Catalyst for metathesis reactions of olefines and a method for preparing it as well as the metathesis reaction concerned

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 "self-disproportionation". 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.dbd.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 .fwdarw.WCl.sub.2 (diol.sub.2)+4HCl (1)
in which diolH.sub.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.fwdarw.W(ArCH.sub.2).sub.2 (diol).sub.2 +MgBr.sub.2 +MgCl.sub.2 ( 2)
in which ArCH.sub.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 .fwdarw.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 .fwdarw.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 .sup.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.sub.3 was separated by filtration. The tungsten oxide was dried by maintaining it at a temperature of 850.degree. 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).sub.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.degree. 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 .fwdarw.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 .sup.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 .fwdarw.[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) (.delta./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.dbd.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 .fwdarw.WCl.sub.2 (pin).sub.2 +4 HCl
WCl.sub.2 (pin).sub.2 +2Mg+2mesBr.fwdarw.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.degree. C.
The catalysts were tested by passing propene through a catalyst bed at 400.degree. C. A WHSV 4h.sup.-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.sub.3 /SiO.sub.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 .sup.1 C-NMR and a .sup.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.degree. 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 (.degree.C.): 400 Activation: N2 ca. 10 1/h 600.degree. 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.degree. 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 (.degree.C.): 400 Activation: N2 ca. 10 1/h 600.degree. 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.sub.4, which is a tungsten complex dissolving in non-polar solvents, and the other one on a water-soluble salt (NH.sub.4).sub.2 WO.sub.4, which is the most common reactant in metathesis catalysts.
EXAMPLE 9
A reference catalyst from WOCl.sub.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.sup.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.degree. 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.degree. C. 2 h W2 ca. 10 1/h 400.degree. C. 1.5 h Temperature (.degree.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.sub.4).sub.2 WO.sub.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.sup.2 /g, The PQ Corporation). They were allowed to absorb at 80.degree. C. for about one hour, after which they were evaporated at 115.degree. C. for 17 hours.
16.7 g of the same solution was impregnated once again, it was allowed to absorb at 80.degree. C. and dried at 115.degree. 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.degree. 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.degree. C. 1.5 h, N2 10 l/h 600.degree. C. 0.5 h Temperature (.degree.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.degree. 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.degree. 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.degree. 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.

Number	Name	Date
3450797	Schafer et al.	Jun 1969
3956178	Greco et al.	May 1976
4550216	Basset et al.	Oct 1985
4559320	Reusser	Dec 1985
4818442	Vanderveen et al.	Apr 1989

Number	Date	Country
0056013	Jul 1982	EPX
0129474	Dec 1984	EPX
0152112	Aug 1985	EPX

Catalyst for metathesis reactions of olefines and a method for preparing it as well as the metathesis reaction concerned

Information

Patent Number

Date Filed

Date Issued

Inventors

Original Assignees

Examiners

Agents

CPC

US Classifications

Field of Search

US

International Classifications

Abstract

Description

Claims

Priority Claims (1)

US Referenced Citations (5)

Foreign Referenced Citations (3)