This invention provides a process for hydrotreating hydrocarbon resins, which process comprises contacting a feedstock comprising a hydrocarbon resin or rosin, under suitable hydrotreating conditions, with a bulk multimetallic catalyst comprised of at least one Group VIII non-noble metal and at least two Group VIB metals and wherein the ratio of Group VIB metal to Group VIII non-noble metal is from about 10:1 to about 1:10. The process according to the invention can achieve increased hydrocarbon resin productivity through increase in throughput volumes and effective catalyst lifetimes. The process of the invention is desirably practiced with a bulk catalyst consisting of only the combination of the metal species with the active metal components. The absence of carrier substrates largely removes the possibility of halogen accumulation on substrate surfaces that, in turn, can acidify metal catalysts such that additional, progressive cracking of the hydrocarbon resin molecules occurs.

This invention relates to a catalytic hydrotreating process useful for hydrocarbon resin and rosin feeds. In particular the invention relates to an improved process for hydrotreating such resins and rosins with hydrogenation metal catalyst compounds having sulfided nickel molybdotungstate catalysts.
Hydrotreating processes for the hydrogenation, desulfurization and denitrogenation of hydrocarbon compounds including such compositions of matter as petroleum fuels, white oils, lubricating oil additives and hydrocarbon resins are well known and practiced industrially. In particular, it is known that heterogeneous catalyst systems, those supported on metal oxide supports, can be advantageously used to facilitate this process. Effective reaction rates require that hydrogen gas molecules and the hydrocarbon compounds come into contact with each other in the presence of an active metal catalyst, and those active metal catalysts are typically affixed within the pores of inert supports. It is generally believed that if the pores are of insufficient design the large hydrocarbon molecules are so restricted in movement into, through and out of the pores that reaction rates are diminished. Accordingly there is a large body of knowledge relating to hydrotreating hydrocarbon compounds with heterogeneous catalysts, see for example the description of U.S. Pat. No. 5,820,749, and documents cited therein. A preferred process of the invention uses a catalyst comprising the metals nickel and/or cobalt and one or both of molybdenum and tungsten on the inert support of that invention.
A nickel molybdotungstate catalyst is disclosed in WO 99/03578. The catalyst is prepared by decomposing a nickel (ammonium) molybdotungstate precursor and sulfiding, either pre-use or in situ, the decomposition product. Suggested uses for the catalyst include desulfurization and denitrogenation.
As is apparent from this document, and those it discusses, increased productivity and run times without catalyst degradation is desirable, particularly for hydrocarbon resins, if color, aromaticity, and softening point characteristics can be retained or improved.
In accordance with this invention there is provided a process for hydrotreating hydrocarbon resins, which process comprises contacting a feedstock comprising a hydrocarbon resin or rosin, under suitable hydrotreating conditions, with a bulk multimetallic catalyst comprised of at least one Group VIII non-noble metal and at least two Group VIB metals and wherein the ratio of Group VIB metal to Group VIII non-noble metal is from about 10:1 to about 1:10. The process according to the invention can achieve increased hydrocarbon resin productivity through increase in throughput volumes and effective catalyst lifetimes.
Hydrocarbon resins prepared from catalytically or thermally polymerized feedstreams and hydrogenated according to the invention exhibit color, aromaticity and softening point characteristics at least equivalent to previously available hydrogenated resins. The process of the invention is desirably practiced with a bulk catalyst consisting of only the combination of the metal species with the active metal components. It is thus usable in fixed bed hydrogenation reactor while avoiding the negative aspects of inert substrate carriers for supporting the catalytically active metal compounds. The absence of carrier substrates largely removes the possibility of halogen accumulation on substrate surfaces that, in turn, can acidify metal catalysts such that additional, progressive cracking of the hydrocarbon resin molecules occurs. This cracking deteriorates important physical properties such as resin softening point, decreases product yields, and reduces effective catalyst life.
A preferred process according to the invention comprises the step of hydrogenating or hydrotreating (used interchangeably herein) a catalytically or thermally prepared hydrocarbon resin in the presence of the above described catalyst. Any of the known processes for catalytically hydrogenating hydrocarbon resins can be modified in accordance with the invention by substituting the catalyst system of the invention, in particular the processes of U.S. Pat. Nos. 5,171,793, 4,629,766 and 4,328,090 and WO 95/12623 are suitable. Each is referred to and incorporated by reference for purposes of U.S. patent practice, and is referred to for description of polymerization processes, monomer selection, hydrogenation processes, and end use applications of the described resins.
Other patent literature describes suitable processes for modification in accordance with the invention. For example, EP 0 082 726 describes a process for the hydrogenation of petroleum resins from catalytic or thermal polymerization of olefin and diolefin containing streams, using nickel-tungsten catalyst on a gamma-alumina support wherein the hydrogen pressure is 1.47xc3x97107xe2x88x921.96xc3x97107 Pa and the temperature is in the range of 250-330xc2x0 C. The feedstreams are said to contain C5 and/or C6 olefin and/or diolefin streams, and, for catalytic polymerization, C8/C9 aromatic olefins, e.g., styrene, vinyl benzene and optionally indene. Thermal polymerization is usually done at 160 to 320xc2x0 C., at a pressure of 9.8xc3x97105 to 11.7xc3x97105 Pa and for a period typically of 1.5 to 4 hours. After hydrogenation the reactor mixture may be flashed and further separated to recover the hydrogenated resin. Steam distillation may be used to eliminate oligomers, preferably without exceeding 325xc2x0 C. resin temperature.
Additional description and information appears in the technical literature. The term hydrocarbon resin as used in the specification and claims include the known low molecular weight polymers derived from cracked petroleum distillates, coal tar, turpentine fractions and a variety of pure monomers. The number average molecular weight is usually below 2000, and physical forms range from viscous liquids to hard, brittle solids. Polymerization feedstreams are derived from the sources described above via various known means and methods of fractionation. Friedel-Crafts polymerization is generally accomplished by use of known Lewis acid catalysts in a polymerization solvent, and removal of solvent and catalyst by washing and distillation. The invention hydrotreating process is particularly suitable for such Lewis acid catalyzed resins due to residual halogen containing reaction products from the polymerization process. Thermal catalytic polymerization is also utilized, particularly for aliphatic, cyclo-aliphatic and aliphatic-aromatic petroleum resins. The preferred hydrocarbon resins are those known to be useful as tackifiers for adhesive compositions, particularly the petroleum resins derived from the deep cracking of petroleum distillates, hydrocarbon resins from pure aromatic monomers, the coumarone-indene resins from coal tar and the polyterpenes derived from turpentine fractions. Included in petroleum resins are those that have been modified with aromatic or terpene containing feedstreams. For additional description of feedstream derivation, monomer composition, methods of polymerization and hydrogenation, reference may be made to patent literature (see Background) and to technical literature, e.g., Hydrocarbon Resins, Kirk-Othmer Encyclopedia of Chemical Technology, v. 13, pp. 717-743 (J. Wiley and Sons, 1995); Encycl. of Poly. Sci. and Eng""g., vol. 7, pp. 758-782 (J. Wiley and Sons, 1987), and the references cited in both of them. Additionally, reference may be made to EP 0 240 253 and its corresponding application U.S. Ser. No. 07/065,792, filed Jun. 27, 1987. All of these references are incorporated by reference for purposes of U.S. patent practice.
The known natural resins will additionally be suitable for hydrotreating in accordance with the invention. The natural resins are traditional materials documented in the literature, see for example, Encycl. of Poly. Sci. and Eng""g., vol. 14, pp. 438-452 (John Wiley and Sons, 1988).
The rosins capable of hydrotreating in accordance with the invention includes any of those known in the art to be suitable as tackifying agents, this specifically includes the esterified rosins. The principal sources of the rosins include gum rosins, wood rosin, and tall oil rosins which typically have been extracted or collected from their known sources and fractionated to varying degrees. Additional background can be obtained from technical literature, e.g., Kirk-Othmer Encycl. of Chem. Tech., vol. 17, pp. 475-478 (John Wiley and son, 1968) and Handbook of Pressure-Sensitive Adhesive Technology, ed. by D. Satas, pp. 353-356 (Van Nostrand Reinhold Co., 1982).
The hydroprocessing, hydrotreating or hydrogenation catalyst used in the practice of the present invention is a bulk multimetallic catalyst comprised of at least one Group VIII non-noble metal and at least one, preferably two, Group VIB metals and wherein the ratio of Group VIB metal to Group VIII non-noble metal is from about 10:1 to about 1:10. It is preferred that the catalyst be a bulk trimetallic catalyst comprised of one Group VIII non-noble metal, preferably Ni or Co and the two Group VIB metals Mo and W. It is preferred that the ratio of Mo to W be about 9:1 to about 1:9.
The preferred bulk trimetallic catalyst compositions used in the practice of the present invention is represented by the formula:
(X)b(Mo)c(W)dOz
wherein X is a Group VIII non-noble metal, the molar ratio of b: (c+d) is 0.5/1 to 3/1, preferably 0.75/1 to 1.5/1, more preferably 0.75/1 to 1.25/1;
The molar ratio of c:d is preferably  greater than 0.01/1, more preferably  greater than 0.1/1, still more preferably 1/10 to 10/1, still more preferably 1/3 to 3/1, most preferably substantially equimolar amounts of Mo and W, e.g., 2/3 to 3/2; and z=[2b+6 (c+d)]/2.
