Tungsten Oxide Nanoflake Self-assembly Nanosphere and Preparing Method

The tungsten trioxide is a η- type wide band gap semiconductor oxide (band gap of about 2.8eV), since the crystal memory in the atomic or electronic defect, the compound stoichiometry deviation occurs, the charge carrier concentration is mainly determined by the concentration of stoichiometric defects (such as oxygen vacancies), it has excellent catalytic and gas sensing performance. Tungsten oxide based gas sensors for the N02, H2S, 03, and NH3, and many other environmentally harmful gases sensitive response, especially for low concentration of nitrogen oxides show ultra-high sensitivity. In addition, the tungsten oxide also has a photochromic, electrochromic properties, photocatalysis, field emission and solar cells have a wide range of applications.
Tungsten Oxide

Tungsten oxide nanosheets self-assembly microsphere preparation, concrete steps are as follows:
(1)In a reaction vessel, the soluble tungsten salt dissolves in deionized water. Dub the concentration of the solution to 0.10~0.80mol L, place 100 ~750W power ultrasonic generator under ultrasonic condition oxalic acid.
(2)0.12~0.47mol of oxalic acid is added, the concentration will be dissolved as 1.00~4.50mol / L  inorganic acid solution.
(3)It was slowly added to the above solution to PH value 0.50~3.50, continued ultrasound 20~150min, the yellow precipitate was washed by centrifugation, and the resulting yellow precipitate was dried at 50~80 °C under 4~20h. Soluble tungsten salt is tungsten hexachloride (WCl6), sodium tungstate (Na2WO4.2H2O), ammonium metatungstate [(NH4) 6W7O24.6H2O] and paratungstate [5 (NH4) 20.12W03.5H2O] one; the inorganic acid are sulfuric acid (H2SO4) 'hydrochloric acid (HCl) and nitric acid (HNO3).

 

Hydrocarbons Hydrocracking with a Sulfided Tungsten Oxide Catalyst

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.

 

Ruthenium-reduced Amorphous Tungsten Oxide Catalyst

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.

 

Method and Apparatus for Preparing Blue Tungsten Oxide by Ammonium Paratungstate Self-reduction

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.

 

Procedure for the Synthesis of Threadlike Tungsten Oxide W5O14

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.

 

Atmospheric Pressure CVD Process for Preparing Fluorine-doped Tungsten Oxide Films

It is well-known in the glass art to coat glass sheets with metallic and/or dielectric materials to impart enhanced solar and optical properties to the glass sheets. For example, it is known to place multiple layers of metals and dielectrics onto glass to produce electrically conductive coatings which are transparent to visible light and yet highly reflective to infrared radiation. It is also known to deposit conductive metal oxides onto glass, such as fluorine-doped tin oxide, which are also highly reflective to infrared radiation.

Tungsten oxide is a transparent semi-conductor, which when doped with fluorine shows an appreciable increase in its infrared absorption and reflection. Hence, fluorine-doped tungsten oxide films are potential candidates as coatings on glass for solar control applications. By reflecting and/or absorbing energy in the infrared, these coatings when applied to glass reduce the energy influx into a building or motor vehicle by as much as 50 percent, thereby reducing the need for air-conditioning systems.

Many techniques for depositing metal and dielectric coatings onto glass are well-known. Examples of conventional deposition techniques include liquid or powder spray pyrolysis, wherein liquids or solid particles containing film forming reactants are sprayed onto the surface of a hot glass ribbon being produced by the well-known float glass process. A more convenient method for depositing coatings onto glass is by way of chemical vapor deposition, wherein vaporized film-forming precursors are reacted at or near the surface of a hot glass ribbon to form the metal or dielectric film thereon. Chemical vapor deposition does not suffer from the problems associated with either liquid or powder spray pyrolysis techniques. That is, the liquid spray pyrolysis technique substantially cools the hot glass ribbon, while the powder spray pyrolysis technique requires a complex, delicate powder handling and delivery system.

A process for providing fluorine-doped tungsten oxide on the surface of a substrate, which process comprises reacting together a tungsten alkoxide, an oxygen-containing compound, and a fluorine-containing compound at the surface of the substrate at a temperature and for a time sufficient to form a film of fluorine-doped tungsten oxide on the substrate.

Method for Preparing Reduced Tungsten Oxide

The present invention relates to a novel method for preparing a solid, reduced, amorphous tungsten oxide. More particularly, it relates to a method for eifecting alkali metal borohydride reduction of a tungstate solution under controlled pH conditions and at ambient temperatures whereby a solid, amorphous precipitate com prising reduced tungsten oxide is recovered.

It is well known that the reduction of solid tungsten trioxide can be effected by means of hydrogen in a closed reaction vessel at elevated temperatures, usually in the range from about 300 C. to about 800 C., and under a positive pressure. Unfortunately, the utilization of elevated temperatures and autogenous pressures substantially increases the cost for preparing reduced tungsten oxide. In addition, a need exists for eifecting the coprecipitation of tungsten with other metallic substances. This cannot be accomplished, if the other substance is adversely affected by elevated temperatures. Hence, attempts have been made to carry out the reduction of a tungstate ion at ambient temperatures and pressures to prepare a useable precipitate. None has been successful. For instance, the treatment of ammonium metatungstate solution with sodium borohydride under alkaline conditions does not result in any reaction. Similarly, recoverable solid product is not obtained when ammonium metatungstate is treated with sodium borohydride under acid conditions. Employing the latter technique, only colloidal tungsten blue, in contradistinction to a precipitate, is formed. If a method for reducing tungsten trioxide in solution to recover a solid, reduced, amorphous tungsten oxide could be found which is inexpensive and straightforward, such a method would fill a long-felt need in the art.

