wherein the silicon comprises about 1 wt. % to about 10 wt. % of the total weight of the catalyst.

3. The catalyst of claim 2, wherein the silicon comprises about 2 wt. % to about 9.1 wt. % of the total weight of the catalyst.

4. A silicoaluminophosphate catalyst having a microporous crystalline framework structure having a composition on an anhydrous basis of:


mR:(SixAlyPz)O2 

wherein:
R is at least one organic templating agent;
m is from 0.02 to 0.3; and
x, y, and z, are selected within the values bounded by the points A, B, C, D, and E on a ternary diagram, where:
















x
y
z




















A
0.01
0.47
0.52



B
0.94
0.01
0.05



C
0.98
0.01
0.01



C
0.39
0.60
0.01



E
0.01
0.60
0.39









the catalyst comprising a plurality of discrete Brønsted acid sites positioned in an interior of the framework, the acid sites comprising silicon isomorphously substituted for phosphorous in the framework; wherein the ratio of silicon to phosphorous is from 0.21:1 to 0.42:1.

5. The catalyst of claim 4, wherein x, y, and z, are selected within the values bounded by the points a, b, c, d, and e on a ternary diagram, where:














x
y
z




















a
0.02
0.49
0.49



b
0.25
0.37
0.38



c
0.25
0.48
0.27



d
0.13
0.60
0.27



e
0.02
0.60
 0.38.

6. The catalyst of claim 5, wherein the catalyst is a SAPO-37 catalyst.

7. The catalyst of claim 4, wherein the catalyst is a silicon-containing aluminophosphate framework with the IZA framework code FAU.

8. The catalyst of claim 4, wherein the at least one organic templating agent is at least one of tetrmethylammonium hydroxide pentahydrate and tetrapropylammonium hydroxide.

9. The catalyst of claim 4, wherein the silicon comprises about 1 wt. % to about 10 wt. % of the total weight of the catalyst.

10. A method of forming a SAPO-37 catalyst, comprising:
adding an aluminum source to a phosphorous source to form an aluminum/phosphorous mixture;
dissolving tetrmethylammonium hydroxide pentahydrate in tetrapropylammonium hydroxide to form a TMAOH/TPAOH solution;
adding fumed silica to the TMAOH/TPAOH solution to form a structural template solution;
adding the structural template solution to the aluminum/phosphorous mixture to form a gel having a ratio of silicon to phosphorous from 0.21:1 to about 0.42:1; and
heating the gel to form the catalyst, the catalyst having a silicon-containing aluminophosphate framework with the IZA framework code FAU and a plurality of discrete Brønsted acid sites positioned in an interior of the framework, the acid sites comprising silicon isomorphously substituted for phosphorous in the framework.

11. The method of claim 5, wherein the aluminum source is aluminum oxide and the phosphorous source is phosphoric acid.

12. The method of claim 5, further comprising:
isolating a product by at least one of centrifuging, filtering, or washing the catalyst; and
drying the isolated catalyst.