The essentially amorphous material has a unique X-ray diffraction pattern showing crystalline peaks at d=2.53 Angstroms and d=1.70 Angstroms.
The mixed metal oxide is readily produced by the decomposition of a precursor having the formula:
(NH4)a(X)b(Mo)c(W)dOZ
wherein the molar ratio of a:b is xe2x89xa61.0/1, preferably 0-1; and b, c, and d, are as defined above, and z=[a+2b+6 (c+d)]/2. The precursor has similar peaks at d=2.53 and 1.70 Angstroms.
Decomposition of the precursor may be effected at elevated temperatures, e.g., temperatures of at least about 300xc2x0 C., preferably about 300-450xc2x0 C., in a suitable atmosphere, e.g., inerts such as nitrogen, argon, or steam, until decomposition is substantially complete, i.e., the ammonium is substantially completely driven off. Substantially complete decomposition can be readily established by thermogravimetric analysis (TGA), i.e., flattening of the weight change curve.
The catalyst compositions used in the practice of the present invention can be prepared by any suitable means. One such means is a method wherein not all of the metals are in solution. Generally, the contacting of the metal components in the presence of the protic liquid comprises mixing the metal component and subsequently reacting the resulting mixture. It is essential to the solid route that at least one of the metal components is added at least partly in the solid state during the mixing step and that the metal of at least one of the metal components which have been added at least partly in the solid state, remains at least partly in the solid state during the mixing and reaction step. xe2x80x9cMetalxe2x80x9d in this context does not mean the metal in its metallic form but present in a metal compound, such as the metal component as initially applied or as present in the bulk catalyst composition.
Generally, during the mixing step either at least one metal component is added at least partly in the solid state and at least one metal component is added in the solute state, or all metal components are added at least partly in the solid state, wherein at least one of the metals of the metal components which are added at least partly in the solid state remains at least partly in the solid state during the entire process of the solid route. That a metal component is added xe2x80x9cin the solute statexe2x80x9d means that the whole amount of this metal component is added as a solution of this metal component in the protic liquid. That a metal component is added xe2x80x9cat least partly in the solid statexe2x80x9d means that at least part of the metal component is added as solid metal component and, optionally, another part of the metal component is added as a solution of this metal component in the protic liquid. A typical example is a suspension of a metal component in a protic liquid in which the metal is at least partly present as a solid, and optionally partly dissolved in the protic liquid.
To obtain a bulk catalyst composition with high catalytic activity, it is therefore preferred that the metal components, which are at least partly in the solid state during contacting, are porous metal components. It is desired that the total pore volume and pore size distribution of these metal components is approximately the same as those of conventional hydrotreating catalysts. Conventional hydrotreating catalysts generally have a pore volume of 0.05-5 ml/g, preferably of 0.1-4 ml/g, more preferably of 0.1-3 ml/g and most preferably of 0.1-2 ml/g determined by nitrogen adsorption. Pores with a diameter smaller than 1 nm are generally not present in conventional hydrotreating catalysts. Further, conventional hydrotreating catalysts have generally a surface area of at least 10 m2/g and more preferably of at least 50 m2/g and most preferably of at least 100 m2/g, determined via the B.E.T. method. For instance, nickel carbonate can be chosen which has a total pore volume of 0.19-0.39 ml/g and preferably of 0.24-0.35 ml/g determined by nitrogen adsorption and a surface area of 150-400 m2/g and more preferably of 200-370 m2/g determined by the B.E.T. method. Furthermore, these metal components should have a median particle diameter of at least 50 nm, more preferably at least 100 nm, and preferably not more than 5000 xcexcm and more preferably not more than 3000 xcexcm. Even more preferably, the median particle diameter lies in the range of 0.1-50 xcexcm and most preferably in the range of 0.5-50 xcexcm. For instance, by choosing a metal component which is added at least partly in the solid state and which has a large median particle diameter, the other metal components will only react with the outer layer of the large metal component particle. In this case, so-called xe2x80x9ccore-shellxe2x80x9d structured bulk catalyst particles are obtained.
An appropriate morphology and texture of the metal component can either be achieved by applying suitable preformed metal components or by preparing these metal components by the above-described precipitation under such conditions that a suitable morphology and texture is obtained. A proper selection of appropriate precipitation conditions can be made by routine experimentation.
As has been set out above, to retain the morphology and texture of the metal components which are added at least partly in the solid state, it is essential that the metal of the metal component at least partly remains in the solid state during the whole process of this solid route. It is noted again that it is essential that in no case should the amount of solid metals during the process of the solid route becomes zero. The presence of solid metal comprising particles can easily be detected by visual inspection at least if the diameter of the solid particles in which the metals are comprised is larger than the wavelength of visible light. Of course, methods such as quasi-elastic light scattering (QELS) or near forward scattering which are known to the skilled person can also be used to ensure that in no point in time of the process of the solid route, all metals are in the solute state.
The protic liquid to be applied in the solid or solution route of this invention for preparing catalyst can be any protic liquid. Examples include water, carboxylic acids, and alcohols such as methanol or ethanol. Preferably, a liquid comprising water such as mixtures of an alcohol and water and more preferably water is used as protic liquid in this solid route. Also different protic liquids can be applied simultaneously in the solid route. For instance, it is possible to add a suspension of a metal component in ethanol to an aqueous solution of another metal component.
The Group VIB metal generally comprises chromium, molybdenum, tungsten, or mixtures thereof Suitable Group VIII non-noble metals are, e.g., iron, cobalt, nickel, or mixtures thereof Preferably, a combination of metal components comprising nickel, molybdenum and tungsten or nickel, cobalt, molybdenum and tungsten is applied in the process of the solid route. If the protic liquid is water, suitable nickel components which are at least partly in the solid state during contacting comprise water-insoluble nickel components such as nickel carbonate, nickel hydroxide, nickel phosphate, nickel phosphite, nickel formate, nickel sulfide, nickel molybdate, nickel tungstate, nickel oxide, nickel alloys such as nickel-molybdenum alloys, Raney nickel, or mixtures thereof. Suitable molybdenum components, which are at least partly in the solid state during contacting, comprise water-insoluble molybdenum components such as molybdenum (di- and tri) oxide, molybdenum carbide, molybdenum nitride, aluminum molybdate, molybdic acid (e.g. H2MoO4), molybdenum sulfide, or mixtures thereof. Finally, suitable tungsten components which are at least partly in the solid state during contacting comprise tungsten di- and trioxide, tungsten sulfide (WS2 and WS3), tungsten carbide, tungstic acid (e.g. H2WO4xe2x80x94H2O, H2W4O13xe2x80x949H2O), tungsten nitride, aluminum tungstate (also meta-, or polytungstate) or mixtures thereof These components are generally commercially available or can be prepared by, e.g., precipitation. e.g., nickel carbonate can be prepared from a nickel chloride, sulfate, or nitrate solution by adding an appropriate amount of sodium carbonate. It is generally known to the skilled person to choose the precipitation conditions in such a way as to obtain the desired morphology and texture.
In general, metal components, which mainly contain C, O and/or H beside the metal, are preferred because they are less detrimental to the environment. Nickel carbonate is a preferred metal component to be added at least partly in the solid state because when nickel carbonate is applied, CO2 evolves and positively influences the pH of the reaction mixture. Further, due to the transformation of carbonate into CO2, the carbonate does not end up in the wastewater.
Preferred nickel components which are added in the solute state are water-soluble nickel components, e.g. nickel nitrate, nickel sulfate, nickel acetate, nickel chloride, or mixtures thereof. Preferred molybdenum and tungsten components which are added in the solute state are water-soluble molybdenum and tungsten components such as alkali metal or ammonium molybdate (also peroxo-, di-, tri-, tetra-, hepta-, octa-, or tetradecamolybdate), Moxe2x80x94P heteropolyanion compounds, Wo-Si heteropolyanion compounds, Wxe2x80x94P heteropolyanion compounds, Wxe2x80x94Si heteropolyanion compounds, Nixe2x80x94Moxe2x80x94W heteropolyanion compounds, Coxe2x80x94Moxe2x80x94W heteropolyanion compounds, alkali metal or ammonium tungstates (also meta-, para-, hexa-, or polytungstate), or mixtures thereof.
Preferred combinations of metal components are nickel carbonate, tungstic acid and molybdenum oxide. Another preferred combination is nickel carbonate, ammonium dimolybdate and ammonium metatungstate. It is within the scope of the skilled person to select further suitable combinations of metal components. It must be noted that nickel carbonate always comprises a certain amount of hydroxy-groups. It is preferred that the amount of hydroxy-groups present in the nickel carbonate be high.
