Abstract:
The invention relates to a catalyst to be utilized in the metathesis reactions of olefines, the catalyst comprising an after-treated tungsten complex containing diol ligands and hydrocarbon ligands, which are benzenes substituted with a lower alkyl group. The invention also relates to a method for preparing a heterogenous catalyst to be used in the metathesis reaction of olefines as well as to a metathesis process for the conversion of olefines.

Description:
BACKGROUND OF THE INVENTION 
     The metathesis, or in other words the disproportionation, of olefines relates to a reaction wherein one or more olefines are converted into olefines having a different molecular weight. An olefine may be disproportionated with itself into an olefine having a higher molecular weight and into an olefine having a lower molecular weight. In this case, the reaction may be called &#34;self-disproportionation&#34;. Two different olefines may also be converted into other olefines by means of the metathesis reaction 
     In order to function, the metathesis reactions of olefines require a catalyst system, which includes a transition metal compound, often a cocatalyst and sometimes also a compound acting as a promoter. The catalyst systems based on tungsten or molybdenum are especially efficient. Such catalysts generally comprise a tungsten or molybdenum oxide on an inorganic carrier, which is e.g. silica or alumina. It is known to add different substances as a promoter to such catalyst. Thus, e.g. according to EP publication 152,112, tungsten oxide or other titanium-containing substances are added to the surface of the catalyst as a promoter According to U.S. Pat. No. 4,559,320, it is known to use a tungsten catalyst on a silica carrier, into which magnesium oxide is additionally mixed. According to EP publication 56,013, a catalyst composition is known comprising a molybdenum oxide or a tungsten oxide on a silica carrier. 
     According to U.S. Pat. No. 3,956,178, a metathesis catalyst of three components is known, which catalyst is prepared from a tungsten compound, an organic ligand and an organo-metallic compound. In this patent, the tungsten compound is a titanium oxychloride and the organic ligand contains a nitrile or ester group. As examples of ligands are mentioned phthalodinitrile, adipo nitrile and ethyl phthalate. 
     According to U.S. Pat. No. 4,550,216, a metathesis catalyst is known, which comprises a compound of tungsten, a halogen and a phenoxy group, which compound is possibly substituted. 
     SUMMARY OF THE INVENTION 
     This invention relates to a catalyst to be used in the metathesis reactions of olefines. The invention also relates to a method of preparing such catalyst. 
     Still further, the invention relates a metathesis process for the conversion of olefines into olefines having a different molecular weight. 
     It is a primary object of the present invention to provide totally new metathesis catalyst from organo-tungsten compounds. 
     It is another object of the invention to provide for the production of the new metathesis catalysts of the present invention. 
     Still further, it is an object of the present invention to provide for a metathesis process for the conversion of olefines into olefines having a different molecular weight. 
     With the above and other objects in view, the new metathesis catalysts of the present invention are mainly characterized in that the same comprise an after-treated tungsten complex which contains diol ligands and hydrocarbon ligands, which are benzenes substituted with a lower alkyl group. The process of after-treating is the process of impregnating a catalyst in a carrier and then calcinating the catalsyt. 
     The inventive method for preparing a catalyst is characterized that 
     a) a complex between an inorganic tungsten salt and a diol is formed, 
     b) the complex obtained is caused to react with a benzyl anion or a benzyl anion substituted with a lower alkyl group for obtaining a tungsten complex containing diol ligands, benzyl ligands or benzyls ligands substituted with a lower alkyl group, and 
     c) the tungsten complex obtained is impregnated into a carrier and calcinated. 
     The inventive metathesis process for the conversion of olefines, wherein the catalyst comprising a tungsten compound converts the olefine into olefines having a different molecular weight, is characterized in that the heterogenous catalyst comprises an after-treated tungsten complex, which contains diol ligands and unsubstituted benzyl ligands or benzyl ligands substituted with a lower alkyl group. 
     The tungsten complexes, in which a diol or a benzene substituted with a lower alkyl group, e.g. mesitylene, are used as ligands may be converted into heterogenous catalysts, which function in the metathesis of olefines at a higher activity than conventional catalysts, in which ammonium tungstenate acts as a precursor. In addition, the preparation of the catalysts is easier, since the quantity of metal is low and the solubility in polar organic solvents is good. 
     The fact that the structures of the inventive synthesized precursors are of a novel type, is based on spectra and the determination of the released HCl. Thus, the inventive catalyst is used in the metathesis reaction, in which C═C bonds decompose and the moieties combine again. For example propene may be prepared from ethylene and 2-butene. 
     The inventive catalyst is prepared from a tungsten complex, in which as ligands are used diols and benzenes substituted with a lower alkyl group. 
     In the first step, an inorganic tungsten salt and a diol form a complex according to the equation (1): 
     
