Patent Publication Number: US-4322566-A

Title: Magnesium oxide catalyst

Description:
This is a division, of application Ser. No. 113,991 filed Jan. 21, 1980, now U.S. Pat. No. 4,269,735. 
    
    
     This invention comprises an improved catalyst for phenolics alkylation. More specifically, this invention comprises a catalyst and a process. The catalyst is magnesium oxide promoted by selected metal ions and sulfate ions. The catalyst is useful in highly selective phenolic methylation reactions. 
     Vapor phase methylation of phenols or magnesium oxide is taught in U.S. Pat. No. 3,479,410 which also requires the presence of 2,4,6-trimethylphenol as an ingredient in the feedstream. The invention is useful for phenols having at least one ortho hydrogen. Japanese publication No. 69-27367 teaches phenol methylation over magnesium oxide catalyst in the presence of an elemental metal such as copper, zinc, molybdenum, tungsten, platinum, and palladium. 
     In addition, U.S. Pat. Nos. 4,060,561 and 4,060,560 teach various reactions over magnesium oxide catalysts promoted with oxides of aluminum, uranium, titanium, cerium, manganese, zinc and iron under specific reaction conditions. U.S. Pat. Nos. 4,110,253 and 4,125,736 teach the use of magnesium oxide catalyst promoted with tungsten oxide, silica sol, and sodium silicate for the disproportionation of highly alkylated phenols with phenol. 
     These catalysts, while useful for many reactions, still produce large amounts of various alkylated by-products which are undesirable in many reactions. 
     There are many catalysts which teach ortho methylated products from the methylation of phenol in the vapor phase. Magnesium oxide itself is a useful catalyst as set forth in U.S. Pat. No. 3,446,856, but requires temperatures in the range of 475° to 600° C. In this temperature range, catalyst life is short and methanol decomposition is high. Manganese sulfate on magnesium oxide has been used for a catalyst and overcomes the objections mentioned for magnesium oxide alone as shown in U.S. Pat. No. 3,873,628. Titanium oxide is known as a catalyst for phenol methylation as set forth in Japan Kokai 78 77,029. Selectivity is shown to be good using a 1/0.05 magnesium oxide/titanium dioxide catalyst. The present invention shows a more active catalyst than the oxides of this reference. 
     In U.S. Pat. No. 3,873,628, manganese sulfate is mixed with magnesium oxide resulting in a catalyst which is an ortho director when an alkyl alcohol is reacted with a phenolic compound. The combination is said to allow the alkylation to proceed at a lower temperature without reducing selectivity to the ortho position. However, the reaction produces sulfur dioxide as a by-product and must be removed before disposal in the atmosphere. 
     Chromium oxide alone as a promoter with magnesium oxide, has also been described in Japan Kokai 79/30,122 and Japan Kokai 79 27,529, respectively. The chrominum oxide on magnesium oxide catalyst described is more active and decomposes less methanol than a corresponding chromium oxide/magnesium oxide catalyst for any given temperature. Uranium oxide/magnesium oxide has also been described in Chem Abstracts 67:73341. 
     Thus it is clear that the prior art catalysts, while useful for various reactions, have hitherto not been sufficiently reactive, do not develop sufficiently high surface area and crush strength necessary for the conditions of these reactions. Most reactions using these catalysts are carried out at such high temperatures that catalyst life is short while product and feedstream decomposition is high. It would therefore be of great benefit to provide an improved catalyst and process that overcomes these rejections. 
     It has now been discovered in accordance with the present invention that a catalyst sufficiently active for methylation of phenols and which operates at low temperatures with accompanying low decomposition of alkylating agent can be obtained by adding to a magnesium oxide base catalyst from about 0.5 to about 15% by weight of a promoter selected from the group consisting of amorphous titanium, uranium, zirconium or chromium ions together with sulfate ions at concentrations of 0.5 to about 15% by weight, and mixtures of these, all based on the total weight of the final catalyst. Surprisingly, this catalyst does not effectively disproportionate phenol materials. 
     In addition the catalysts of the present invention can optionally contain up to about 3% by weight of graphite as a pelletizing lubricant. The graphite has no significant effect on product distribution. 
     The materials produced using the catalyst and process of the instant invention are useful as modifiers for phenol formaldehyde resins, as chemical intermediates to phenol derivatives in the synthesis of Vitamin E and in polymerization processes such as the preparation of polyphenyleneoxide (PPO), a high performance thermoplastic. 
     The catalysts of the present invention are formed using special preparations. In addition to the catalysts found to be effective in the present invention, many other catalysts were tested. In general, catalysts were prepared by dissolving 2.8 grams of metal sulfate in about 12 cubic centimeters (cc) of water. The solution was then added to 25 grams (g) of magnesium oxide catalyst (Harshaw MG-0601, trademark of and sold by Harshaw Chemical Company), the solution evaporated to dryness and then calcined in air for two hours at about 500° C. 
     However, not all sulfates are water soluble and special preparations were required for titanium, zirconium, uranium, molybdenum, cerium, vanadium, and tin which were tested. 
     Vanadium sulfate promoted catalyst was obtained by forming a solution of VO(C 2  O 4 ) 2   -2  and (NH 4 ) 2  SO 4  by simple mixing. This mixture was then added to magnesium oxide and the balance of the procedure was carried out. 
     Titanium sulfate promoted catalyst was prepared by diluting 3 cubic centimeters (cc) of tetraisopropyl titanate to 10 cc volume with isopropanol. This solution was added to magnesium oxide and the solvent removed under vacuum. An ammonia sulfate (NH 4 ) 2  SO 4  solution was added to incorporate sulfate anion, followed by drying and calcination. 
     Molybdenum sulfate promoted catalyst was prepared by dissolving molybdenum trioxide (MoO 3 ) in aqueous NH 3  and adding the solution to magnesium oxide. After drying, a solution of ammonia sulfate (NH 4 ) 2  SO 4  was added, followed by drying and calcination. 
     Zirconium sulfate promoted catalyst was prepared by adding sulfuric acid to zirconium sulfate to increase the solubility of ZrOSO 4  before impregnation of magnesium oxide. 
     Uranium sulfate promoted catalyst was prepared by dissolving uranium nitrate in water and adding the solution to magnesium oxide. The mixture was dried and ammonium sulfate was added. The catalyst was formed by the subsequent drying and calcination step described. 
     Tin sulfate promoted catalyst was prepared by dissolving stannous chloride (SnCl 2 ) in ammonia sulfate solution, adding to magnesium oxide, drying and calcining. 
     Cerium sulfate promoted catalyst was prepared by the same method described for uranium, using cerium nitrate. 
     These preparations of the catalysts of the instant invention are not the only ones possible, and are used simply to illustrate methods which can be used. It is apparent from data obtained that most metal sulfates are not effective catalysts, and in fact, most are poor catalysts. 
    