An alternative method of preparing the catalysts used in the practice of the present invention is to prepare the bulk catalyst composition by a process comprising reacting in a reaction mixture a Group VIII non-noble metal component in solution and a Group VIB metal component in solution to obtain a precipitate. As in the case of the solid route, preferably, one Group VIII non-noble metal component is reacted with two Group VIB metal components. The molar ratio of Group VIB metals to Group VIII non-noble metals applied in the process of the solution route is preferably the same as described for the solid route. Suitable Group VIB and Group VIII non-noble metal components are, e.g. those water-soluble nickel, molybdenum and tungsten components described above for the solid route. Further Group VIII non-noble metal components are, e.g., cobalt or iron components. Further Group VIB metal components are, e.g. chromium components. The metal components can be added to the reaction mixture in solution, suspension or as such. If soluble salts are added as such, they will dissolve in the reaction mixture and subsequently be precipitated. Suitable Group VIB metal salts which are soluble in water are ammonium salts such as ammonium dimolybdate, ammonium tri-, tetra- hepta-, octa-, and tetradecamolybdate, ammonium para-, meta-, hexa-, and polytungstate, alkali metal salts, silicic acid salts of Group VIB metals such as molybdic silicic acid, molybdic silicic tungstic acid, tungstic acid, metatungstic acid, pertungstic acid, heteropolyanion compounds of Moxe2x80x94P, Moxe2x80x94Si, Wxe2x80x94P, and Wxe2x80x94Si. It is also possible to add Group VIB metal-containing compounds which are not in solution at the time of addition, but where solution is effected in the reaction mixture. Examples of these compounds are metal compounds which contain so much crystal water that upon temperature increase they will dissolve in their own metal water. Further, non-soluble metal salts may be added in suspension or as such, and solution is effected in the reaction mixture. Suitable non-soluble metals salts are heteropolyanion compounds of Coxe2x80x94Moxe2x80x94W (moderately soluble in cold water), heteropolyanion compounds of Nixe2x80x94Moxe2x80x94W (moderately soluble in cold water).
The reaction mixture is reacted to obtain a precipitate. Precipitation is effected by adding a Group VIII non-noble metal salt solution at a temperature and pH at which the Group VIII non-noble metal and the Group VIB metal precipitate, adding a compound which complexes the metals and releases the metals for precipitation upon temperature increase or pH change or adding a Group VIB metal salt solution at a temperature and pH at which the Group VIII non-noble metal and Group VIB metal precipitate, changing the temperature, changing the pH, or lowering the amount of the solvent. The precipitate obtained with this process appears to have high catalytic activity. In contrast to the conventional hydroprocessing catalysts, which usually comprise a carrier impregnated with Group VIII non-noble metals and Group VIB metals, said precipitate can be used without a support. Unsupported catalyst compositions are usually referred to as bulk catalysts. Changing the pH can be done by adding base or acid to the reaction mixture, or adding compounds, which decompose upon temperature, increase into hydroxide ions or H+ ions that respectively increase or decrease the pH. Examples of compounds that decompose upon temperature increase and thereby increase or decrease the pH are urea, nitrites, ammonium cyanate, ammonium hydroxide, and ammonium carbonate.
In an illustrative process according to the solution route, solutions of ammonium salts of a Group VIB metal are made and a solution of a Group VIII non-noble metal nitrate is made. Both solutions are heated to a temperature of approximately 90xc2x0 C. Ammonium hydroxide is added to the Group VIB metal solution. The Group VIII non-noble metal solution is added to the Group VIB metal solution and direct precipitation of the Group VIB and Group VIII non-noble metal components occurs. This process can also be conducted at lower temperature and/or decreased pressure or higher temperature and/or increased pressure.
In another illustrative process according to the solution route, a Group VIB metal salt, a Group VIII metal salt, and ammonium hydroxide are mixed in solution together and heated so that ammonia is driven off and the pH is lowered to a pH at which precipitation occurs. For instance when nickel, molybdenum, and tungsten components are applied, precipitation typically occurs at a pH below 7.
Independently from whether the solid or solution route is chosen the resulting bulk catalyst composition preferably comprises and more preferably consists essentially of bulk catalyst particles having the characteristics of the bulk catalyst particles described above.
The bulk catalyst composition can generally be directly shaped into hydroprocessing particles. If the amount of liquid of the bulk catalyst composition is so high that it cannot be directly subjected to a shaping step, a solid liquid separation can be performed before shaping. Optionally the bulk catalyst composition, either as such or after solid liquid separation, can be calcined before shaping.
The median diameter of the bulk catalyst particles is at least 50 nm, more preferably at least 100 nm, and preferably not more than 5000 xcexcn and more preferably not more than 3000 xcexcm. Even more preferably, the median particle diameter lies in the range of 0.1-50 xcexcm and most preferably in the range of 0.5-50 xcexcm.
If a binder material is used in the preparation of the catalyst composition it can be any material that is conventionally applied as a binder in hydroprocessing catalysts. Examples include silica, silica-alumina, such as conventional silica-alumina, silica-coated alumina and alumina-coated silica, alumina such as (pseudo)boehmite, or gibbsite, titania, zirconia, cationic clays or anionic clays such as saponite, bentonite, kaoline, sepiolite or hydrotalcite, or mixtures thereof. Preferred binders are silica, silica-alumina, alumina, titanic, zirconia, or mixtures thereof. These binders may be applied as such or after peptization. It is also possible to apply precursors of these binders that, during the process of the invention are converted into any of the above-described binders. Suitable precursors are, e g., alkali metal aluminates (to obtain an alumina binder), water glass (to obtain a silica binder), a mixture of alkali metal aluminates and water glass (to obtain a silica alumina binder), a mixture of sources of a di-, tri-, and/or tetravalent metal such as a mixture of water-soluble salts of magnesium, aluminum and/or silicon (to prepare a cationic clay and/or anionic clay), chlorohydrol, aluminum sulfate, or mixtures thereof.
If desired, the binder material may be composited with a Group VIB metal and/or a Group VIII non-noble metal, prior to being composited with the bulk catalyst composition and/or prior to being added during the preparation thereof. Compositing the binder material with any of these metals may be carried out by impregnation of the solid binder with these materials. The person skilled in the art knows suitable impregnation techniques. If the binder is peptized, it is also possible to carry out the peptization in the presence of Group VIB and/or Group VIII non-noble metal components.
If alumina is applied as binder, the surface area preferably lies in the range of 100-400 m2/g, and more preferably 150-350 m2/g, measured by the B.E.T. method. The pore volume of the alumina is preferably in the range of 0.5-1.5 ml/g measured by nitrogen adsorption.
Generally, the binder material to be added in the process of the invention has less catalytic activity than the bulk catalyst composition or no catalytic activity at all. Consequently, by adding a binder material, the activity of the bulk catalyst composition may be reduced. Therefore, the amount of binder material to be added in the process of the invention generally depends on the desired activity of the final catalyst composition. Binder amounts from 0-95 wt. % of the total composition can be suitable, depending on the envisaged catalytic application. However, to take advantage of the resulting unusual high activity of the composition of the present invention, binder amounts to be added are generally in the range of 0.5-75 wt. % of the total composition.
The catalysts of this invention are typically activated by a sulfiding agent in the presence of hydrogen. The sulfur compounds that can be used include H2S, carbon disulfide, methyldisulfide, ethyldisulfide, propyldisulfide, isopropyldisulfide, butyldisulfide, tertiary butyldisulfide, thianaphthene, thiophene, secondary dibutyldisulfide, thiols, sulfur containing hydrocarbon oils and sulfides such as methylsulfide, ethylsulfide, propylsulfide, isopropylsulfide, butylsulfide, secondary dibutylsulfide, tertiary butylsulfide, dithiols and sulfur-bearing gas oils. Any other organic sulfur source that can be converted to H2S over the catalyst in the presence of hydrogen can be used. The catalyst may also be activated by an organo sulfur process as described in U.S. Pat. No. 4,530,917 and other processes described therein and this description is incorporated by reference into this specification.
Generic hydrogenation treating conditions include reactions in the temperature of about 100xc2x0 C.-350xc2x0 C. and pressures of between five atmospheres (506 kPa) and 300 atm. (30390 kPa) hydrogen, for example, 10 to 275 atm. (1013 kPa to 27579 kPa). In one embodiment the temperature is in the range including 180xc2x0 C. and 320xc2x0 C. and the pressure is in the range including 15195 kPa and 20260 kPa hydrogen. The hydrogen to feed volume ratio to the reactor under standard conditions (25xc2x0 C., 1 atoms. pressure) typically can range from 20-200, for water-white resins 100-200 is preferred.
Catalyst activity decreases over time due to carbonaceous deposition onto the catalyst support, this can be eliminated or removed by regenerating the catalyst bed with high pressure hydrogen at temperatures between about 310xc2x0 C.-350xc2x0 C. High pressure here means, for example, at least about 180 bar. This regeneration is best accomplished in the absence of hydrocarbon feed to the reactor, e.g., during interruption of the hydrogenation process.
Hydrogenated polymeric resins of the invention specifically include hydrocarbon resins suitable as tackifiers for adhesive compositions, particularly adhesive compositions comprising polymeric base polymer systems of either natural or synthetic elastomers, including such synthetic elastomers as those from styrene block copolymers, olefinic rubbers, olefin derived elastomers or plastomers, and various copolymers having elastomeric characteristics, e.g., ethylene-vinyl ester copolymers. Such adhesive compositions find particular utility in hot melt adhesive and pressure sensitive adhesive applications such as those for adhesive tapes, diaper tabs, envelopes, note pads, and the like. Often compatibility of the tackifier with polymeric base polymer systems is best achieved by selection of a hydrocarbon resin that is high in aromatic monomer content. Concurrently it is sought to select a tackifier that has color characteristics commensurate with those of the base polymer system, preferably both the polymer system and its tackifier will be essentially transparent and low in chromophores, that is, color. Retention of this low color characteristic is important during heating operations such as those present in formulation by melt processing and application of the adhesive compositions to substrate materials under elevated temperatures. Adequate hydrogenation is known to achieve desirable heat stability of low color properties in polymeric hydrocarbon resins made from either aliphatic or aromatic monomers, or mixes thereof. Both objectives can be achieved by use of the process of the present invention.