It is, therefore, a principal object of the present invention to obtain recoverable solid, reduced, amorphous tungsten oxide from a tungstate solution. It is a further object of the invention to provide a procedure whereby reduced tungsten oxide is obtained in solid, amorphous form utilizing ambient temperatures and atmospheric pressures. Other objects and advantages will be noted from the ensuing detailed description.

Solution-Processable Tungsten Oxide Buffer Layers And Electronics Comprising

The present invention relates to the field of organic electronics, such as OLEDs and OPVs . It particularly provides intermediates and material s suitable for manufacturing such rgamc ej.ect.ronj.cs, to spcciiic manur ccu lny cinous ana to It is known to use buffer layers in organic electronics, such as organic light emitting diodes (OLED) or organic photovoltaic cells (OPV) , in order to increase device efficiency. These layers typically have a thickness below lOOnm to retain optical transparency and a low serial resistance . Such layers may comprise WO3 and/or M0O3, which exhibit remarkably deep lying electronic states and are strongly n-doped by oxygen vacancies. Meyer et al. {Adv. Mater . 2008 , 20, 3839—3843 ) disclose efficient hole-i j ection into organic materials with deep-lying HOMO levels from an ITO electrode covered with a M0O3 or WO3 hole inj ection layer (HIL) (also called hole transport layer (HTL) ) . Simplified device structures consisting only of one or two organic layers can therefore be realized. M0O3 and WO3 hole injection layers mentioned above are typically manufactured by thermal evaporation under high vacuum; which is disadvantageous in terms of low-cost , large-area manufacturing processing .

Meyer et al . (Adv. Mater . , Ger . 23, 70 2011 ) and Stubhan et al . (Appl . Phys . Lett . 98 , 253308 2011 ) disclose suspensions comprising M0O3 nanoparticles useful for the solution processing of M0O3 HIL layers in organic electronics . Both documents are silent about the coating type . However, the processes disclosed therein are considered disadvantageous . First, as the solvent (xylene) can damage active organic layers in OLEDs or OPVs . Therefore, applications of the suspensions disclosed therein are limited to inorganic functional layers . Second, as a polymeric dispersing agent is used for the particle stabilization. Upon application of the suspension and drying-off the xylene, the dispersing agent remains in deposited M0O3 layers . This non-volatile organic.

 

Hydrocarbons Hydrocracking with Sulfided Tungsten Oxide Catalys

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 in such a way as greatly to enhance their activity and general elfectiveness for purposes of hydrocracking low-nitrogen content hydrocarbon oils. It has been found that tungsten sulfide catalysts of 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., at an elevated pressure of Patented Dec. 27, 1966 ICC at least about p.s.i.g., 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. The present invention includes the above-described method of activating the composite hydrocracking catalysts, the activated catalysts obtained therefrom, as well as methods of hydrocracking hydrocarbon oils having a low-nitrogen content in the presence of such catalysts.


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Interlayers Comprising Stabilized Tungsten Oxide Agents

Poly(vinyl butyral) (PVB) is commonly used in the manufacture of polymer layers that can be used as interlayers in light-transmitting laminates such as safety glass or polymeric laminates. Safety glass often refers to a transparent laminate comprising a plasticized poly(vinyl butyral) interlayer disposed between two sheets of glass. Safety glass often is used to provide a transparent barrier in architectural and automotive openings. Its main function is to absorb energy, such as that caused by a blow from an object, without allowing penetration through the opening or the dispersion of shards of glass, thus minimizing damage or injury to the objects or persons within an enclosed area. Safety glass also can be used to provide other beneficial effects, such as to attenuate acoustic noise, reduce UV and/or IR light transmission, and/or enhance the appearance and aesthetic appeal of window openings.

Interlayers often comprise, in addition to their polymeric component, various agents that function to alter the spectrum of radiation that is transmitted through the finished glazing product. Those agents, however, often are unstable or cause undesirable effects in a finished laminate.

The present invention includes polymer interlayers that are used in multiple layer glazing panels. Interlayers of the present invention comprise a thermoplastic polymer, a plasticizer, a tungsten oxide agent, and a stabilizing agent that prevents the degradation of the tungsten oxide agent. Interlayers incorporating such components have improved ultraviolet light blocking character, and also maintain optical quality over time.


Tungsten Manufacturer & Supplier: Chinatungsten Online - http://www.chinatungsten.com
Tel.: 86 592 5129696; Fax: 86 592 5129797
Email:    sales@chinatungsten.com
Tungsten News & Tungsten Prices, 3G Version: http://3g.chinatungsten.com
Tungsten News & Tungsten Prices, WML Version: http://m.chinatungsten.com

 

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