    
     The invention is more concretely described with reference to the examples below wherein all parts and percentages are by weight unless otherwise specified. The examples are provided to illustrate the present invention and not to limit it. 
     EXAMPLE 1 
     The Catalyst 
     The catalyst is magnesium oxide base promoted with Ti +4  and sulfate ions. The magnesium oxide carrier is a high surface area magnesium oxide (such as Merck Maglite D). Various sources of sulfate ion are possible, but one preferred component is magnesium sulfate. Titanium is well dispersed in the catalyst and the X-ray analysis does not reveal any well crystallized titanium compounds. Magnesium oxide is treated with a small amount of isopropanol followed by addition of titanium tetraisopropoxide diluted with isopropanol. Any method of titanium tetraisopropoxide addition which creates a good dispersion on the magnesium oxide surface will produce a selective catalyst. 
     Catalyst Preparation 
     While various preparations are possible for the above described catalyst, the following procedure is preferred. The raw materials (on a 100 part by weight basis) necessary are: 
     
         ______________________________________                                    
Magnesium oxide   77.8   parts                                            
Titanium tetraisopropoxide                                                
                  6.5    parts                                            
Magnesium sulfate 5.4    parts                                            
Graphite          1.7    parts                                            
Silica sol        8.6    parts - 30% aqueous                              
                            solution                                      
______________________________________                                    
 
    
     In preparing the catalyst, magnesium oxide is treated with titanium tetraisoproxide before any aqueous additions. X-ray analysis is used to evaluate success. The silica sol is added as a 30 weight percent solution. Magnesium sulfate is added as an aqueous solution. Water content is adjusted as desired for tableting (3/16&#34; diameter tablets are commercial size). Surface area of the final material falls in the range of 80-150 m 2  /g. The tablets were calcined in air at 500° C. for 3 hours. 
     The catalyst operated continuously for 19 days or 456 hours. No deactivation was noticed at the conclusion of the test. The final run was a high conversion phenol methylation. The final 72 hour product was collected and distilled. Analysis by gas/liquid chromatography is given below in weight percent (w/o). 
     
                       TABLE 1                                                     
______________________________________                                    
Composition           Feed   Product                                      
______________________________________                                    
Methanol              57.27  35.93                                        
Water                 9.09   16.87                                        
Anisole                      0.08                                         
Phenol                33.64  2.30                                         
o-Methylanisole              0.20                                         
o-Cresol                     10.66                                        
m,p-Cresol + 2,6-Dimethylanisole                                          
                             0.25                                         
2,6-Xylenol                  29.98                                        
2,4-Xylenol                  0.66                                         
2,4,6-Trimethylanisole       0.14                                         
2,4,6-Trimethylphenol        2.74                                         
2,3,6-Trimethylphenol        0.16                                         
High Boilers                 0.03                                         
                             100.00                                       
______________________________________                                    
 Conditions: LHSV = 1.4, 470° C., 20 PSIG                          
 
    
     EXAMPLE 2 
     A run was made with the preferred catalyst using recycle methanol. Reaction conditions were 468° C., LHSV=2.0 and 20 PSIG. The results are set forth in Table 2. 
     