         WCl.sub.6 +2 diolH.sub.2 →WCl.sub.2 (diol.sub.2)+4HCl (1) 
    
     in which diolH 2  =a diol compound, preferably a picanol or trans-1,2-cyclohexane diol. 
     Thereafter, the tungsten oxide obtained reacts with a bromide of a benzene substituted with a lower alkyl group, in this example with a mesitylene bromide, and a metallic magnesium for obtaining a catalyst precursor in accordance with the equation (2): 
     
         WCl.sub.2 (diol).sub.2 +2ArCH.sub.2 Br+2 Mg→W(ArCH.sub.2).sub.2 (diol).sub.2 +MgBr.sub.2 +MgCl.sub.2                      ( 2) 
    
     in which ArCH 2  is a mesitylene ligand. 
    
    
     DESCRIPTION OF PREFERRED EMBODIMENTS 
     The examples which follow are given to further illustrate the present invention. The scope of the invention is not meant to be limited thereto. 
     The syntheses were made in a nitrogen atmosphere using a Schlenck technique. The solvents, except for the tetrahydrofurane, were dried by calcium hydride and distilled, and the tetrahydrofurane was dried with a sodium-benzophenon mixture before the distillation. The diols were sublimated before use. 
     The hydrochloride released in the reactions was determined by bubbling the reaction solution with nitrogen and by passing the solution into an 0.10M NaOH solution, which was titrated. 
     For the determination of the tungsten content and the chlorine content of the products, the same were decomposed by means of a concentrated nitric acid. The chloride was potentiometrically nitrated and the tungsten was gravimetrically determined as an oxide. As for the catalysts, the tungsten was determined by means of XRF. 
     The infrared spectra were run in nujol (JASCO IR-810), the NMR spectra were run in carbon tetrachloride or deuterochloroform (JEOL JNM-PMX 60, JEOL GSX-400). 
     The catalysts were tested in a microreactor in a quartz-glass tube, through which the purified propylene was passed (molecular sieves and copper catalyst). A sample of the gas flow passed through the catalyst was taken automatically at intervals of one hour and a gas chromatogram (column Chrompackin Fused Silica) was run. 
     EXAMPLES 1-3 
     A reaction of tungsten hexachloride with trans-1,2-cyclohexane diol 
     EXAMPLE 1 
     A reaction of tungsten hexachloride and trans-1,2-cyclohexane diol in a substance quantity ratio 1:1 
     
         WCl.sub.6 +chdH.sub.2 →WCl.sub.4 (chd)+2 HCl 
    
     1.635 g (4.12 mmol) of tungsten hexachloride was dissolved in a Schlenk tube, in 15.0 ml of carbon tetrachloride. 0.4214 g (3.63 mmol) of trans-1,2-cyclohexane diol was added to the solution. The solution was admixed with a magnet mixer, and it was allowed to reflux for one hour. Thereafter, acid formation was no longer observed. The liquid phase was evaporated under an underpressure, i.e., sub-atmospheric pressure. The product was a black solid substance, which dissolved in 1,2-dimethoxy ethane and methanol. On the basis of an IR-spectrum, there was no organic moiety in the product. The test was repeated by using hexane as a solvent, whereby the product was similar to that obtained above. 
     EXAMPLE 2 
     A reaction of tungsten hexachloride and trans-1,2-cyclohexane diol in a substance quantity ratio 1:2 
     