Hydrogenation process for hydrocarbon resins


A system to sanitize water in a whirlpool bathtub, spa, swimming pool, and other water vessels comprising improvements to U.S. Pat. No. 6,395,167 and incorporating an integral top fill antimicrobial injector not in the prior art. The system also practices the adding of antimicrobial additives to the water vessel system components, which include but are not limited to the system""s piping, pump, jets, acrylic sheet and fiberglass/resin reinforcements.

The present invention relates to combining a replaceable filter and a suction device in a closed loop home or hotel whirlpool bath, hydrotherapeutic baths, and other bathing receptacles. The present invention also relates to a safety oriented pop off faceplate and an antimicrobial liquid dispenser. In addition, antimicrobial additives may be placed in one or more components of the water vessel system.
Whirlpool-type baths have been employed to treat discomfort resulting from strained muscles, joint ailments and the like. More recently, such baths have been used increasingly as means of relaxing from the daily stresses of modern life. A therapeutic effect is derived from bubbling water and swirling jet streams that create an invigorating hydro massage of the user""s body.
To create the desired whirlpool motion and hydro massage effect, a motorized water pump draws water through a suction fitting in a receptacle, such as a bathtub. The user first fills the bathtub. Then the user activates the closed loop whirlpool system. The water travels through a piping system and back out jet fittings. Jet fittings are typically employed to inject water at a high velocity into a bathtub. Usually the jet fittings are adapted to aspirate air so that the water discharged into the receptacle is aerated to achieve the desired bubbling effect. (See for instance, U.S. Pat. No. 4,340,039 to Hibbard et al., incorporated herein by reference from U.S. Pat. No. 6,395,167 to Mattson, Jr. et al. (xe2x80x9cMattsonxe2x80x9d) which is incorporated herein by reference.
Generally, whirlpool baths are designed as with a normal bathtub to be drained after each use. However, debris in the form of dead skin, soap, hair and other foreign material circulates throughout the piping and pump system. This debris does not completely drain and over time, accumulates in the piping system and may cause a health risk. Therefore, a filtration system designed for whirlpool baths was desirable. Mattson provides for a filtration system which filters debris in the water with respect to whirlpool baths. The present invention improves upon the Mattson filtration system for whirlpool baths. Before Mattson, filtration systems were found only in indoor and outdoor pools.
For some time, whirlpool bath manufacturers have tried to devise a way to incorporate a filtration system on a closed loop whirlpool bath. Although many problems exist, compliance with the plumbing codes is the major obstacle faced in using a filtration system for a whirlpool bath. Until Mattson, there was no filtration system that specifically designed for a drain down whirlpool bath that allows a whirlpool bath to pass requirements set forth by the current plumbing code.
Whirlpool baths must meet stringent drain down code requirements set up by the American Society of Mechanical Engineers (ASME). The code that governs whirlpool baths is entitled xe2x80x9cWhirlpool Bath Appliancesxe2x80x9d (ASME A112.19.7M 1995). Section 5 of this code covers water retention and provides: xe2x80x9cwhirlpool bath appliances shall be of such design as to prevent retention of water in excess of 44 ml. (1xc2xd fl oz) for each jet and suction filter.xe2x80x9d
The average whirlpool bath has a six-jet system and has one suction fitting. In order to meet code, a six-jet/one suction system configuration may only retain 10xc2xd ounces of water in the complete whirlpool bath system after draining. Most quality whirlpool baths, however, retain less than 4 ounces of water in the whirlpool bath system after draining. The filter part of the system cannot retain over 6xc2xd ounces of water, because the total water retention would then exceed 10xc2xd ounces. Mattson is currently the only known filtration system designed for whirlpool baths that retains less than 6xc2xd ounces of water. The complete filtration system of the present invention, however, retains less than 4 ounces of water and as little as 2 ounces of water; so most whirlpool bath companies could use it on their whirlpool bath models and pass the drain down codes for whirlpool baths.
Another important consideration in developing a filtration system for whirlpool baths is the ease of replacing the filter. To eliminate access panels on the underside of the whirlpool bath which are used to access the filter, the filtration system was designed so the filter could be replaced from inside the bath. Therefore, the most logical choice for a filter location is in the suction fitting. However, placing the filter in the suction fitting presents a different range of design concerns. For example, placing a filter in the suction fitting may cause undue stress on the pump motor.
The suction filter must pass the codes set up by ASME for suctions which include a variety of load and structural tests. The code for suctions from ASME is titled Suction Fittings For Use in Swimming Pools, Spas, Hot Tubs, and Whirlpool Bathtub Appliances (ASME/IAMPO reaffirm 1996). Presently there is only one patented whirlpool bathtub suction filter that passes ASME code to be placed on a whirlpool bathtub. See Mattson incorporated herein. The present invention provides a cavity that houses a filter that could be installed in such a way that the filter is replaced from the inside of a whirlpool bath.
The filter was designed to be small to meet the drain down requirements. Because of its small size, however, it also had to be very efficient. Therefore, the present invention has a specially designed filter core. The core is engineered with varying spaced and sized holes along the length of the core. This design allows water to be drawn through the entire filter. Without this design, the filter would only pull water through about 20% of the filter near the outlet.
Other problems in whirlpool bathtub and spa use are encountered when a user""s hair is twisted and entrapped in the whirlpool bath pump impeller. Hair entrapment occur when a bather""s hair becomes entangled in a suction fitting drain cover as the water and hair are drawn powerfully through the drain. The Consumer Product Safety Commission has issued a safety alert article entitled xe2x80x9cChildren Drown and More Are Injured From Hair Entrapment In Drain Covers For Spas, Hot Tubs, And Whirlpool Bathtubsxe2x80x9d (CPSC Document #5067). The safety alert urges consumers to ask their spa, hot tub, and whirlpool bathtub dealers for drain covers that meet voluntary standard ASME/ANSI A112.19.8M 1987) to help reduce hair entrapment. The present invention meets the voluntary ASME/ANSI standard.
The present invention also provides a new faceplate cover which is easily removable. The faceplate also has to pass the heavy load, impact and hair entrapment tests set out by ASME/IAMPO. One cover embodiment has a radius and back ribbing on it and a removable insert support to pass the strength tests. The preferred embodiment faceplate is flat with structural fins on its back side, thus eliminating the removable insert. Each cover has a sufficient number of sized holes to pass the prescribed hair entrapment tests. The result is the fluid suction filter device that is especially made just for whirlpool baths.
In the safety alert CPSC Document #5067, the Consumer Product Safety Commission suggests that consumers shut down the spa until the drain cover is replaced in the event that the consumer discovers the drain cover missing or broken. The present invention allows the water system to shut itself down if the faceplate drain cover is missing or broken by means of a non-electric cavitation mechanism. The water system is also shut down if a clog occurs.
It is found that even after debris is filtered from a whirlpool bathtub, trace amounts of bacteria still can grow in a whirlpool bathtub. In fact, even if normal tap water where to be run through the closed looped system of a whirlpool bathtub, trace amounts of bacteria can form in the whirlpool bathtub""s closed looped piping system. To eliminate these trace bacteria, a special filter core with an antimicrobial chamber was developed.
This antimicrobial chamber emits antimicrobial agents to kill the trace bacteria that may grow in the whirlpool bathtub""s closed looped piping system, upon initial whirlpool bathtub activation and between usages. However, most of the antimicrobial agents would dissipate as soon as they enter the inside of the bathtub where people bathe. In other words, due to breakdown and dissipation, the antimicrobial agents do not build up in the bath water as the whirlpool operates. Therefore, the user may activate the antimicrobial dispenser mechanism to distribute antimicrobial agents at will or on a timed basis. The antimicrobial dispenser is a top filled design not known in the prior art. Another embodiment teaches the use of multiple chambers wherein each chamber is used for additional additives desired by the user.
Only a very small amount of antimicrobial agent is necessary to kill the bacteria in the closed looped piping system since the filter helps to trap hair, soap and other debris which provides food for bacterial growth. Without the filter a greater amount of antimicrobial agent would need to be introduced into the system to kill the bacteria and this excessive amount could irritate the skin of sensitive bathers.
Another integral part of creating a total water vessel sanitation system is to include antimicrobial additives in each component of the water vessel. With respect to whirlpool bathtubs and spas, this would include at least the system""s water and air pipes, pump, and pump impellor. The surfaces of whirlpool bathtubs and spas are comprised primarily of a thermo-formed acrylic or plastic sheet or gelcoat paint. Therefore, in a total water sanitation system, the acrylic or plastic sheet or the gelcoat paint would require antimicrobial additives. The fiberglass and resin reinforcement backing of the whirlpool bathtub and spa are impregnated with antimicrobial additives as are the whirlpool bathtub jets and suctions. While the technology exists to add antimicrobial additives to a whirlpool bathtub and spa component, there is no prior art that suggests that antimicrobial additives be placed in one or more component or in combination with all components to provide for optimum protection from bacteria.