                       TABLE 2                                                     
______________________________________                                    
Composition           Feed   Product                                      
______________________________________                                    
Methanol              57.27  33.47                                        
Water                 9.09   16.42                                        
Anisole                      0.16                                         
Phenol                33.64  4.22                                         
o-Methylanisole              0.27                                         
o-Cresol                     13.63                                        
m,p-Cresol + 2,6-Dimethylanisole                                          
                             0.32                                         
2,6-Xylenol                  27.66                                        
2,4-Xylenol                  1.01                                         
2,4,6-Trimethylanisole       0.15                                         
2,4,6-Trimethylphenol        2.52                                         
2,3,6-Trimethylphenol        0.15                                         
High Boilers                 0.02                                         
______________________________________                                    
 
    
     Initially the temperature and space velocity must be controlled to achieve good selectivity. However, 2,4,6-trimethylphenol output rapidly decreases. 
     EXAMPLE 3 
     Example 3 was carried out to show the effect of varying times and conditions using a standard feed of 56.57 percent methanol, 9.10 percent water, 25.75 percent phenol and 8.58 percent o-cresol. The reactor was at atmospheric pressure. The results are set forth in Table 3. 
     
                       TABLE 3                                                     
______________________________________                                    
Time, hours  16        45      87      208                                
°C.   443       462     462     464                                
LHSV         2.0       2.0     2.0     1.4                                
Product Composition                                                       
Anisole      0.81      0.44    0.23    0.17                               
Phenol       23.94     12.35   11.11   16.21                              
o-Methylanisole                                                           
             0.63      0.58    0.41    0.22                               
o-Cresol     44.99     34.90   31.75   37.50                              
m,p-Cresol   Tr        0.75    0.62    0.37                               
2,6-Dimethylanisole                                                       
2,6-Xylenol  22.90     43.94   49.81   42.46                              
2,4-Xylenol  3.63      1.89    1.37    0.96                               
2,4,6-Trimethylanisole                                                    
             Tr        0.21    0.22    0.11                               
2,4,6-Trimethylphenol                                                     
             2.89      4.61    4.28    1.90                               
2,3,6-Trimethylphenol                                                     
             0.21      0.28    0.20    0.10                               
High Boilers Tr        0.05    Tr      Tr                                 
______________________________________                                    
 
    
     EXAMPLE 4 
     A silica-free catalyst was prepared using 180 g magnesium oxide powder (Merck Maglite D), 15 g titanium tetraisopropoxide and 6.25 g MgSO 4 . Surface area of the tableted and calcined (500° C., 2 hrs.) catalyst was 116 m 2  /g. The catalyst had a lower crush strength than catalysts prepared with silica having similar ingredients. Analysis of the reaction product at 465° C. reaction temperature, 1.4 LHSV, 20 psig is given in table 4. The feed was a 5:1 mole ratio of methanol to phenolics containing 9.1% water. 
     
                       TABLE 4                                                     
______________________________________                                    
Cresylics Composition Feed   Product                                      
______________________________________                                    
Anisole                      0.79                                         
Phenol                75     4.32                                         
0-Methylanisole              0.55                                         
o-Cresol              25     41.07                                        
m,p-Cresol + 2,6-Dimethylphenol                                           
                             0.42                                         
2,6-Xylenol                  43.71                                        
2,4-Xylenol                  3.34                                         
2,4,6-Trimethylphenol        5.54                                         
2,3,6-Trimethylphenol        0.26                                         
______________________________________                                    
 
    
     EXAMPLE 5 
     An experiment was carried out to illustrate the effect of higher titanium and magnesium sulfate levels. The catalyst was prepared as previously described except the composition of the catalyst was changed compared to the previous examples (100 part by weight basis). 
     
         ______________________________________                                    
magnesium oxide        70.9   parts                                       
magnesium sulfate      9.8    parts                                       
titanium tetraisopropoxide                                                
                       9.8    parts                                       
silica sol             7.9    parts                                       
graphite               1.6    parts                                       
______________________________________                                    
 
    
     The surface area of the catalyst was 128 m 2  /g. Results were compared at 16 and 48 hours. Differences between Example 5 and Example 1 were apparent. Example 5 produced higher anisole and 2,4,6-trimethylphenol levels which are undesirable. The feed composition was 56.57 percent methanol, 9.10 percent water 25.75 percent phenol and 8.58 percent o-cresol. The reaction was carried out at an LHSV of 2.0 and temperature of 456° C. The results are set forth in Table 5. 
     