         WCl.sub.6 +2chdH.sub.2 →WCl.sub.2 (chd).sub.2 +4 HCl 
    
     1.276 g (3.22 mmol) of tungsten hexachloride and 0.7474 g (6.44 mmol) of trans-1,2-cyclohexane diol were dissolved in 15.0 ml of carbon tetrachloride. The solution was admixed and it was allowed to reflux for one and a half hours. Thereafter, acid formation was no longer observed. After the evaporation of the liquid phase, a red-brown substance was obtained, which dissolved well in toluene, chloroform, 1,2-dimethoxy ethane and methanol. It dissolved poorly in carbon tetrachloride, and it did not dissolve at all in hexane. From the compound were measured IR and  1  H NMR spectra (cf. Table 1). On the basis of these, the compound contains cyclohexane diolato groups bound to the tungsten. 
     69.6 mg of the cyclohexane compound of tungsten prepared was decomposed with 0.5 ml of concentrated nitric acid and 9.5 ml of water was added to the mixture. The released chloride ions were titrated potentiometrically by using a calomel and silver electrode. According to the determination, the compound contained 13.7% of chlorine. 
     For the determination of the tungsten, 102.2 mg of the compound prepared was admixed into 15.0 ml of concentrated nitric acid and 15.0 ml of water. The mixture was cooked for half an hour, whereafter a pale yellow WO 3  was separated by filtration. The tungsten oxide was dried by maintaining it at a temperature of 850° C. for two hours. The oxide was weighed and according to the weight the quantity of tungsten obtained was 42.4%. If it is assumed that the four chloroligands of tungsten hexachloride are replaced with two biserrate cyclohexane diolato ligands, the WCl(chd) 2  thus obtained would contain 14.7% of chlorine and 38.1% of tungsten. 
     EXAMPLE 3 
     A reaction of tungsten hexachloride and trans-1,2-cyclohexane diol in the cold was effected by dissolving 1.899 g (4.79 mmol) of tungsten hexachloride in 20.0 ml of 1,2-dimethoxyethane and adding 1.112 g (9.59 mmol) of trans-1,2-cyclohexane diol to the solution. The solution was maintained at a temperature of -15° C. and it was admixed by a magnet mixer. After mixing of five hours, no removal of the acid was observed. The solvent was evaporated under an underpressure, i.e., sub-atmospheric pressure. The product was a dark-brown, tough oily substance, which turned blue in connection with the sampling. The dark-blue colour possibly results from the reduction of the tungsten. 
     EXAMPLES 4 and 5 
     A reaction of tungsten hexachloride and pinacol 
     EXAMPLE 4 
     A reaction of tungsten hexachloride and pinacol in a substance quantity ratio 1:1 
     
         WCl.sub.6 +pinH.sub.2 →WCl.sub.4 (pin)+2 HCl 
    
     0.807 g (2.04 mmol) of tungsten hexachloride was dissolved in 15.0  ml of carbon tetrachloride. 0.2405 g (2.04 mmol) of pinacol was added to the solution, and it was allowed to reflux for two hours, after which no acid was removed. The liquid phase was evaporated from a green solution when subjected to an underpressure, i.e., sub-atmospheric pressure. The product was a green solid substance, which rapidly turned blue when coming into contact with air. The decomposition was very rapid, due to which IR--and  1  H NMR-spectra could not be measured from the compound. The green and blue colours relate to reduced tungsten compounds. 
     EXAMPLE 5 
     A reaction of tungsten hexachloride and pinacol in substance quantity ratio 1:2 
     
         2WCl.sub.6 +4pinH.sub.2 →[WCl(pin).sub.2 ].sub.2 +4 HCl+Cl.sub.2 
    
     1.600 g (4.04 mmol) of tungsten hexachloride was dissolved in 25.0 ml of carbon tetrachloride and 0.9645 g (8.16 mmol) of pinacol was added to the solution. All of the pinacol did not dissolve in this step. The reaction mixture was mixed with a magnet mixer, and it was allowed to reflux for four hours. After this, no acid formation could be observed. When the reaction advanced, the pale green solution turned dark blue. After the evaporation of the liquid phase, the product obtained was a strongly blue powdery substance. An IR-spectrum was measured from the product (cf. Table 1). 
     105.9 mg of the compound prepared was decomposed by mixing it in 0.5 ml of concentrated nitric acid. After this, 9.5 ml of water was added to the mixture, and the chloride content was determined. The content obtained was 7.6% (the calculated content was 7.7%). 
     
                       TABLE 1______________________________________Characteristic IR absorptions and 1H NMRspectra of alkoxo compounds of tungsten      Absorption peaks      of IR spectrum 1H NMR spectrumCompound   (cm.sup.-1)    (δ/ppm)______________________________________WCl.sub.2 (chd).sub.2      1040     C--O      1.2      1000               3.6      900-600  W--O      3.7WOCl.sub.2 (chd).sub.2      1040     C--O      1000     W--O      900-600  W--O[WCl(pin.sub.2)].sub.2      1140     C--O      960-620  W--OWOCl.sub.2 (pin)      1140     C--O      980      W═O      960-600  W--OW(chd).sub.2 (mes).sub.2      1.2;1.8                         2.2;2.4                         3.8                         6.9W(mes).sub.2 (pin).sub.2      1160     C--O      2.3;2.4      960-900            6.9______________________________________ chd = cyclohexane diolato ligand mes = mesitylene ligand pin = pinacolato ligand 
    
