Abstract: The present disclosure provides a method for isolation and purification of sodium sulfide (Na2S) formed during desulfurization of petroleum residue. The process involves treating a sludge containing Na2S obtained during desulfurization of petroleum residue with a mixture of at least one organic solvent and water.

Abstract: The present invention provides an adsorbent for removing sulfur from cracking gasoline or diesel fuel. The adsorbent has excellent abrasion-resistance and desulfurization activity. The adsorbent comprises from about 5 to about 35 wt % of alumina, from about 3 to about 30 wt % of silica, from about 10 to about 80 wt % of at least one oxide of metal selected from Groups IIB and VB, from about 3 to about 30 wt % of at least one metal accelerant selected from Groups VIIB and VIII, and from about 0.5 to about 10 wt % of at least one oxide of metal selected from Groups IA and IIA, based on the total weight of the adsorbent.

Abstract: A reaction system and method for removing heteroatoms from oxidized-heteroatom-containing hydrocarbon streams and products derived therefrom are disclosed. An oxidized-heteroatom-containing hydrocarbon feed is reacted in a reaction system thereby forming non-ionic hydrocarbon products. The products derived therefrom are useful as transportation fuels, lubricants, refinery intermediates, or refinery feeds.

Abstract: Hydrogen sulfide evolution from asphalt or heavy fuel oil may be reduced or eliminated using an additive to act as a scavenger. Zinc, in conjunction with an additional metal selected from Fe, Mn, Co, Ni, Cr, Zr, when present in the form of nano-particles of an oxide, borate or carboxylate is an effective component is preventing or mitigating the evolution of hydrogen sulfide. The nano-particles may be used neat or as a dispersion. These metals may also be complexed and used in the form of a solution. Molybdenum, when used with one or both of Fe and Zn is also a useful in any of these forms for the same purpose.

Abstract: The invention provides an adsorbent for removing sulfur from cracking gasoline or diesel fuel, which adsorbent comprises: (1) a carrier consisting of a source of silica, an inorganic oxide binder, and at least one oxide of metal selected from Groups IIB, VB and VIB; (2) at least one accelerant metal which is capable of reducing the sulfur in oxidized state to hydrogen sulfide and has a ?<0.5, wherein ?=(the amount in percentage of accelerant metal in crystal phase)/(the amount in percentage of accelerant metal in the adsorbent). The active components in the adsorbent can be evenly dispersed on the carrier in a matter close to monolayer dispersion, and which greatly improves the activity of the adsorbent. The preparation method and the use of the above adsorbent are provided.

Abstract: An adsorbent for desulfurizing cracking gasoline or diesel fuel comprising 1) pillared clay, (2) inorganic oxide binder, (3) an oxide of one or more metals selected from Groups IIB, VB and VIB, and (4) at least one metal accelerant selected from cobalt, nickel, iron and manganese. The adsorbent exhibits excellent abrasion-resistant strength and desulfurization performance.

Abstract: Methods and systems for contacting a crude feed that has a total acid number (TAN) of at least 0.3 with one or more catalysts produces a total product that includes a crude product are described. The one or more catalysts may include a first catalyst and a second catalyst. The crude product is a liquid mixture at 25° C. and 0.101 MPa and the crude product has a TAN of at most 90% of the TAN of the crude feed. One or more other properties of the crude product may be changed by at least 10% relative to the respective properties of the crude feed.

Abstract: A method and apparatus for upgrading a hydrocarbon feedstock is provided. The method includes the steps of (a) supplying a hydrocarbon feedstock to an oxidation reactor, wherein the hydrocarbon feedstock is oxidized in the presence of a catalyst under conditions sufficient to selectively oxidize sulfur compounds present in the hydrocarbon feedstock; (c) separating the hydrocarbons and the oxidized sulfur compounds by solvent extraction; (d) collecting a residue stream that includes the oxidized sulfur compounds; and (e) supplying the residue stream to a gasifier to produce a syngas stream and a hydrogen sulfide stream.

Abstract: The desulfurization of fossil fuels is provided by the combination of fossil fuels with an aqueous mixture of ozone or hydrogen peroxide and a Tetraoctylphosphonium salt phase transfer catalyst, and the mixture is then subjected to reactive mixing to form oxidize sulfur compounds in the fuel. The polar oxidized sulfones species are removed via another mixing step. The desulfurization device can be in the form of a portable device which provides for continuous mixing-assisted desulfurization for the removal of sulfur containing compounds from fossil fuels such as diesel fuel.

Abstract: The desulfurization catalyst for catalytic cracked gasoline according to the present invention has high performance in removal of sulfur compounds in gasoline fractions. This catalyst contains particulate vanadium oxide having the average particle diameter in the range from 0.1 to 10 ?m at the content in the range from 0.3 to 3 weight % calculated as that of V2O5. The porous spherical particles of inorganic oxide are made of crystalline aluminosilicate zeolite and a porous inorganic oxide matrix, and furthermore contain antimony.