                       TABLE 5                                                     
______________________________________                                    
Cresylics Composition 16 hrs. 48 hrs.                                     
______________________________________                                    
Anisole               1.17    2.97                                        
Phenol                18.58   22.06                                       
o-Methylanisole       0.94    1.85                                        
o-Cresol              38.90   37.73                                       
2,6-Dimethylanisole + m,p-Cresol                                          
                      1.52    2.34                                        
2,6-Xylenol           27.73   25.53                                       
2,4-Xylenol           3.28    2.52                                        
2,4,6-Trimethylanisole                                                    
                      0.60    0.60                                        
2,4,6-Trimethylphenol 6.74    4.06                                        
2,3,6-Trimethylphenol 0.38    0.32                                        
High Boilers          0.17    Tr                                          
                      100.00  100.00                                      
______________________________________                                    
 
    
     EXAMPLE 6 
     An example was carried out to illustrate the effect of various levels of (NH 4 ) 2  SO 4  [ammonium sulfate]. 
     Magnesium oxide powder (180 g) was mixed with 40-60 g isopropanol. Titanium tetraisopropoxide (25 g) was added to the MgO and well mixed. Silica sol in 30% aqueous solution and varying amounts of ammonium sulfate were added. 
     The water content was adjusted by drying and graphite added before tableting. All catalysts were calcined 2 hours at 550° C. in air prior to use. Three cases were studied. 
     
         ______________________________________                                    
Case 1              4g (NH.sub.4).sub.2 SO.sub.4                          
Case 2             16g (NH.sub.4).sub.2 SO.sub.4                          
Case 3             25g (NH.sub.4).sub.2 SO.sub.4                          
______________________________________                                    
 
    
     A very small amount of dimethyl sulfide was detected in the reactor effluent. More dimethyl sulfide is observed when ammonium sulfate is used than when magnesium sulfate is used. Also ammonium sulfate has the disadvantage that ammonia is released when the ammonium sulfate is added to the magnesium oxide-titanium tetraisopropoxide mixture. The results of this experiment are set forth in Table 6. 
     
                       TABLE 6                                                     
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               Product                                                    
            Feed Case 1    Case 2  Case 3                                 
______________________________________                                    
Temperature °C.                                                    
                 465       465     468                                    
Pressure, PSIG   40        30      40                                     
LHSV             1.2       1.2     1.4                                    
Methanol      56.57  Approx. 40 percent                                   
Water         9.10   Approx. 16 percent                                   
Pheonlics                                                                 
Distribution, w/o                                                         
Anisole              1.78      2.39  0.44                                 
Phenol        75.00  18.35     4.14  1.40                                 
o-Methylanisole      0.64      1.42  0.45                                 
o-Cresol      25.00  53.37     39.85 30.89                                
m,p-Cresol +                                                              
2,6-Dimethyl-                                                             
anisole              1.04      0.72  0.31                                 
2,6-Xylenol          20.84     41.29 62.16                                
2,4-Xylenol          2.65      4.62  1.18                                 
2,4,6-Trimethylanisole                                                    
                     0.08      0.16  0.06                                 
2,4,6-Trimethylphenol                                                     
                     1.15      4.22  2.94                                 
2,3,6-Trimethylphenol                                                     
                     0.20      0.71  0.14                                 
High Boilers         Tr        0.48  0.03                                 
______________________________________                                    
 
    
     EXAMPLE 7 
     An experiment was carried out to determine the effect of sodium on the catalyst composition using the following ingredients: 
     90 g Merck Maglite D magnesium oxide powder 
     12 g titanium tetraisopropoxide 
     2 g sodium sulfate 
     3 g sodium silicate 
     2 g graphite 
     The catalyst was prepared following the procedures outlined previously. The order of addition was magnesium oxide, titanium tetraisopropoxide, sodium sulfate, sodium silicate and graphite. The catalyst was tableted and calcined in air at 500° C. for 2 hours. As table 7 shows, the conversion to 2,6-xylenol is impeded by this catalyst composition. Anisoles were also very high. 
     
         ______________________________________                                    
Reaction Conditions:                                                      
                Feed-5/1 mole ratio methanol/                             
                   cresylics with 9.1% H.sub.2 O.                         
Temperature     462° C.                                            
LHSV            1.4                                                       
______________________________________                                    
 
    
     
                       TABLE 7                                                     
______________________________________                                    
Cresylics Composition Feed   Product                                      
______________________________________                                    
Anisole                      4.20                                         
Phenol                75     11.15                                        
o-Methylanisole              2.88                                         
o-Cresol              25     45.02                                        
m,p-Cresol + 2,6-Dimethylanisole                                          
                             1.65                                         
2,6-Xylenol                  25.23                                        
2,4-Xylenol                  6.08                                         
2,4,6-Trimethylphenol        3.79                                         
______________________________________                                    
 
    
     EXAMPLE 8 
     An experiment was carried out to show the effect of replacing MgSO 4  with CaSO 4 . The catalyst was prepared by mixing 180 g magnesium oxide (Merck Maglite D) with 20 cc isopropanol. The treated magnesium oxide was sprayed with a solution of 15 cc titanium tetraisopropoxide in 15 cc of isopropanol during constant mixing of the magnesium oxide. CaSO 4 .2H 2  O (17.9 g) was added followed by 20 g of a 30% aqueous solution of silica sol. The mixture was dried, sieved and tableted. The catalyst was calcined 2 hours at 500° C. The catalyst (15 cc) was loaded into a 1/2&#34; diameter electrically heated stainless steel reactor. The feedstock for the reaction and the product are described in table 8. The catalyst is not quite as active or selective as catalysts prepared using MgSO 4  in place of CaSO 4 . 
     