U.S. Pat. No. 6,395,167 (2002) to Mattson, Jr. et al. discloses a whirlpool bath with combination suction fixture and disposable filter. The housing of the suction filter is one to two feet long. A correspondingly sized replaceable filter is mounted into the filter housing lengthwise.
U.S. Pat. No. 6,283,308 (2001) to Patil et al. discloses a bacteriostatic filter cartridge having elements impregnated with an anti-microbial agent.
U.S. Pat. No. 5,799,339 (1998) to Perry et al. discloses a suction device for a spa or jetted tub with a turbulence reduction design to reduce the possibility of entangling a user""s hair in the faceplate.
The main aspect of the present invention is to provide a suction fixture and replaceable filter combination apparatus in a whirlpool bath.
Another aspect of the present invention is to provide a safety plate for the suction intake which resists hair entrapment.
Another aspect of the present invention is to provide a pop off suction faceplate and a pop out filter core to provide safety features to prevent drowning.
Another aspect of the present invention is to provide a non-electric safety cavitation port to cause cavitation which shuts down motor operation if the filter is absent or improperly inserted.
Another aspect of the present invention is to provide a minimal water retention filter to retain less than 6xc2xd ounces of water after drain down.
Another aspect of the present invention is to provide a housing which is readily retrofitable and/or incorporated into a new whirlpool bath that retains minimal water.
Another aspect of the present invention is to reduce bacteria or microbes in a closed loop system of a whirlpool bathtub.
Another aspect of the present invention is to provide a total water vessel sanitation which includes antimicrobial additives in each component of the water vessel system.
Other aspects of this invention will appear from the following description and appended claims, reference being made to the accompanying drawings forming a part of this specification wherein like reference characters designate corresponding parts in the several views.
The suction filter is comprised of the filter core, the filter, and the filter housing. The filter core has a plurality of water draw holes having increasing diameters extending away from the water outlet. These holes provide for water draw along the entire length of the filter, instead of just making use of the filter at the outlet and of the filter. These increasing and decreasing holes provide for optimum water draw through the filter that surrounds the core. The filter core has a 2xe2x80x3 inside diameter (I.D.) to assure over 200 GPM water flow draw rates. Without this I.D., you would not be able to get 200 GPM to run through the filter core allowing a combination filter suction an overall 200 GPM rating. No other manufacturer makes a filter for whirlpool bathtubs or even a filter that fits into a housing outlet with a 2xe2x80x3 I.D. The core is made from injected plastic but could be machined from metal or a variety of other materials.
The filter core has an antimicrobial chamber that houses antimicrobial additives. The antimicrobial chamber measures approximately 1xe2x80x3 to 8xe2x80x3 in length and xc2xd to 2xe2x80x3 in diameter. The antimicrobial additives used in the antimicrobial chamber could be slow dissolving chlorine, bromine, or a variety of other antimicrobial additives. The cover to the antimicrobial chamber has an adjusting hole opening which can be increased or decreased by turning the main body of the antimicrobial chamber in one direction or another. The more the antimicrobial chamber is screwed on, the smaller the hole opening becomes. The antimicrobial chamber has one hole but could have multiple holes or slots. The filter core""s plastic is injected with antimicrobial additives during the injected molding process and inhibits any germ growth on the core between uses.
Multiple chambers may be added on the filter core along with the antimicrobial chamber for the addition of other additives. For example, the filter core may have a built in ion exchange chamber allowing for a built in water softener that softens the bathwater. It may also have a fragrance chamber that emits fragrances into the bathwater. Both of these items are not known in prior art for a suction filter core for a whirlpool bathtub or spa.
Water flows past the antimicrobial chamber creating a vacuum which pulls a small quantity of antimicrobial additive from the chamber, thereby mixing it with the water. The amount of antimicrobial additives mixed into the water is in sufficient quantities to kill the trace bacteria that may grow between whirlpool bath usages in a filtered whirlpool bathtub system. The antimicrobial additives dissipate by the time the antimicrobial additives mix and enter the larger volume of water in the bathing area.
A filter which is generally treated with antimicrobial additives either slips over the filter core or is bonded onto the core making a one-piece filter core combination. Although the filter could be pleated or non-pleated, the preferred embodiment has a two staged pleat filter media. The first pleat has larger holes which allow larger sized particles and debris to pass through the antimicrobial treated filter pleat. The second pleat has smaller openings allowing only microscopic debris particles to pass through the treated filter pleat. Although microscopic debris may accumulate in the space between the inner and outer pleats, both filter media are impregnated with antimicrobial agents, which kill bacteria which would accumulate on the pleats. Together, the inner and outer pleat create a halo effect killing of the bacteria which accumulates between the inner and outer filter media. This layered filter design is important in decreasing the build up of debris on the outer layer of the filter which nearest to the bather.
The filter media is preferably made out of polypropylene or other media that will accept antimicrobial agents. In the spa industry, polyester media is used. Polypropylene media can be treated in the manufacturing process with antibacterial agents, whereas polyester media cannot. In the whirlpool industry, however, filters were not used on whirlpool baths until an approved filtration system for whirlpool baths under the Mattson ""167 patent.
The preferred filter is designed to retain less than 3 ounces of water.
The housing of the suction filter is generally cylindrical having a diameter of four inches to two feet. The filter housing is tapered from front to back to allow water to drain back into the tub after shutdown. The preferred housing is the only known housing that has tapered sides of the inner wall to allow water to drain back into the whirlpool bathtub when the whirlpool bathtub system is deactivated whether the unit is installed facing left or right. The filter housing has a sharp radius end opposite the outlet end, thus allowing the housing to be fitted into the side wall of a tub through a standard size opening cut.
The filter housing is mounted to the inner tub wall by using a screw nut between the housing mounting flange and the inner tub wall. A gasket or silicone can be used between the outer tub wall and the screw nut to prevent leaks.
The filter core now fits into the filter housing in axial alignment with the filter housing""s inlet opening. In other words, the filter is now perpendicular from that of U.S. Pat. No. 6,395,167. The filter core has two slots cut into the end that fits into the outlet of the filter housing. The filter housing has two male ridges which make the preferred filter core the only filter core that fits the preferred housing. As set forth above, the filter core is designed with varying sized holes and slots. The holes furthest from the outlet port are larger than the holes near the outlet port. This allows water to pull through the entire filter.
The filter housing has a safety cavitation port located at the inside wall of the housing. Placing a cavitation port at the inside wall of a suction fitting is not known in prior art.
The faceplate cover described below has a cavitation port fin which covers the non-electric cavitation port when the faceplate cover is attached to the filter housing. The cavitation port fin is one of four available cavitation port fins designed to fit into a receiving bracket adjacent to the cavitation port hole. If the filter were removed or if a person tried to operate the unit without the filter core covering this hole, air from the tube would be drawn into the pump and the pump would cavitate (draw more air than water). Since people have drowned by getting their hair caught in a suction cover while their head is below the tub waterline, this is an important feature. No user could run the unit without the filter in place. This feature also reduces the chance of drawing contaminants into the whirlpool bath system. Once contaminants such as hair are entrapped in the pump""s impeller, the entire whirlpool bath system becomes contaminated until someone physically opens the whirlpool bath pump (a long and time consuming process usually requiring a professional), frees the entrapped hair, and sanitizes the complete system.
The filter core has a gasket that slides over the nonelectric safety cavitation port. Without this gasket, the replaceable filter core could rub against the filter housing outlet and cause wear over the years to the filter housing outlet.
The suction filter has been downsized to fit more whirlpool bathtubs. The downsized version attaches to the whirlpool bathtub with a nut which eliminates the attachment screws of U.S. Pat. No. 6,395,167. With the smaller filter design, however, filter replacement is likely to occur more often.
The present invention has two lights that are placed in a visible position on the whirlpool bathtub. The lights are hooked up to the whirlpool bathtub pump with a vacuum switch. If the combination suction filter, filter media (removable filter) accumulates enough debris, this blockage on the filter triggers a vacuum switch, which senses the blockage, and a preferably red indicator light comes on that indicates to the bather that it is time to remove and clean the removable filter or simply replace it. Otherwise a preferably green indicator light stays on indicating to the bather that the filter is not ready for replacement.
The present invention also provides another means to indicate when to replace the filter. The end cap of the filter is treated with a special chemical in the manufacturing process which creates a color reaction when the end cap is introduced to water. The first color would indicate the filter is not ready for replacement. The second color would indicate the filter should be replaced. For example, the end cap is white before water submersion. Once water is introduced to it, the reaction begins and the end cap will slowly turn to black over a predetermined period of time. During whirlpool bathtub operation but before the predetermined period of filter life time, the end cap color will range from white to varying shades of grey until it becomes totally black. Once it turns totally black, the bather knows it is time to replace the filter. This reaction may be have a time release factor and can last from 1 to 360 days depending upon the amount of chemicals used in the end cap manufacturing.