Abstract: A method of desulfurizing/refining a hydrocarbon oil by which sulfur compounds are diminished to an extremely low concentration at a relatively low equipment cost and operating cost. The method of desulfurizing/refining a hydrocarbon oil comprises bringing a hydrocarbon oil containing at least one sulfur compound selected from the group consisting of thiophene compounds, benzothiophene compounds, and dibenzothiophene compounds and optionally further containing aromatic hydrocarbons into contact with a solid acid catalyst and/or an activated carbon having a transition metal oxide supported thereon to thereby desulfurize the oil. The solid acid catalyst preferably is a solid ultrastrong-acid catalyst selected among sulfuric acid radical/zirconia, sulfuric acid radical/alumina, sulfuric acid radical/tin oxide, sulfuric acid radical/iron oxide, tungstic acid/zirconia, and tungstic acid/tin oxide.

Abstract: Provided are processes for removing sulfur-containing compounds from fuel, comprising contacting the fuel in liquid phase with air to oxidize the sulfur-containing compounds, the contacting being carried out in the presence of at least one transition metal oxide catalyst, wherein the catalyst is supported on a porous support and wherein the porous support comprises a support material selected from the group consisting of a titanium oxide, a manganese oxide and a nanostructured material of the aforementioned support materials.

Abstract: The present invention relates to the novel catalytic composition having a high specific activity in reactions involving hydroprocessing of light and intermediate petroleum fractions, and preferably in hydrodesulphurization and hydrodenitrogenation reactions. The inventive catalyst contains at least one element of a non-noble metal from group VIII, at least one element from group VIB and, optionally, a group one element of the VA group, which are deposited on a novel catalytic support comprising of an inorganic metal oxide from group IVB, consisting of an (1D) one-dimensional nanostructured material having nanofibers and/or nanotube morphology with high specific surface area of between 10 and 500 m2/g.

Abstract: A simple, compact process for cleansing hydrocarbon fuel such as jet fuel is disclosed. This process involves subjecting the fuel to an oxidative desulfurization process in a desulfurization reactor followed by passing the fuel through an adsorption bed. The cleansed desulfurized fuel may then be utilized directly in generation of hydrogen for fuel cell applications.

Abstract: A method of reforming a sulfur containing hydrocarbon involves contacting the sulfur containing hydrocarbon with a sulfur tolerant catalyst containing a sulfur tolerant precious metal and a non-sulfating carrier so that the sulfur tolerant catalyst adsorbs at least a portion of sulfur in the sulfur containing hydrocarbon and a low sulfur reformate is collected, and contacting the sulfur tolerant catalyst with an oxygen containing gas to convert at least a portion of adsorbed sulfur to a sulfur oxide that is desorbed from the sulfur tolerant catalyst.

Abstract: A method of reforming a sulfur containing hydrocarbon involves contacting the sulfur containing hydrocarbon with a sulfur tolerant catalyst containing a non-sulfating carrier and one or more of a sulfur tolerant precious metal and a non-precious metal compound so that the sulfur tolerant catalyst adsorbs at least a portion of sulfur in the sulfur containing hydrocarbon and a low sulfur reformate is collected, and contacting the sulfur tolerant catalyst with an oxygen containing gas to convert at least a portion of adsorbed sulfur to a sulfur oxide that is desorbed from the sulfur tolerant catalyst.

Abstract: Catalysts amenable to oxidizing sulfur compounds and systems and methods of using these catalysts to effect the removal of sulfur from crude oil and crude oil distillates are disclosed. The catalyst is disposed with a titanyl moiety which serves to selectively coordinate sulfur compounds and affect their oxidation. The titanyl may be bound within a polymer or on the surface of a polymer or on the surface or in the pores of an inorganic support. The resulting oxidized sulfur compounds are readily separated from the initial crude oil or crude oil distillate streams by traditional separation techniques arrayed as described in the systems and methods disclosed.

Abstract: Heat from solar or nuclear heat sources is applied to provide at least a portion of the heat used in a cyclic petroleum refining process in which a hydrocarbon feedstream is contacted with a solid particulate contact material in a first step to treat the feedstream after which the solid contact material is separated or disengaged from the treated feedstream and regenerated in a separate regeneration zone before being returned to the first step for contact with additional feedstream. The entire cycle may be characterized as including an endothermic step, generally a reduction, and an exothermic step, generally an oxidation, with heat from the exothermic step being transferred from the exothermic step to the endothermic step by means of the circulating contact material. The application of the nuclear or solar heat may be applied to whichever step of the process requires heat from external sources.

