Catalytic hydrocracking of petroleum oils, shale oils and hydrogenated coal distillates having relatively highnitrogen contents has been previously carried out at relatively severe conditions, i.e., temperatures of 400 C. or more, and at hydrogen pressures of 200 atmospheres or more, utilizing a variety of catalysts, with similar results as regards conversion, product selectivity and catalyst aging. Many of these catalysts have been found to give substantially equivalent results under these severe conditions because the large quantity of nitrogen in the feed poisons a relatively greater number of the active sites on the more active catalysts and efiectively masks. Some of the differences that would normally distinguish these catalysts from each other. The overall results obtained in these cases are attributable in part to the catalytic effect of the partially deactivated catalysts, but also is significant part to the non-catalytic effect of the relatively severe process conditions.

The present invention relates to activation of tungsten hydrocracking catalysts  to enhance their activity and general elfectiveness for purposes of hydrocracking low-nitrogen content hydrocarbon oils.

It has been found that tungsten sulfide catalysts greatly improved activity and selectivity, and which exhibits relatively low rates of deactivation for purposes of hydrocracking hydrocarbon oil feed stocks having low-nitrogen contents, can be obtained by the use of the special sulfiding techniques of this invention. Thus, it has been found that improved tungsten sulfide catalysts are obtained by contacting tungsten oxide that has been composited with an activate, acidic, siliceous cracking support, such as a silicaalumina cracking catalyst, with hydrogen gas containing a minor proportion of a sulfiding agent at a temperature in the range of about 300 to 900 F., particularly 400 to 800 F., particularly in the range of about 100 to 1000 p.s.i.-g., and especially about 2.00 to 600 p.s.'i.g., for a period effective to convert at least a substantial proportion of the tungsten to a sulfided form.

Hydrogen sulfide is an example of a preferred sulfiding agent, but other equivalent materials containing divalent sulfur can be used. The catalysts activated as described above are especially adapted for use in hydrocracking hydrocarbon oils having a low-nitrogen content below about 15 p.p.m. and preferably below about 1 p.p.m., particularly when such hydrocracking is carried out at temperatures in the range of about 600 to 750 F. and at hydrogen partial pressures in the range of about 750 to 2000 p.s.i.g., and at liquid hourly space velocities in the range of about 0.5 to 8, preferably about 1 to 5 liquid volumes of oil per volume of catalyst per hour. However, the invention is not limited to the use of such conditions.

Blue tungsten oxide can be used to produce tungsten powder. The melting point of tungsten is up to about 3410 ℃, it is of high hardness, ductility is strong, at room temperature without air erosion, because tungsten has these characteristics, which make tungsten  powder  widely used in many fields, such as preparing high proportion alloy, automatic watches pendulum, telecommunications vibrator, balance board aircraft, anti-χ rays, α-rays, γ-ray protection plates and the like.

At present, domestic production of blue tungsten oxide is based on using ammonium paratungstate as raw material in the port of ammonia gas or liquid ammonia fed by the decomposition of nitrogen, hydrogen or mixed gas directly into hydrogen, in a feed port of the suction fan, ammonia or nitrogen, hydrogen gas or hydrogen gas feed port access from the out, after a tube, is discharged from the feed port, when the discharge port access is ammonia, the ammonia gas in the furnace tube will be the role of tungsten oxide is decomposed into nitrogen and hydrogen, the hydrogen which will be reduced to tungsten trioxide, can be obtained at the discharge port of blue tungsten oxide; when the discharge port pass into the mixed gas by the decomposition of ammonia nitrogen and hydrogen formed, then where will the hydrogen reduction of tungsten trioxide blue tungsten oxide, can be obtained at the discharge port of blue tungsten oxide; when the discharge port is passed directly into the hydrogen, the hydrogen gas into the tungsten trioxide will be reduced to blue tungsten oxide.