     EXAMPLE 6 
     Preparation of dimesitylene dipinacolato tungsten 
     0.613 g (1.55 mmol) of tungsten hexachloride was dissolved in 10.0 ml of toluene. 0.994 g (3.10 mmol) of tetrabutyl ammonium nitrate and 3.10 mmol of pinacol, dissolved in 15.0 mol of toluene, were added to the solution The solution was mixed and it was allowed to reflux for six hours. As the reaction advanced, two liquid layers formed in the vessel, the lower one of which layers was an orange and the upper one a yellow solvent. The orange solvent was dissolved in 10.0 ml of tetrahydrofurane, and 3.1 mmol (0.08 g) of magnesium and 3.1 mmol (9.47 ml) of bromine mesitylene were added to the solution. The solution was separated by decantation from a non-reacting magnesium and the salt formed. The solvent was removed from the yellow solution by evaporating the solution under an underpressure, i.e., sub-atmospheric pressure. 
     A 1H NMR spectrum and an IR spectrum were measured from the brown yellow oily product (Table 1). The compound formed in the reaction contained a mesitylene ligand and a pinacolato ligand bound to the tungsten. 
     
         WCl.sub.6 +1pinH.sub.2 →WCl.sub.2 (pin).sub.2 +4 HCl 
    
     
         WCl.sub.2 (pin).sub.2 +2Mg+2mesBr→W(mes).sub.2 (pin).sub.2 +MGCl.sub.2 +MgBr.sub.2 
    
     PREPARATION AND TESTING OF CATALYSTS 
     The catalysts were prepared by separately impregnating each precursor (in one catalyst the diol was pinacol and in the other trans-1,2-cyclohexane diol) from THF into silica (PQ Corporation, CS-1231) and by calcinating with nitrogen at 600° C. 
     The catalysts were tested by passing propene through a catalyst bed at 400° C. A WHSV 4h -1  conversion was observed in connection with both catalysts to be ca. 50%. (WHSW=weight hourly space velocity, i.e. 1 g of the feeding rate (g) flowing through the quantity of the catalyst per hour.) In the reference catalyst WO 3  /SiO 2 , which contained the same quantity of tungsten (2%), the conversion was clearly below 50%. See Tables 2,3 and 4. 
     EXAMPLE 7 
     The sample was dimesitylene dipinacolato tungsten. 
     A  1  C-NMR and a  1  H-NMR was run from the sample with a 400 MHz device. The spectra may be fitted into the assumed structure. 
     The sample was known to dissolve in THF, due to which a catalyst impregnated from this solution was prepared, which catalyst contained 0.1294 g of the sample and 0.4450 g of silica. A calcination was performed in a nitrogen flux (ca. 10 l/h, 600° C., 1 h). During the calcination it was observed that a green and brown oil condensed in the reactor tube. It was allowed to react with propene, and test results showing the activity of the metathesis catalyst are shown in Table 2. 
     