                       TABLE 8                                                     
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2,6-Xylenol Synthesis Using a                                             
CaSO.sub.4 Promoted Ti.sup.+4 /MgO Catalyst                               
            Feed                                                          
______________________________________                                    
Hrs, Culm            23      30    70    94                               
Temperature, °C.                                                   
                     465     462   460   465                              
Pressure, PSIG       20      25    40    40                               
LHSV                 1.4     1.8   1.4   1.4                              
Composition,                                                              
Cresylics - w/%                                                           
Anisole              0.81    0.76  0.72  0.73                             
Phenol        75     8.69    20.49 21.77 18.12                            
o-Methylanisole      1.17    0.72  0.69  0.78                             
o-Cresol      25     21.35   37.85 37.28 39.07                            
m,p-Cresol,          1.38    1.07  0.91  0.83                             
2,6-Dimethylanisole                                                       
2,6-Xylenol          45.23   28.34 31.16 32.99                            
2,4-Xylenol          3.41    4.05  2.70  2.82                             
2,4,6-Trimethylanisole                                                    
                     0.39    0.13  Tr    Tr                               
2,4,6-Trimethylphenol                                                     
                     16.71   6.14   4.70 4.31                             
2,3,6-Trimethylphenol                                                     
                     0.48    0.19  Tr    Tr                               
High Boilers         0.38    0.26   0.07  0.32                            
                     100.00  100.00                                       
______________________________________                                    
 .sup.1 feed contains 9.10 w/% H.sub.2 O in addition to 56.57 w/% methanol
 cresylics are 34.33 w % of sample                                        
 
    
     EXAMPLES 9-22 
     Various metal sulfates were evaluated at standardized conditions of 460° C., 1 LHSV atmospheric pressure and a 5 to 1 methanol to phenol mole ratio. The feed contained 9% weight water and was passed over catalysts containing 2.8 gram metal sulfate per 25 gram magnesium oxide catalyst. A wide range of metal sulfate promoters for magnesium oxide catalysts were tested. In carrying out the tests, it was considered desirable to make ortho cresol and 2,6-xylenol. Mixtures containing 2,4-xylenol, 2,4,6-trimethylphenol and higher boiling components were considered undesirable. 
     A summary of results from these direct comparisons are set forth in Table 9 below. 
     
                       TABLE 9                                                     
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METAL SULFATES EVALUATED FOR                                              
PHENOL METHYLATION                                                        
Metal    Example  Comments                                                
______________________________________                                    
Magnesium                                                                 
         9        Poor selectivity, rapid deactivation                    
Titanium 2        High activity and good selectivity                      
Vanadium 10       High methanol decomposition                             
Chromium 23       High selectivity, good activity                         
Manganese                                                                 
         11       U.S. Pat. No. 3,873,628                                 
Iron     12       Rapid deactivation in 20 hours                          
Cobalt   13       Poor selectivity, rapid activity decline                
Nickel   14       Poor activity                                           
Copper   15       Poor activity                                           
Zinc     16       Poor activity                                           
Zirconium                                                                 
         17       Fair activity, good selectivity                         
Molybdenum                                                                
         18       Rapid deactivation 16 hours                             
Cerium   19       High methanol decomposition                             
Uranium  22       Good activity and selectivity                           
Tin      20       Low conversion                                          
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     It is readily apparent that a wide range of results are obtained using various metal sulfates. 
     The feedstock for all evaluations was the same. Methanol mole ratio was 5 to 1 methanol to phenol. Water content of the feed was 9.1% to extend catalyst life. Unless otherwise stated, the magnesium oxide was in the form of 1/8 inch diameter tablets. The tests utilized a commercially available magnesium oxide (Harshaw MC-0601-T, product of the Harshaw Chemical Company). The feed was vaporized in a preheated segment of 1/8 inch line and passed over the catalyst at 1.0 liquid hourly space velocity (LHSV) at 460° C. The product was analyzed for phenolic content by gas liquid chromatography (GLC). Gas evolution was measured as representative of methanol decomposition in the reactor. 
     EXAMPLE 9 
     Magnesium sulfate was used as the source of sulfate ion. The initial product was primarily 2,4,6-trimethylphenol and the activity decreased rapidly overnight (17 hours). The results are shown in Table 10. 
     
                       TABLE 10                                                    
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Cresylics Composition, w/o                                                
                      1 hr    17 hrs                                      
______________________________________                                    
Anisole               2.18    1.73                                        
Phenol                31.52   57.81                                       
o-Methylanisole       1.11    0.57                                        
o-Cresol              9.46    11.93                                       
2,6-Dimethylanisole   1.73    0.60                                        
m,p-Cresol                                                                
2,6-Xylenol           18.66   12.29                                       
2,4-Xylenol           4.10    2.54                                        
2,4,6-Trimethylanisole                                                    
                      1.66    0.25                                        
2,4,6-Trimethylphenol 26.53   11.86                                       
2,3,6-Trimethylphenol 0.79    0.11                                        
High Boilers          2.26    0.31                                        
______________________________________                                    
 
    
     EXAMPLE 10 
     A catalyst was prepared with vanadium ions and tested in the standard run. Results are shown in Table 11. 
     