Another inlet orifice may be added to the filter housing of the present invention. This orifice can be hooked up in tandem to a skimmer filter in a spa in order to filter water which may bypass a filtration system. Currently spas, like whirlpool bathtubs, have one or multiple suction fittings that draw water into a pump and back out through jets. Although spas also have skimmers filters that draw surface water through the filters into a pump and back through the jets, the majority of the water passing through other suction points bypasses the filters in the skimmer causing contaminated water to circulate through the system. Most of the other suction points do not have filters. By replacing standard spa suction fittings with the present invention suction filter and hooking the outlet of the spa skimmer to one of the present invention suction filters, all water in a spa is filtered.
The faceplate shown in FIGS. 4A through 4D slides into the housing to cover the suction filter assembly. The faceplate has a radius shape to prevent a limb from being sucked up against it which could entrap a body part. ASME hair entrapment standards are met using a plurality of slots or holes. Impact and load tests are met.
In the preferred embodiment faceplate shown in FIGS. 4B, 4C, support ribs (also known as support bars) are built into the faceplate and fit into receiving slots in the faceplate housing. This creates a solid part and allows it to pass impact and load tests called out by ASME code. This is the only suction faceplate for whirlpool bathtubs and spas that is designed with the structured supports in the faceplate. This allows a filter to be installed in the suction housing or replaced and still pass these test. All other known suctions have the main structured support as part of the body (housing) and these supports cannot be removed. See U.S. Pat. No. 5,799,339 to Perry et al. which represents all other known suctions. FIG. 5 of U.S. Pat. No. 5,799,339 shows a face view of the support. FIG. 3 shows how FIG. 5 screws in permanently into body 20 of FIG. 3. These supports (26b, 28b called a guide) cannot be removed once the suction is installed.
The preferred faceplate is larger than standard faceplates because of the size of the removable filter. Mattson teaches the combination of a filter and a suction in a single device. The faceplate has slots to allow a larger volume of water to pass through it. Because of the increased size of the faceplate the slots have to be designed and engineered in a radiating pattern. This is very important for the plastic injected molding process.
With the present design over a horizontal (see Perry ""339 patent) or vertical design, the pressure of the injected plastic from the injection point of the mold (usually the injection point of a mold is located in the center of the mold) hits the small end of the slots instead of the wide end of the slots. The shorter end of the slot can withstand a great deal more pressure over time before failure than if the pressure were subjected to the wide side of the slots. This allows for much longer mold life and a more pleasing finished product. The radiating pattern of slots gives a straight-line flow to the outer edge of the faceplate part. U.S. Pat. No. 5,799,339 FIG. 4 shows a standard slot opening arrangement that represents the arrangement of slots used by manufacturers of slotted face faceplates. U.S. Pat. No. 6,038,712 to Chalberg et al. FIG. 2 shows circular hole openings which represent how other faceplates are made. Slots are preferable over circular holes to increase flow.
The preferred embodiment faceplate housing eliminates the drain down slots of the original design because water now evacuates through the bottom slots of the faceplate.
To prevent people""s hair or body parts from getting trapped in the exposed hole where the faceplate cover is removed during whirlpool bath operation, current ASME plumbing code requires that all suction faceplate covers be engineered so the faceplate cannot be removed without the use of a tool. Most suction covers attach the faceplate to the housing with a screw and a screwdriver is needed to remove the screw. See U.S. Pat. No. 6,038,712 FIG. 2 which shows screw hole openings and U.S. Pat. No. 5,799,339 FIG. 3 number 22 which shows the screw. There are some suction manufacturers that have a non-electric cavitation device in the faceplate of the suction, see Chalberg U.S. Pat. No. 6,038,712. If the face of the suction is restricted significantly, the unit cavitates and the suction against the faceplate decreases. However, these designs are still dangerous. Hair can still become twisted in the faceplate before the unit shuts down. It is thought that if hair enters the Chalberg ""712 cover and the cover is blocked to cease suction action, the hair can be easily removed. However, when hair enters a suction cover a vortex may form behind the cover causing the hair to twist and tangle, thereby preventing removal. Once the hair is trapped, you need a tool like a screwdriver by code to take the faceplate off. The entrapped hair can trap the head of the user under the tub""s waterline. Therefore, people still can drown with these devices.
As stated above, the code requirement for a tool to remove the faceplate is to prevent body parts or hair from getting trapped in the exposed housing support cross members (which are an integral nonremovable part of the suction body in the event that the faceplate of current suctions is removed. But because the preferred embodiment suction filter will not operate without the filter in place, there is no need for the screw. The faceplate preferably attaches to the faceplate housing with magnets. The magnet hole openings of the housing are recessed for flush mounting. They also are flat recessed.
With the design of the present invention, there is no danger of limb entrapment because the system would simply not operate. If someone did get his or her hair caught in the preferred faceplate while the filter was in place, the whole faceplate pops off easily as the faceplate is held in place by magnets. As soon as the faceplate pops off, the cavitation fin which normally covers the safety cavitation port would move out of place. Once the non-electric cavitation port is uncovered, the pump cavitates, thereby immediately preventing body limbs or hair from becoming entrapped in the exposed suction opening. The suction cover has a pull-tab on the cover to allow the bather to easily remove the cover when the whirlpool bath pump is in operation if desired. Depending on the alignment of the faceplate with the faceplate housing, the pull tab could be at any of four locations, i.e., bottom, top, left, or right.
If the unit were to run without the faceplate cover, and hair is caught in the exposed filter, the filter itself also pops out easily. Therefore, there is no chance of getting entrapped if the filter is removed, because the unit will also cavitate under these circumstances.
With the present invention, we plan to have ASME revise their codes for suction covers to allow them to be removable without a tool such as a screwdriver.
U.S. patent application Ser. No. 09/417,156 SORENSEN, EDWIN C. shows a break away drain cover for a spa. Sorensen operates a magnetically actuated switch transmitting an electrical signal. It does not have a safe non-electrical safety cavitation port like the present invention. People are concerned when any electrical signal is transmitted in a water vessel. U.S. patent application Ser. No. 2001/0013373 WRIGHT, JAMES R. shows a drain cover which is similar to the drain cover of Sorensen.
Both these inventions are drain covers and not suction fittings because they do not conform to ASME suction fitting codes. Neither pass the ASME code requirements set out in Section 4 for xe2x80x9cSuction Fittings For Use in Swimming Pools, Spas, Hot Tubs, and Whirlpool Bathtub Appliancesxe2x80x9d (ASME/ANSI A112.19M-1987 reaffirm 1996) and Section 7 ASME A112.19.7M-1995, the hair entrapment test. Sorensen uses a xe2x80x9csnap fitxe2x80x9d to attach the faceplate to a drain wall fitting that may present a wear problem over the years as the cover is repeatedly put on and taken off. The present invention uses earth magnets that will last the lifetime of the spa or bath it is placed on.
Further, the Sorensen invention does not claim, when used in conjunction with a whirlpool bath instead of a spa, that it will allow the whirlpool bath to meet the drain down requirements of ASME A112.19.7M-1995, xe2x80x9cWhirlpool Bathtub Appliances.xe2x80x9d The present invention does so claim. Another advantage of the present invention over Sorensen is that the non-electric cavitation safety feature (combination port hole, air tube, faceplate, cavitation fin) costs a fraction of what a signal-transmitting device would cost to manufacture. Therefore, while there is prior art for electronics-based breakaway covers in a variety of inventions, there is no prior art for a breakaway cover that utilizes a cost saving non-electrical cavitation port. Being non-electrical makes the present invention very safe for whirlpool bath, spa and swimming pool applications.
The faceplate back support ribbing is designed in an X pattern, which offers outstanding structural integrity. The circular ribbing adds tremendous strength to the center impact point of the faceplate.
The faceplate is designed to protrude less than xc2xdxe2x80x3 into the tub when attached to the faceplate housing. This streamlined design protrudes much less than most current suctions adding more room to the bathing area of the whirlpool bathtub.
The slotted holes on the top, sides and bottom of the faceplate extend outward keeping in line with the radiating design pattern on the face of the faceplate. This makes it an easier part to inject with plastic.
Because the center faceplate is an area that would have a high fluid intake flow, the center of the faceplate is solid. This solid center section evens out the water flow across the rest of the faceplate so that there are no areas of high flow that would create unwanted areas of high suction force.
Support bars (or ribs) are integrally formed on the backside of the faceplate. The support bars are at right angles to each other and extend between opposite sidewalls of the faceplate. The support bars do not obstruct any of the faceplate slots formed in the face and sidewalls of faceplate. This configuration advantageously prevents hair from entering a faceplate slot and becoming entangled by wrapping around both sides of a support bar.
The faceplate housing has a flange that provides a resting area for the peripheral ledge of the faceplate when the faceplate is attached to the housing. This resting area allows for weaker magnets to be used to keep the faceplate attached to the faceplate housing.