                                           TABLE 2__________________________________________________________________________ACTIVITY OF A METATHESIS CATALYST__________________________________________________________________________  No. of run:            L2  Date:                  Feb 12-14, 1990  PRECURSOR:             Dimesitylene dipinacolato tungsten  Carrier:               SiO2 PQ cs-1231 0.6-1.6 mm  Mass of catalyst (g):  0.3445  Area of catalyst (m.sup.2 /g):                         310  Molar mass of metal (g/mol):                         183.85  Content of metal (%):  2.5  Temperature (°C.):                         400  Activation:            N2 ca. 10 1/h 600° C. 1 h  Propylene flow (1/h):  1-6__________________________________________________________________________         Trans-2-  Cis-2-       PropyleneTime   Ethylene   Propylene         butene              1-butene                   butene                       Others                           Butenes                                conversion                                      Activity(h)   (%)  (%)   (%)  (%)  (%) (%) (%)  (%)   (g/gh)                                           Notes__________________________________________________________________________0.0   11.968   44.553         14.058              6.673                   10.667                       12.071                           31.408                                51.4  82.5 propylene                                           1.0 l/h1.0   9.008   48.017         18.137              3.918                   14.128                       6.792                           36.183                                53.1  85.22.0   8.632   47.618         17.600              4.371                   13.646                       8.133                           36.617                                52.9  84.93.0   8.855   47.136         17.239              4.603                   13.403                       8.764                           35.245                                52.9  84.94.0   8.307   47.424         17.282              4.663                   13.401                       8.923                           35.346                                52.8  84.85.0   8.361   46.489         17.337              4.634                   13.427                       8.752                           35.398                                52.8  84.86.0   8.195   47.515         17.344              4.556                   13.440                       8.950                           35.340                                52.7  84.77.0   8.089   47.620         17.374              4.530                   13.485                       8.902                           35.389                                52.7  84.68.0   8.769   47.548         17.402              4.346                   13.503                       8.432                           35.251                                52.7  84.69.0   8.625   47.670         17.434              4.371                   13.559                       8.341                           35.364                                52.7  84.610.0   8.341   47.402         17.375              4.504                   13.482                       8.896                           35.361                                52.8  84.811.0   8.519   47.363         17.391              4.408                   13.496                       8.823                           35.295                                52.8  84.812.0   8.484   47.609         17.524              4.407                   13.575                       8.401                           35.506                                52.8  84.813.0   8.352   47.728         17.626              4.215                   13.740                       8.339                           35.581                                52.8  84.814.0   8.391   47.816         17.711              4.198                   13.738                       8.146                           35.647                                52.8  84.815.0   8.331   47.781         17.748              4.224                   13.789                       8.127                           35.761                                52.9  84.916.0   8.387   47.874         17.828              4.179                   13.897                       7.835                           35.904                                52.9  85.017.0   8.413   47.778         17.747              4.152                   13.774                       8.136                           35.673                                52.8  84.818.0   8.225   50.010         19.921              2.266                   15.728                       3.850                           37.915                                53.2  172.6                                           propylene                                           2.0 l/h19.0   8.332   50.285         20.038              2.199                   15.803                       3.343                           38.040                                53.2  172.420.0   8.344   50.377         20.082              2.121                   15.836                       3.240                           38.039                                53.1  172.321.0   7.680   53.256         20.195              1.276                   16.280                       1.313                           37.751                                51.5  322.7                                           propylene                                           3.9 l/h22.0   7.511   54.390         19.787              1.136                   16.145                       1.031                           38.068                                50.6  316.623.5   7.678   54.717         19.654              1.077                   16.027                       0.847                           36.758                                50.2  314.324.5   7.338   56.002         19.275              0.968                   15.683                       0.734                           35.926                                49.0  480.4                                           propylene                                           6.1 l/h25.5   7.069   59.615         17.895              0.000                   14.937                       0.484                           32.832                                45.2  443.126.5   6.978   60.337         17.542              0.000                   14.704                       0.439                           32.246                                44.5  435.827.5   7.063   60.643         17.401              0.000                   14.626                       0.267                           32.027                                44.2  433.028.5   7.078   60.635         17.707              0.000                   14.611                       0.269                           32.018                                44.2  432.929.5   7.093   60.968         17.216              0.000                   14.473                       0.250                           31.689                                43.8  429.130.5   7.179   60.829         17.298              0.000                   14.501                       0.193                           31.799                                44.0  430.531.5   6.931   60.849         17.407              0.000                   14.617                       0.196                           32.024                                44.1  432.132.5   6.793   61.454         17.088              0.000                   14.422                       0.243                           31.510                                43.5  425.933.5   7.101   61.974         17.223              0.000                   14.449                       0.253                           31.672                                43.8  429.034.5   7.171   61.716         17.371              0.000                   14.572                       0.270                           31.943                                44.1  432.135.5   7.046   61.250         17.102              0.000                   14.356                       0.246                           31.458                                43.5  426.336.5   6.947   61.015         17.293              0.000                   14.545                       0.200                           31.838                                43.9  430.137.5   6.621   61.092         16.870              0.000                   14.160                       0.257                           31.030                                42.8  419.738.5   6.692   61.793         17.033              0.000                   14.297                       0.185                           31.330                                43.2  423.139.5   6.744   61.868         16.939              0.000                   14.206                       0.242                           31.145                                43.0  431.440.5   6.512   62.036         16.972              0.000                   14.229                       0.251                           31.201                                43.0  431.241.5   6.488   62.767         16.563              0.000                   13.969                       0.240                           30.505                                42.2  413.042.5   6.416   62.807         16.596              0.000                   13.222                       0.959                           29.818                                41.6  407.443.5   6.423   63.292         16.263              0.000                   13.795                       0.227                           30.058                                41.6  407.5__________________________________________________________________________ 
    
     The tungsten content of an unused catalyst was 2.1% and after the reaction 2.5%. 
     EXAMPLE 8 
     The sample was dimesitylene bis(cyclohexane diolato) tungsten. 
     0.29 g of the sample and 0.94 g of silica were impregnated. 0.5425 g of the catalyst was packed in the reactor and a calcination was performed with nitrogen (ca. 10 1/h, 600° C., 1 h). A brown greenish oil was observed during the calcination. It was allowed to react with propene, and test results showing the activity of the metathesis catalyst are shown in Table 3. 
     