                       TABLE 11                                                    
______________________________________                                    
Cresylics Composition, w/o                                                
                     1 hr.  17 hrs                                        
______________________________________                                    
Anisole              0.78    0.09                                         
Phenol               3.90   80.32                                         
o-Methylanisole      0.29   Tr                                            
o-Cresol             13.16  17.92                                         
2,6-Dimethylanisole  0.34   Tr                                            
m,p-Cresol                                                                
2,6-Xylenol          51.22   1.67                                         
2,4-Xylenol          2.22                                                 
2,4,6-Trimethylanisole                                                    
                     0.38                                                 
2,4,6-Trimethylphenol                                                     
                     26.74                                                
2,3,6-Trimethylphenol                                                     
                     0.26                                                 
High Boilers         0.71                                                 
______________________________________                                    
 
    
     Methanol decomposition observed was 100 cc of gas in 15 min. 
     EXAMPLE 11 
     Manganese ions were tested experimentally in the test reaction. Results are shown in Table 12. 
     
                       TABLE 12                                                    
______________________________________                                    
Cresylics Composition, w/o                                                
                    100 hrs.                                              
______________________________________                                    
Anisole             0.39                                                  
Phenol              24.13                                                 
o-Methylanisole     0.06                                                  
o-Cresol            25.36                                                 
m,p-Cresol          0.11                                                  
2,6-Dimethylanisole                                                       
2,6-Xylenol         45.92                                                 
2,4-Xylenol         0.44                                                  
2,4,6-Trimethylanisole                                                    
                    0.10                                                  
2,4,6-Trimethylphenol                                                     
                    3.49                                                  
                    100.00                                                
______________________________________                                    
 
    
     EXAMPLE 12 
     Iron ions were tested in the standardized test. Results are set forth in table 13. 
     
                       TABLE 13                                                    
______________________________________                                    
Cresylics Composition, w/o                                                
                      2.5 hrs.                                            
                              24 hrs.                                     
______________________________________                                    
Anisole               1.38    0.51                                        
Phenol                13.27   73.13                                       
o-Methylanisole       0.46    Tr                                          
o-Cresol              37.94   23.69                                       
m,p-Cresol            0.33    Tr                                          
2,6-Dimethylanisole                                                       
2,6-Xylenol           36.16   2.39                                        
2,4-Xylenol           3.65    Tr                                          
2,4,6-Trimethylanisole                                                    
                      Tr      Tr                                          
2,4,6-Trimethylphenol  6.68   0.23                                        
2,3,6-Trimethylphenol  0.13   Tr                                          
High Boilers          Tr      0.05                                        
______________________________________                                    
 
    
     EXAMPLE 13 
     Cobalt ions were tested experimentally under the standardized conditions. The results are set forth in Table 14. 
     
                       TABLE 14                                                    
______________________________________                                    
Cresylics Composition w/o                                                 
                      2.5 hrs.                                            
                              20 hrs.                                     
______________________________________                                    
Anisole               1.47    0.49                                        
Phenol                8.09    62.24                                       
o-Methylanisole       1.22    Tr                                          
o-Cresol              17.51   31.67                                       
m,p-Cresol + 2,6-Dimethylanisole                                          
                      1.23    Tr                                          
2,6-Xylenol           44.32   5.25                                        
2,4-Xylenol           2.08    Tr                                          
2,4,6-Trimethylanisole                                                    
                      0.77    Tr                                          
2,4,6-Trimethylphenol 21.42   0.25                                        
2,3,6-Trimethylphenol 0.82    0.10                                        
High Boilers          1.08    Tr                                          
______________________________________                                    
 
    
     EXAMPLE 14 
     Nickel ions were tested experimentally under standard conditions. The results are set forth in Table 15. 
     
                       TABLE 15                                                    
______________________________________                                    
Cresylics Composition, w/o                                                
                      2 hrs.  20 hrs.                                     
______________________________________                                    
Anisole               1.77    0.28                                        
Phenol                43.01   71.27                                       
o-Methylanisole       0.88    Tr                                          
o-Cresol              9.37    26.01                                       
2,6-Dimethylanisole + m,p-Cresol                                          
                      2.32    Tr                                          
2,6-Xylenol           22.24   2.34                                        
2,4-Xylenol           2.20    0.10                                        
2,4,6-Trimethylanisole                                                    
                      0.79    Tr                                          
2,4,6-Trimethylphenol 15.74   Tr                                          
2,3,6-Trimethylphenol 0.67    Tr                                          
High Boilers          0.93    Tr                                          
                      100.00  100.00                                      
______________________________________                                    
 
    
     EXAMPLE 15 
     Copper ions were tested experimentally in the standard test conditions. The results are set forth in Table 16. 
     