An important feature of the present invention suction filter is the use of an antimicrobial system that is air actuated by depressing a button located on the inside wall or rim of a whirlpool bathtub. When the button is depressed, antimicrobial additives are injected via a tube into the outlet opening of the suction filter. This allows the bather the opportunity to inject a larger amount of antimicrobial additives into the whirlpool bathtub prior to entering the bathtub to give an added safeguard that all bacteria is killed in a whirlpool bath that has not been in operation for an extended period of time. Depressing the button not only injects antimicrobial additives into the outlet of the housing, it disperses the additives. When the tub is filled with water, the injected additives travel first to the pump housing in a high concentration (the pump housing is found to be the place where bacteria growth is the highest) and then throughout the rest of the closed looped piping system, all the while killing bacteria. The greater the period between uses, the more likely a larger amount of bacteria can form in the whirlpool bathtub""s piping system. This safeguard ensures that when activated, the whirlpool bathtub will be bacteria-free even if months have passed since the whirlpool bathtub system was operated.
The present suction filter device could be designed in other configurations than its current square-shaped form. The unit could also be designed in a round form or any other shape or size. The filter and filter core could also be made shorter, longer, larger or smaller. The filter could be made smaller for less money to be disposable after each whirlpool bath use. The filter could even be designed in such a way to be incorporated into existing suctions with modification of those suctions. The filter media that filters the water could be pleated or wrapped without pleating around a filter core.
The housing could be designed to incorporate multiple filters. The ridges and slots at the end of the filter core could be made in a variety of shapes or locations to ensure the use of only one filter.
The main body housing could be vacuum formed and become an integral part of the whirlpool bathtub.
The magnets holding the faceplate to the housing could be larger or smaller and arranged in various other locations on each part. The amount of magnets used could be increased or decreased. The faceplate could also be attached using various snap-on configurations. An installation-sealing gasket could be used. The slope in the sidewalls of the housing could be increased or decreased. The overall size of the suction filter could be increased or decreased.
The housing body, faceplate or filter core could be made from other material than injected plastic; it could be stamped or machined out of metal or other material.
The radiating slotted design of the faceplate could have a radiating round hole design.
The safety cavitation hole could be placed anywhere rearward on the outlet of the housing and be various sizes or have multiple openings.
The filter could have various sanitizing materials in its core such as slow dissolving chlorine tablets or other sanitizing material incorporated into the filter core.
The screw nut that attaches the housing to the sidewall of the whirlpool bathtub could have a washer or use locking nuts and have varying sizes and be made out of a variety of materials, including plastic and nylon or some space age material.

Non-electric sanitation water vessel system


A protective device for the interior of a motor vehicle has a protective structure which has a planar shape in a protective position and which is seated for movement by a drive mechanism between at least two positions. The protective structure is connected with at least one guide element that can be entrained by at least one coupling member with transfer structure to the drive mechanism. The at least one coupling member is provided with at least one picking-up element that acts in transverse direction to the direction of movement of the coupling member and that entrains, releases or picks up the guide element with limited entraining force during movement of the coupling member. The protective device is usable for cargo area coverings, cargo area dividers and sun-protection roller blinds.

This application claims the priority of German patent document 199 44 948.1, filed Sep. 20, 1999, the disclosure of which is expressly incorporated by reference herein.
The present invention relates to a protective device for the interior of a motor vehicle having a protective structure, which can be spread out in a protective position to an at least approximately planar shape and which is seated for being transferred by a drive mechanism between at least two positions, the protective structure being connected with at least one guide element that can be entrained with transfer means of the drive mechanism by at least one coupling member.
A protective device according to the invention may be designed either as a horizontally movable cargo area covering, or as a separating device with a vertically extensible divider net, or as a roller blind for use as a sun shield for at least one window of a motor vehicle.
A protective device in the form of a cargo area covering has been known from German Patent Document DE 198 25 353 A1. The known cargo area covering comprises a horizontally extensible roller blind that can be moved, by electric drive means, between a home position in which the cargo area is exposed and a protective position in which the cargo area is covered. The covering roller blind comprises at its front endxe2x80x94viewed in the pull-out directionxe2x80x94a pull-out bar whose opposite ends project laterally beyond the roller blind that serves as the protective structure. These ends form guide elements that are respectively retained in a U-shaped upwardly open coupling member. Each coupling member is fixed to a toothed belt, serving as a transfer element, that extends in the pull-out direction, i.e. in horizontal alignment. Each toothed belt can be operated by means of an electric drive motor. The two drive motors can be controlled in a mutually co-ordinated way so that the pull-out bar and, thus, the covering roller blind can be pulled out or retracted in parallel. The ends of the pull-out bar that serve as guide elements can be removed from the coupling member in upward direction. Similarly, the pull-out bar can be reinserted between the coupling members from the top, whereby the covering roller blind can be connected again with the drive means.
If the pull-out bar were to hit against an obstruction when being pulled out or being retracted by the drive means, then the drive means and/or the pull-out bar may be damaged. In order to prevent any such occurrence there would be the possibilityxe2x80x94not disclosed in German Patent Document DE 198 25 353 A1xe2x80x94to monitor the load of the drive motors and to cause the direction of the drive to be reversed if an increase in load should be detected. Such devices are generally known in connection with the automatic opera-ion of vehicle window panes.
Now, it is an object of the present invention to provide a protective device of the kind described above that guarantees, by simple means, perfect and safe movement of the protective structure even in the case of trouble.
This object is achieved by the fact that at least one coupling member is provided with at least one picking-up element that has a limited retaining force for the force-dependent picking-up, entraining and release of the guide element during movement of the coupling member. Depending on whether the counter-force, that acts on the protective structure and the at least one guide element, is greater or smaller than the limited entraining force of the at least one picking-up element, the guide element is picked up from a stationary position, released from a position in which it has been entrained by the coupling member orxe2x80x94in the case of forces smaller than the retaining forcexe2x80x94entrained by the coupling member for common movement.
The solution according to the invention is suited for both, protective structures with only a single guide element and for protective structures having two or more guide elements. Depending on the particular configuration, a single coupling member or a plurality of coupling members may be provided. The drive means may have a single drive unit or a plurality of drive units. The drive unit comprises preferably a single central electric drive that imparts, by suitable synchronisation, a parallel guiding effect to the protective structure via two guide elements arranged on opposite sides. The solution according to the invention guarantees that the respective protective structure, be it a divider net, a covering roller blind of a cargo area covering, or a sun-protection roller blind, can be automatically transferred by the drive means into the desired position. Since when a load higher than that of the drive means occurs the at least one guide element and, thus, the protective structure will be uncoupled from the drive means, no overloading of the drive means can occur.
Due to the force-dependent coupling or uncoupling the at least one guide element will be released from the coupling member automatically and forcedly in the event the protective structure should hit upon an obstruction, while the coupling member will be moved on by the drive means. When the coupling member overruns the position of the guide element the next timexe2x80x94preferably in the opposite directionxe2x80x94the guide element will be automatically picked up again and carried off with the movement of the coupling member.
Uncoupling can be achieved in a simple way by the fact that the protective structure is moved manually in the direction of movement or in a direction opposite to the direction of movement of the drive means, whereby the protective structure is uncoupled. Thus, the coupling member has only a limited coupling force in the respective direction of movement of the at least one coupling member, through its at least one picking-up element. When this coupling force (entraining force) is exceeded, the protective structure is released from the at least one coupling member. Similarly, the guide element and, thus, the protective structure is connected again with the at least one coupling member as soon as the coupling member reaches once more the position of the guide element in the course of the corresponding reverse movement. It is, therefore, important that the guide element be always guided in the path of movement of the coupling member. The guide element remains in this path of movement even after it has been uncoupled, so that when the coupling member and the guide element meet the next time they are coupled once more. Thus, by overloading the coupling beyond the limited entraining force, i.e. coupling force, the at least one guide element and, thus, the protective structure will be detached form the drive means. Consequently, in case of a current failure, this also allows easy operation by hand without there being any needxe2x80x94as is the case with systems of the prior artxe2x80x94for manually re-engaging the at least one guide element in the coupling member later. Picking up of the at least one guide element and, thus, of the protective structure by the at least one coupling member is always effected automatically and, thus, forcedly in the solution according to the invention. The invention thus provides considerably improved operating comfort as compared to the prior art.
Overloading by obstructions found in the path of the protective structure is avoided. The at least one coupling member may be seated in horizontal or in vertical vehicle-mounted guides or in similar guides that are inclined in space. The guides may be parallel or non-parallel one relative to the other. In the case of non-parallel guides, length-compensation means are provided for the guide elements and the protective structure between the guides. The at least one coupling member is in any case forcedly guided in the same way as the at least one guide element of the protective structure in order to be able, as a result of the identical path of movement, to pick up the respective guide element every time it meets it.
In order to achieve a limited entraining force for the at least one picking-up element, the picking-up element may me movable in mechanically spring-loaded fashion. It is however also contemplated according to certain embodiments to provide the picking-up element and the guide element of the protective structure with corresponding magnetic elements. Embodiments with other force-locking or shape-locking connections with corresponding force limitation are also contemplated by the invention.
According to certain embodiments of the invention each coupling member is seated for linear movement in a vehicle-mounted guide section to which the corresponding guide element is also associated. This guarantees that the coupling member will S find the guide section again, after it has been transitorily separated from the coupling member, as soon as it passes once more the position of the guide element.
According to a further development of certain referred embodiments of the invention, the at least one picking-up element of the coupling member is mechanically active and seated to move transversely to the direction of movement of the coupling member, against the force of a return spring, between a holding position and releasing position. Consequently, the at least one picking-up element forms a force-dependent locking element of simple and safe structure, due to the mechanical function.