                                           TABLE 3__________________________________________________________________________ACTIVITY OF A METATHESIS CATALYST__________________________________________________________________________    No. of run:           L3    Date:                 Mar 29-30, 1990    PRECURSOR:            Dimesitylene bis(cyclohexane                          diolato)tungsten    Carrier:              SiO2 PQ cs-1231 0.6-1.6 mm    Mass of catalyst (g): 0.5425    Area of catalyst (m.sup.2 /g)                          310    Molar mass of metal (g/mol):                          183.85    Content of metal (%): 1.4    Temperature (°C.):                          400    Activation:           N2 ca. 10 1/h 600° C. 1 h    Propylene flow (1/h): 1-6__________________________________________________________________________         Trans-2-  Cis-2-       PropyleneTime   Ethylene   Propylene         butene              1-butene                   butene                       Others                           Butenes                                conversion                                      Activity(h)   (%)  (%)   (%)  (%)  (%) (%) (%)  (%)   (g/gh)                                           Notes__________________________________________________________________________0.0   12.598   49.667         17.446              3.150                   12.732                       4.407                           33.328                                50.2  91.3 propylene                                           1.0 l/h1.0   6.436   58.076         18.076              0.000                   15.182                       2.230                           33.258                                46.2  336.6                                           propylene                                           4.0 l/h2.5   10.345   56.415         18.114              0.368                   14.361                       0.397                           32.843                                46.6  339.53.5   7.526   53.699         21.545              0.000                   16.867                       0.363                           38.412                                51.8  377.019.0   10.712   53.494         19.494              0.516                   15.124                       0.540                           35.134                                49.6  361.120.0   10.041   56.116         18.476              0.415                   14.531                       0.421                           33.422                                47.2  343.720.5   7.759   53.112         21.451              0.000                   17.001                       0.677                           38.452                                52.1  379.221.5   6.335   55.258         21.064              0.000                   16.707                       0.636                           37.771                                50.6  368.722.5   5.283   62.775         17.421              0.000                   14.371                       0.150                           31.792                                43.2  471.7                                           propylene                                           6.0 l/h23.5   6.543   60.468         18.108              0.000                   14.678                       0.203                           32.786                                44.9  490.024.0   9.026   62.826         15.344              0.000                   12.627                       0.117                           27.971                                40.0  437.525.0   6.449   60.353         18.183              0.000                   14.825                       0.190                           33.008                                45.1  492.426.0   6.273   61.226         17.784              0.000                   14.542                       0.175                           32.326                                44.2  482.9__________________________________________________________________________ 
    
     The tungsten content of an unused catalyst was 1.4% and the corresponding percentage after the reaction was 1.9%. 
     REFERENCE EXAMPLES 9-10 
     Two reference catalyst were prepared and tested. One of the catalysts was tungsten oxide chloride WOCl 4 , which is a tungsten complex dissolving in non-polar solvents, and the other one on a water-soluble salt (NH 4 ) 2  WO 4 , which is the most common reactant in metathesis catalysts. 
     EXAMPLE 9 
     A reference catalyst from WOCl 4 , a low tungsten content. 
     0.18 g of tungsten oxychloride was added gradually to and by simultaneously mixing with 1.28 g. of silica in dichloromethane (0.6-1.6 mm, 310 m 2  /g, The PQ Corporation). They were allowed to absorb at room temperature for about 3 hours, after which they were evaporated in a vacuum. The tungsten content was determined to be 2.3%. 
     0.5302 g of the catalyst was loaded into a reactor tube, calcinated with air at 600° C. and flushed with nitrogen. It was tested in a metathesis reaction of propene at flows 1.0-6.0 1/h. The tungsten content after the run was 2.2%. 
     