                       TABLE 16                                                    
______________________________________                                    
Cresylics Composition, w/o                                                
                      1 hr.   4 hrs.                                      
______________________________________                                    
Anisole               1.12    0.86                                        
Phenol                32.83   53.76                                       
o-Methylanisole       0.28    Tr                                          
o-Cresol              38.80   36.38                                       
2,6-Dimethylanisole   0.25    0.10                                        
m,p-Cresol                                                                
2,6-Xylenol           21.63   7.78                                        
2,4-Xylenol           2.35    0.79                                        
2,4,6-Trimethylanisole                                                    
                      Tr      Tr                                          
2,4,6-Trimethylphenol 2.66     0.33                                       
2,3,6-Trimethylphenol 0.08    Tr                                          
High Boilers          Tr      Tr                                          
                      100.00  100.00                                      
______________________________________                                    
 
    
     EXAMPLE 16 
     Zinc ions were tested under standard conditions. The results are set forth in Table 17. 
     
                       TABLE 17                                                    
______________________________________                                    
Cresylics Composition, w/o                                                
                      16 hrs.                                             
______________________________________                                    
Anisole               0.47                                                
Phenol                73.72                                               
o-Methylanisole       Tr                                                  
o-Cresol              23.97                                               
m,p-Cresol + 2,6-Dimethylanisole                                          
                      Tr                                                  
2,6-Xylenol           1.69                                                
2,4-Xylenol           Tr                                                  
2,4,6-Trimethylanisole                                                    
                      Tr                                                  
2,4,6-Trimethylphenol 0.15                                                
2,3,6-Trimethylphenol Tr                                                  
High Boilers          Tr                                                  
______________________________________                                    
 
    
     EXAMPLE 17 
     Zirconium ions were tested under standard conditions. The results are set forth in Table 18. 
     
                       TABLE 18                                                    
______________________________________                                    
Cresylics Composition, w/o                                                
                      4 hrs.  28 hrs.                                     
______________________________________                                    
Anisole               4.61    3.32                                        
Phenol                4.96    42.93                                       
o-Methylanisole       2.65    0.29                                        
o-Cresol              28.47   42.94                                       
2,6-Dimethylanisole   1.04    0.35                                        
m,p-Cresol                                                                
2,6-Xylenol           31.21   7.56                                        
2,4-Xylenol           9.57    2.01                                        
2,4,6-Trimethylanisole                                                    
                      0.28    Tr                                          
2,4,6-Trimethylphenol 15.63   0.42                                        
2,3,6-Trimethylphenol 0.90    0.10                                        
High Boilers          0.68    0.08                                        
                      100.00  100.00                                      
______________________________________                                    
 
    
     EXAMPLE 18 
     Molybdenum ions were tested under standard conditions. The results are set forth in Table 19. 
     
                       TABLE 19                                                    
______________________________________                                    
Cresylics Composition, w/o                                                
                      2 hrs.  16 hrs.                                     
______________________________________                                    
Anisole               1.11     0.28                                       
Phenol                38.33   93.37                                       
o-Methylanisole       0.44    Tr                                          
o-Cresol              28.39    6.01                                       
m,p-Cresol + 2,6-Dimethylanisole                                          
                      0.41    Tr                                          
2,6-Xylenol           23.38    0.38                                       
2,4-Xylenol           1.98                                                
2,4,6-Trimethylanisole                                                    
                      0.19                                                
2,4,6-Trimethylphenol 5.32                                                
2,3,6-Trimethylphenol 0.28                                                
High Boilers          0.17                                                
                      100.00  100.00                                      
______________________________________                                    
 
    
     EXAMPLE 19 
     Cerium ions were tested under standard conditions. The catalyst was prepared containing Ce 2  (SO 4 ) 3  /MgO. Methanol decomposition as measured by the volumn of gas evolved from the reactor was 100 ml in 3 minutes. This compares to 100 ml in 30 minutes for the TiO 2  /SO 4   --  /MgO catalyst described in this invention whereby material balance the methanol decomposition as a percentage of initial methanol was 6 percent. Methanol loss with the cerium catalyst was thus about 50 percent which is highly undesirable. 
     EXAMPLE 20 
     Tin ions were tested under standard conditions. The results are shown in Table 20. 
     
                       TABLE 20                                                    
______________________________________                                    
Cresylics Composition, w/o                                                
                      1.5 hrs.                                            
                              19 hrs.                                     
______________________________________                                    
Anisole               3.10     1.42                                       
Phenol                15.95   63.14                                       
o-Methylanisole       1.16    Tr                                          
o-Cresol              38.72   30.64                                       
2,6-Dimethylanisole + m,p-Cresol                                          
                      0.93    0.20                                        
2,6-Xylenol           25.36   3.26                                        
2,4-Xylenol           6.79    0.56                                        
2,4,6-Trimethylanisole                                                    
                      0.10    0.15                                        
2,4,6-Trimethylphenol 7.55    0.43                                        
2,3,6-Trimethylphenol 0.24    0.10                                        
High Boilers          0.10    0.10                                        
                      100.00  100.00                                      
______________________________________                                    
 
    
     EXAMPLE 21 
     The titanium sulfate/magnesium oxide catalyst was used in a phenolics methylation using the feedstock and conditions previously described. A typical product obtained on a phenolics only basis is set forth in Table 21. The results are based on GLC analysis. 
     