As a result of the above-described method for preparing the required blue tungsten oxide, which leads to the need to increase the consumption of ammonia, resulting in increased processing costs; and by the decomposition of ammonium paratungstate Most ammonia with drawn from the inlet at the fan discharge to the atmosphere, the atmosphere is contaminated, thereby affecting the health of the people.

A method of preparing ammonium paratungstate from reducing preparation blue tungsten oxide, which is based on ammonium paratungstate 5 (NH4) 2O · 12WO3 · 5H2O as raw material, characterized in that: it comprises the following steps:.
a: Ammonium paratungstate gets heated and is decomposed into tungsten trioxide WO3, ammonia NH3 and water vapor H2O; under the heating temperature 400 ℃ ~ 600 ℃;.
b: From tungsten oxide catalyst to ammonia NH3 decomposition, the thermal decomposition of the ammonia NH3 then is further decomposed into nitrogen N2 and hydrogen H2;.
c: By controlling the reaction temperature and proper furnace gas pressure, the reduction of tungsten trioxide WO3 and tungsten blue oxide WO2.9 is made under temperature 550 ℃ ~ 800 ℃; furnace gas  pressure is 0-2 mbar.

This invention relates to improved catalysts for reacting carbon monoxide and carbon dioxide with hydrogen to form methane and water. More specifically, this invention relates to a multi-component catalyst containing ruthenium, with or without platinum, which catalyst is beneficated with a specific tungsten oxide.

Heretofore, many kinds of metallic catalyst have been utilized in various supported and nonsupported forms to promote the reaction of carbon monoxide and carbon dioxide with hydrogen to form methane and water. These reactions are the basis of the standard Fischer-Tropsch reaction for the synthesis of hydrocarbons from carbon monoxide or carbon dioxide and hydrogen. In addition, these same reactions are employed in the clean-up reformer product gases before introduction into fuel cells, or before nitrogenation in ammonia synthesis plants. Most of the catalysts used in these reactions are primarily nickel-based and operate at relatively high temperatures, about 400C. Further, they do not selectively methanate CO in the presence of CO In addition, they require a relatively large reactor size, and the reaction conditions are relatively severe.

We have discovered catalysts that can methanate carbon monoxide and/or carbon dioxide by reaction with hydrogen. These catalysts include ruthenium met als having minor amounts of reduced amorphous tungsten oxide admixed therewith. The ruthenium may be used alone or in mixtures and with platinum. We have discovered, unexpectedly, that the minor amounts of reduced amorphous tungsten oxide admixed with the ruthenium have a synergistic effect in a methanation process. In addition, the methanation activity is quite unexpected in view of the fact that tests show that there is no net effective carbon monoxide chemical reaction in an operating fuel cell using such materials under electrical potential as electrodes. These catalysts could also find utility as fuel cell electrodes and hydrocarbon conversion catalysts.

The present invention relates to a procedure for the synthesis of threadlike tungsten oxide W5O14 in the presence of nickel at temperatures lower than 1000° C. The procedure enables the synthesis of electrically conductive tungsten oxides having rodlike or threadlike forms. The present invention relates to the field of chemical technology, more specifically, to inorganic chemistry, of tungsten oxides obtained in the form of nanostructures by means of physico-chemical processing.

Represented is a procedure for the synthesis of a highly homogeneous phase of the W5O14 compound from the vapor phase, in the presence of nickel, by means of a chemical transport method in a closed quartz ampoule.

As an alternative example, a procedure is represented for the synthesis of the W5O14 compound in a through-flow reaction vessel. Both procedures yield electrically conductive threadlike crystals of the W5O14 compound. The synthesis is performed in vapor phase. Tungsten enters the reaction as a pure phase or via WS2±x, x≈4, previously synthesized from the elements, and/or the source of tungsten may also be tungsten oxides WO3−Y, 0≦y≦1. Nickel may enter the reaction via NiI2, Ni(OH)2 and/or atomic nickel.