According to a further development of certain preferred embodiments of the invention, two coupling members, each entraining, releasing or picking up a guide element of the protective structure, are arranged on opposite sides for synchronous linear movement. Those embodiments are particularly well suited for use of the protective device as cargo area covering, where the opposite ends of a pull-out section, which serves as guide element, are each laterally held at limited force in corresponding coupling members that are guided for linear movement.
According to a further development of certain preferred embodiments of the invention, each coupling member has two picking-up elements which are adjusted to opposite directions of movement of the coupling member. The two picking-up elements preferably accommodate the respective guide element between them.
According to a further development of certain preferred embodiments of the invention, the one picking-up element is stronger, with respect to its entraining force, than the other picking-up element. This is of advantage when a tensile or pressure force is exerted upon the protective structure in the direction of movement, independent of the drive means. This is the case, in particular, with cargo area coverings in which the covering roller blind is held on a roller blind shaft that is loaded by a return spring. If the covering is then pulled out by hand, this guarantees that the covering roller blind will return to its home position immediately after unlocking. The described configuration is provided in order to prevent the respective tensile force or pressure force from being added to the drive force of the drive means and from thereby causing the at least one guide element to get detached from the picking-up element.
According to a further development of certain preferred embodiments of the invention, at least one stationary stop, serving to secure the protective structure in different positions, is associated to the at least one guide element, which stop can be transferred, by means of the at least one coupling member, into a releasing position in which it permits the protective structure to move. Consequently, such stationary movable stops are also found in the path of movement of the at least one coupling member so that when the stops are overrun by the at least one coupling member they will be forcedly transferred into the releasing position. This guarantees that the protective structure will be retained in the respective position by the stop so long as it is not picked up by the coupling member.
According to a further development of certain preferred embodiments of the invention, the stops are configured as spring-loaded, elastically resilient blocking elements provided with ramps for the respective coupling member. One thereby achieves simple releasing of the stops as soon as the coupling member passes the corresponding position of the respective stop. Preferably, corresponding stops are provided at least for the two end positions of the protective structure, i.e. a home position and a fully pulled-out protective position. Basically, however, it is also possible to provide only a single stop for the pulled-out protective position if the protective structure is held in the home position by a corresponding return spring.

Protective device for the interior of a motor vehicle


The back portion of an omega-back earring is formed by investment casting and then heat-treated to have spring gold characteristics. A rear surface of the ornamental front portion of the earring includes a depression to present a concave profile which is complementary to the convex profile of the pushing part of the rear portion of the earring. In a non-identical mirror-image pair of earrings, a design element such as a small precious stone is provided on only one of the earring pair, at an inconspicuous spot, to aid the wearer in distinguishing the right earring from the left earring.

This invention relates generally to jewelry and more particularly to earrings.
Omega-back earrings are well known. Somewhat typical examples of omega-back earrings are illustrated in U.S. Pat. Nos. 4,907,424 and 5,165,258.
Earrings of this type include a decorative portion which is worn on the outside or front surface of the earlobe. A pin or post projects inwardly from the decorative portion of the earring and is intended to be inserted through a hole in the earlobe. A rear portion of the earring is attached to the decorative portion by a hinge at the bottom of the decorative portion. The upper end of the rear portion of the earring is in the form of a loop. When the earring is in a closed condition attached to the wearer""s ear, the loop of the rear portion of the earring presses against the back of the wearer""s earlobe and the post from the front of the earring extends through the loop.
In general, omega-back earrings represent a desirable combination of secure attachment to the wearer""s ear and relative comfort. But comfort in an earring is almost always a relative matter, and it would be highly desirable to improve even omega-back earrings from the point of view of the wearer""s comfort. It would also be desirable to reduce the cost of manufacture of omega-back earrings.
Earrings are generally sold in pairs. In many cases, the two earrings making up the pair are identical and may be interchangeably worn on either ear. However, other earring designs call for a pair of earrings in which the two earrings are not identical, but rather are mirror-images of each other, with one piece intended for wearing only on the right ear, and the other intended for wearing only on the left ear. One disadvantage of such mirror-image earring pairs, not heretofore remarked in the prior art, is that the wearer often finds, upon putting on the earrings, that she has mistakenly placed the left earring on her right ear or vice versa. It would be desirable to prevent this sort of inconvenience. It is to be recognized that this problem may be encountered in omega-back earrings and other types of earrings as well.
It is an object of the invention to provide an improved omega-back earring.
It is a further object to provide an omega-back earring that is more comfortable to wear than prior art designs.
It is another object of invention to provide a method of making an omega-back earring at lower cost and with greater convenience than conventional methods.
It is still a further object of the invention to provide a pair of non-identical mirror-image earrings in which the right earring can be easily distinguished from the left earring.
A first aspect of the invention provides an improvement in an pair of earrings, where one of the earrings is intended for wearing on a user""s left ear, the other of the earrings is intended for wearing on the user""s right ear, the earrings have respective ornamental surfaces for facing in a direction oriented outwardly from the ear on which the respective earring is worn, the respective ornamental surfaces are non-identical mirror-images of each other, and the improvement includes providing on one of the earrings a design feature not present on the other of the earrings, with the design feature being for distinguishing the first one of the earrings from the other one of the earrings to indicate to the user on which ear the first one of the earrings is to be worn. The design feature may be a precious or semi-precious stone located on a rear surface of the first one of the earrings, the rear surface being oriented in the direction opposite to the respective ornamental surface of the first one of the earrings. For example, the design feature may be a small ruby mounted on the rear of the front portion of the right earring.
A second aspect of the invention provides an improvement in an omega-back earring having a front portion for adorning an outward surface of a wearer""s ear and a back portion mounted by a hinge to the front portion, the front portion having a first surface for facing in a direction oriented outwardly from the wearer""s ear and a second surface for contacting the wearer""s earlobe, the front portion also having a post extending from the second surface, the post being arranged to be inserted through a hole pierced in the wearer""s earlobe, the back portion including a loop for defining an aperture through which the post is inserted when the earring is attached to the wearer""s ear in a closed condition, the loop defining a convex configuration relative to the wearer""s earlobe when the earring is attached to the wearer""s ear in a closed condition. The improvement in accordance with this aspect of the invention provides that the second surface of the front portion has a bowl-like region from which the post extends, the bowl-like region being arranged to define a concave configuration relative to the wearer""s earlobe, the concave configuration being complimentary to the convex configuration defined by the loop by the back portion, the loop of the back portion and the bowl-like region of the front portion being for engaging therebetween the wearer""s earlobe when the earring is attached to the wearer""s ear in the closed condition. The bowl-like region on the rear (second) surface of the front portion of the earring may also be employed with a rear portion loop that does not define a convex configuration.
According to a third aspect of the invention, an omega-back earring includes a front member for adorning an outward surface of a wearer""s ear, the front member having a front surface for facing in a direction oriented outwardly from the wearer""s ear, and a rear surface for contacting the wearer""s earlobe, the front member including a post extending from the rear surface for being inserted through a hole pierced in the wearer""s earlobe, the front member having a hinge portion at a lower end of the front member, the earring also including a rear member for engaging a rear surface of the wearer""s earlobe, the rear member including a loop at a upper end of the rear member, the loop being arranged to define an aperture through which the post is inserted when the earring is attached to the wearer""s ear in a closed condition, the rear member having a hinge portion at a lower end of the member, the respective hinge portions of the front and rear members cooperating to form a hinge by which the rear member is pivotable between the closed condition and open condition, the rear member being formed by investment casting as a single, unitary body, and being composed entirely of spring gold.
According to a fourth aspect of the invention, there is provided a method of manufacturing a hinged earring, the method including the steps of providing a front portion of the earring, forming a rear portion of the earring by investment casting from a material that includes gold, processing the rear portion of the earring to harden the rear portion so that the rear portion has characteristics of spring gold, and assembling the front portion and the processed rear portion to form the hinged earring. The processing of the rear portion of the earring preferably includes heat-treating the rear portion at a first temperature and then water quenching the rear portion, followed by heat-treating the rear portion again at a lower temperature, and then air cooling.
An earring provided in accordance with the foregoing aspects of the invention provides the following advantages:
The provision of a distinctive design element on one, but not the other, of a mirror-image pair of earrings enables the wearer to quickly and easily distinguish between the right earring and the left earring before putting on the earrings, thereby preventing the possible inconvenience of initially placing the earrings on the wrong ear. In addition, this feature, by guiding the wearer to a correct placement of the earrings, helps to assure that precious stones or other design elements, intended to be prominently displayed, actually receive the intended prominence.
In addition, the concave region provided on the rear surface of the front of the earring substantially enhances the wearer""s comfort by more appropriately distributing forces applied by the earring to the wearer""s earlobe.
Furthermore, the above-mentioned technique for forming a one-piece rear portion of an omega-back earring of spring gold reduces the cost of manufacture and assembly of omega-back earrings.
The foregoing and other objects, features and advantages of the invention will be further understood from the following detailed description of the preferred embodiments thereof and from the drawings, wherein like reference numerals identify like components and parts throughout.

Design feature for distinguishing one earring of a set from the other