                       TABLE 21                                                    
______________________________________                                    
Ti/SO.sub.4 /MgO Catalyst                                                 
Component         w/o                                                     
______________________________________                                    
Anisole           1.0                                                     
Phenol            16.8                                                    
o-Methylanisole   0.1                                                     
o-Cresol          49.7                                                    
2,6-Xylenol       30.1                                                    
2,4-Xylenol       1.0                                                     
2,4,6-Trimethylphenol                                                     
                  1.2                                                     
Higher Boilers    0.1                                                     
                  100.00                                                  
______________________________________                                    
 
    
     This catalyst was operated for approximately 100 hours with no apparent loss in activity. 
     EXAMPLE 22 
     The uranium sulfate/magnesium oxide catalyst was prepared as described above. The reaction was carried out using the feedstock and conditions set forth. The phenolics product from the reactor was analyzed using GLC and had the composition set forth in Table 22 below. 
     
                       TABLE 22                                                    
______________________________________                                    
UO.sub.2 SO.sub.4 /MgO Catalyst                                           
Component         w/o                                                     
______________________________________                                    
Anisole           0.8                                                     
Phenol            29.1                                                    
o-Methylanisole   0.4                                                     
o-Cresol          36.7                                                    
p-Cresol                                                                  
2,6-Dimethylanisole                                                       
                  0.3                                                     
2,6-Xylenol       28.3                                                    
2,4-Xylenol       1.7                                                     
2,4,6-Trimethylphenol                                                     
                  2.3                                                     
High Boilers      0.4                                                     
______________________________________                                    
 
    
     EXAMPLE 23 
     A chromium sulfate/magnesium oxide catalyst was used in a reaction under the standard test conditions set forth above. Phenolics product was again analyzed using GLC. The results are as set forth in Table 23 below. 
     
                       TABLE 23                                                    
______________________________________                                    
Cr.sub.2 (SO.sub.4).sub.3 /MgO Catalyst                                   
Component         w/o                                                     
______________________________________                                    
Anisole           1.8                                                     
Phenol            14.3                                                    
o-Methylanisole   0.4                                                     
o-Cresol          46.6                                                    
m-p-Cresol        0.2                                                     
2,6-Xylenol       27.8                                                    
2,4-Xylenol       5.0                                                     
2,4,6-Trimethylphenol                                                     
                  3.8                                                     
High Boilers      0.1                                                     
                  100.00                                                  
______________________________________                                    
 
    
     EXAMPLE 24 
     A titanium dioxide/magnesium oxide catalyst was prepared by adding three cubic centimeters tetraisopropyltitanate to 9 cubic centimeters of isopropanol. The mixture is then impregnated on 25 grams of magnesium oxide catalyst (Harshaw MG-0601). The catalyst was then dried and calcined as described for standard conditions set forth above. The catalyst was then used in the standard conditions described above and the product was analyzed using GLC. The results are set forth in Table 24 below. 
     
                       TABLE 24                                                    
______________________________________                                    
TiO.sub.2 /MgO Catalyst                                                   
Component         w/o                                                     
______________________________________                                    
Anisole           1.9                                                     
Phenol            61.5                                                    
o-Cresol          31.6                                                    
m,p-Cresol        0.5                                                     
2,6-Xylenol       3.2                                                     
2,4,6-Xylenol     1.1                                                     
2,4,6-Trimethylphenol                                                     
                  0.2                                                     
                  100.00                                                  
______________________________________                                    
 
    
     When compared, the results of Table 24 as contrasted to Table 21, show that the titanium oxide promoted magnesium oxide catalyst is much less active than those of the present invention containing amorphous titanium ions and sulfate ions. 
     The catalysts disclosed herein give methylation at lower methanol mole ratios with high amounts of ortho cresol, and high amounts of 2,6-xylenol as principle products, and very low amounts of by-products. This product distribution is important because of the ability to make one pass and obtain high proportions of desired products. In contrast, the titanium dioxide/magnesium oxide catalyst set forth in Example 5 gives very little 2,6-xylenol, an important material. 
     Phenol methylation is carried out at temperatures of from about 420° to about 500° C. (preferred 440°-470° C.) and a LSHV of from about 0.1 to about 10, although 0.5 to about 3.0 is preferred. No pressures above atmospheric are necessary, although the reaction will proceed at higher pressures. Pressures of from atmospheric to 5 atmospheres is preferred. Water added to feed is not necessary during methylation reactions since water is formed during the reaction. 
     Representative examples of alkylating agents useful in this practice of the present invention are methanol, ethanol, isopropanol, butanol and others known to those skilled in this art. Of these, methanol is preferred because polymerization and degradation do not occur. 
     Throughout this specification and claims the terminology m,p-cresol is used to indicate a mixture of meta and para-cresol. 
     While certain embodiments and details have been shown for the purpose of illustrating this invention, it will be apparent to those skilled in this art that various changes and modifications may be made herein without departing from the spirit and scope of the invention.