                                           TABLE 4__________________________________________________________________________ACTIVITY OF A METATHESIS CATALYST Micro 1__________________________________________________________________________   Code of run:            WOCl4   Date:                   Apr 18-20, 1990   PRECURSOR:              W(O)Cl4   Carrier:                SiO2 PQ cs-1231 0.6-1.6 mm   Mass of catalyst before run (g):                           0.5302   after run (g)           0.3014   Content of metal before run (%):                           2.3   after run (%):          2.2   Activation:             air ca 10 1/h 600° C.                           2 h W2 ca. 10 1/h                           400° C. 1.5 h   Temperature (°C.)                           400   Propylene flow (1/h):   1-6__________________________________________________________________________         Trans-2-  Cis-2-       PropyleneTime   Ethylene   Propylene         butene              1-butene                   butene                       Others                           Butenes                                conversion                                      Activity(h)   (%)  (%)   (%)  (%)  (%) (%) (%)  (%)   (g/gh)                                           Notes__________________________________________________________________________1.0   3.196   86.581         4.883              0.590                   4.674                       10.147                           0.076                                15.0  31.2 propylene                                           1.0 l/h2.0   3.086   78.327         7.352              0.659                   3.451                       11.462                           7.125                                18.0  37.53.0   4.627   77.705         8.788              0.736                   8.504                       18.028                           0.000                                25.8  53.84.0   4.323   75.581         9.936              0.816                   9.344                       20.096                           0.000                                28.5  59.55.0   4.313   74.458         10.519              0.721                   9.989                       21.229                           0.000                                30.0  62.56.0   4.471   73.174         10.975              0.714                   10.396                       22.085                           0.000                                31.2  65.07.0   4.900   72.095         11.523              0.796                   10.687                       23.006                           0.000                                32.4  67.58.0   5.082   71.506         11.694              0.673                   11.046                       23.413                           0.000                                32.9  68.79.0   5.151   70.984         11.931              0.648                   11.286                       23.865                           0.000                                33.5  69.910.0   5.234   70.247         12.292              0.632                   11.595                       24.519                           0.000                                34.4  71.711.0   5.391   69.997         12.379              0.608                   11.625                       24.612                           0.000                                34.5  72.012.0   5.683   69.477         12.505              0.598                   11.737                       24.840                           0.000                                34.9  72.813.0   5.633   68.700         12.998              0.715                   11.954                       25.667                           0.000                                35.9  74.914.0   5.794   68.688         12.884              0.576                   12.058                       25.518                           0.000                                35.8  74.615.5   5.652   68.269         13.270              0.694                   11.115                       26.079                           0.000                                36.4  76.016.5   6.011   68.169         13.069              0.559                   12.192                       25.820                           0.000                                36.2  75.617.5   5.969   67.759         13.371              0.655                   12.246                       26.272                           0.000                                36.8  76.718.5   5.981   67.889         13.241              0.543                   12.345                       26.129                           0.000                                36.6  76.319.5   5.947   67.879         13.298              0.527                   12.349                       26.174                           0.000                                36.6  76.420.5   2.472   85.064         6.129              0.000                   6.334                       12.463                           0.000                                18.0  150.3                                           propylene                                           4.0 l/h21.5   2.610   85.665         6.212              0.000                   6.514                       12.726                           0.000                                18.4  153.522.5   2.792   84.778         6.076              0.000                   6.354                       12.430                           0.000                                18.0  150.423.5   2.757   84.937         6.073              0.000                   6.233                       12.306                           0.000                                17.9  148.924.5   1.941   87.884         4.923              0.000                   5.252                       10.175                           0.000                                14.8  185.2                                           propylene                                           6.0 l/h25.5   2.068   87.968         4.836              0.000                   5.129                       9.965                           0.000                                14.5  181.826.5   2.044   88.475         4.592              0.000                   4.889                       9.481                           0.000                                13.8  173.3                                           propylene27.5   4.639   74.452         10.445              0.513                   9.952                       20.910                           0.000                                29.6  61.8 1.0 l/h28.5   5.275   71.696         11.784              0.000                   11.244                       23.028                           0.000                                32.5  67.829.5   5.573   70.538         12.366              0.000                   11.522                       23.888                           0.000                                33.7  70.330.5   5.796   70.116         12.388              0.000                   11.700                       24.088                           0.000                                34.0  70.931.5   5.737   69.872         12.525              0.000                   11.865                       24.390                           0.000                                34.4  71.732.5   5.755   69.650         12.631              0.000                   11.964                       24.595                           0.000                                34.6  72.233.5   5.751   69.383         12.891              0.000                   11.975                       24.866                           0.000                                35.0  72.934.5   5.839   69.325         12.746              0.000                   12.090                       24.836                           0.000                                35.0  72.935.5   5.783   69.297         12.809              0.000                   12.111                       24.920                           0.000                                35.0  73.136.5   5.626   69.041         13.014              0.000                   12.319                       25.333                           0.000                                35.5  74.037.5   6.069   68.330         13.304              0.000                   12.297                       25.601                           0.000                                36.0  75.038.5   5.885   68.303         13.408              0.000                   12.404                       25.812                           0.000                                36.2  75.539.5   6.112   68.219         13.220              0.000                   12.448                       25.668                           0.000                                36.1  75.240.5   6.020   68.177         13.407              0.000                   12.396                       25.903                           0.000                                36.2  75.541.5   6.025   68.316         13.263              0.000                   12.423                       25.686                           0.000                                36.1  75.242.5   5.921   68.312         13.287              0.000                   12.480                       25.767                           0.000                                36.1  75.4__________________________________________________________________________ 
    
     EXAMPLE 10 
     A reference catalyst from (NH 4 ) 2  WO 4 , normal tungsten content. 
     A 3.9% water solution of ammonium tungstate 35.30 g was added gradually to and by simultaneously mixing with 19.96 g of silica (0.6-1.6 mm, 310 m 2  /g, The PQ Corporation). They were allowed to absorb at 80° C. for about one hour, after which they were evaporated at 115° C. for 17 hours. 
     16.7 g of the same solution was impregnated once again, it was allowed to absorb at 80° C. and dried at 115° C. for 23 hours. The metallic content was determined to be 5.8%. 
     0.3782 g of the catalyst was loaded into a reactor tube, calcinated with air at 600° C. and flushed with nitrogen. It was tested in a metathesis reaction of propene at flows 0.1-4.1 l/h. The tungsten content after the run was 6.3%. 
     The test results of the activity of the metathesis catalyst are shown in Table 5. 
     
                                           TABLE 5__________________________________________________________________________ACTIVITY OF A METATHESIS CATALYST__________________________________________________________________________   No. of run:             Test 15   Date:                   Jul 31-Aug 3, 1989   PRECURSOR:              (NH4)2WO4   Carrier:                Silica PQ cs-1231 0.6-1.6 mm   Mass of unused catalyst (g):                           0.3782   Mass of catalyst used (g):                           0.3664   Metal content before run (%):                           5.8   Metal content after run (%):                           6.3   Activation:             air ca. 10 l/H 600° C. 1.5 h,                           N2 10 l/h 600° C. 0.5 h   Temperature (°C.):                           400   Propylene flow (l/h):   0.9-4.09__________________________________________________________________________         Trans-2-  Cis-2-       PropyleneTime   Ethylene   Propylene         butene              1-butene                   butene                       Others                           Butenes                                conversion                                      Activity(h)   (%)  (%)   (%)  (%)  (%) (%) (%)  (%)   (g/gh)                                           Notes__________________________________________________________________________1.01   4.378   76.505         6.668              1.891                   5.505                       5.503                           14.064                                21.6  14.2 400° C.                                           1.1 l/h2.0   6.111   73.233         9.204              2.322                   7.628                       1.502                           19.154                                28.2  18.64.0   7.635   66.508         11.827              2.563                   9.650                       1.817                           25.040                                35.2  23.27.0   8.939   61.344         13.676              3.210                   10.795                       2.036                           27.681                                40.4  26.68.0   9.015   61.178         13.850              3.004                   10.910                       2.043                           27.764                                40.5  26.711.0   9.151   60.485         14.429              2.686                   11.417                       1.832                           28.532                                41.4  27.312.0   9.034   60.840         14.450              2.389                   11.498                       1.789                           28.337                                41.1  27.116.0   9.361   59.583         15.055              2.339                   11.879                       1.783                           29.273                                42.4  28.017.0   9.334   59.596         15.081              2.302                   11.922                       1.765                           29.305                                42.4  28.018.0   9.529   59.902         15.304              2.499                   11.959                       1.807                           29.762                                43.1  28.419.0   9.455   59.027         15.305              2.351                   12.058                       1.804                           29.714                                43.0  28.420.0   9.412   59.227         15.297              2.321                   12.044                       1.699                           29.622                                42.9  28.321.0   9.535   59.134         15.672              2.176                   12.290                       1.193                           30.138                                43.3  28.622.0   11.956   59.594         15.110              3.487                   10.751                       2.102                           29.348                                44.8  13.6 400° C.                                           0.52 l/h23.0   12.006   56.245         14.814              3.896                   10.524                       2.515                           29.234                                43.8  13.624.0   11.970   56.583         14.565              3.956                   10.375                       2.551                           28.896                                43.4  13.527.5   12.574   57.121         13.803              4.160                   9.797                       2.545                           27.760                                42.2  13.128.5   9.341   59.644         14.912              2.526                   11.846                       1.731                           29.284                                42.4  28.0 400° C.                                           1.1 l/h__________________________________________________________________________ 
    
     As shown in Tables 2-5, in the product distribution, the ratio between ethene and butenes, the molar ratio is not 1:1 which is required by theory (the ratio of the weight percentages was ca. 1:2), since some ethene disappears from the system before the analysis. The conversion and the activity have been calculated from the butene observed. 
     While the invention has been described with respect to the production of particular catalysts and the use thereof in particular metathesis reactions of olefines, it is to be understood that variations and modifications of the invention can be made. Such modifications are meant to be comprehended within the meaning and scope of the claims herein.