Abstract: A composition and process for removing sulfur from middle distillate petroleum hydrocarbon fuels. The composition includes an alumina component and a carbon component. The composition is present in an amount effective to adsorb sulfur compounds from the fuel. The alumina component and the carbon component preferably collectively comprise a composite material. The composition can further include a sulfur component, preferably a metal sulfide or sulfur oxide. The composition can also further include at least one compound having a Group VI or Group VIII metal from the periodic table.

Abstract: The present invention relates to improving heavy crude oil, and extra through a scheme considering the use of ionic liquids catalysts based on Mo and Fe catalyst is highly miscible with crude oil and are in the homogeneous phase crude oil. Furthermore, this invention relates to improving heavy crude in two stages, the first ionic liquid catalyst, and the second supported catalyst. The API gravity crude is increased from 12.5 to 19 points in the first stage and viscosities up to 5600-1600 decreased from 60-40 cSt certain to 37.8 ° C. While in the second stage, you get an upgraded crude oil with 32.9 ° API, viscosity of 4.0 cSt, reduction in total sulphur content of 0.85 wt % nitrogen and 0295 ppm by weight, respectively. As a considerable reduction of asphaltenes from 28.65 to 3.7% weight.

Abstract: A process is provided for producing low sulfur diesel by hydrotreatment of suitable feed in the presence of a bulk metal catalyst. The feed is exposed under effective hydrotreating conditions to a catalyst including at least one Group VI metal, at least one Group VIII metal, and Niobium. Treatment of the feed results in production of a liquid diesel product, which is separated from a gas phase product that is also produced during the hydrotreatment.

Abstract: Methods and systems for contacting of a crude feed with one or more catalysts produces a total product that includes a crude product are described. At least one of the catalysts is an uncalcined catalyst. The crude product is a liquid mixture at 25° C. and 0.101 MPa. The crude product has a nitrogen content of at most 90% of the nitrogen content of the crude feed. One or more other properties of the crude product may be changed by at least 10% relative to the respective properties of the crude feed.

Abstract: A process for removing sulfur-containing compounds from fuel, said process comprising contacting the fuel in liquid phase with air to oxidize the sulfur-containing compounds, said contacting being carried out in the presence of at least one transition metal oxide catalyst, wherein the catalyst is supported on a porous support and wherein the porous support comprises a support material selected from the group consisting of a titanium oxide, a manganese oxide and a nanostructured material of the aforementioned support materials.

Abstract: Oil soluble catalysts are used in a process to hydrodesulfurize petroleum feedstock having a high concentration of sulfur-containing compounds and convert the feedstock to a higher value product. The catalyst complex includes at least one attractor species and at least one catalytic metal that are bonded to a plurality of organic ligands that make the catalyst complex oil-soluble. The attractor species selectively attracts the catalyst to sulfur sites in sulfur-containing compounds in the feedstock where the catalytic metal can catalyze the removal of sulfur. Because the attractor species selectively attracts the catalysts to sulfur sites, non-productive, hydrogen consuming side reactions are reduced and greater rates of hydrodesulfurization are achieved while consuming less hydrogen per unit sulfur removed.

Abstract: Systems and method for contacting a crude feed that has a total acid number of at least 0.1 with one or more catalysts produces a total product that includes a crude product are described. At least one of the catalysts includes vanadium. The crude product is a liquid mixture at 25° C. and 0.101 MPa, and the crude product has a TAN of at most 90% of the TAN of the crude feed. One or more other properties of the crude product may be changed by at least 10% relative to the respective properties of the crude feed.

Abstract: An adsorbent for desulfurizing cracking gasoline or diesel fuel comprising 1) pillared clay, (2) inorganic oxide binder, (3) an oxide of one or more metals selected from Groups IIB, VB and VIB, and (4) at least one metal accelerant selected from cobalt, nickel, iron and manganese. The adsorbent exhibits excellent abrasion-resistant strength and desulfurization performance.

Abstract: A hydrocarbon desulfurization system that circulates fluidizable solid particles through a fluidized bed reactor, a fluidized bed regenerator, and a fluidized bed reducer to thereby provide for substantially continuous desulfurization of a hydrocarbon-containing fluid stream and substantially continuous regeneration of the solid particles. A novel transport system is employed for transporting the solid particles between the reactor, the regenerator, and the reducer. The transport system uses close-coupled vessels and gravity flow between various vessels to minimize equipment cost and particle attrition.

Abstract: The present invention pertains to a sulfur-containing catalyst composition suitable for the hydrotreating of hydro-carbon feeds which comprises a Group VIB metal component selected from molybdenum, tungsten, and mixtures thereof, a Group V metal component selected from vanadium, niobium, tantalum, and mixtures thereof, and a Group VIII metal component selected from nickel, cobalt, iron, and mixtures thereof, the metal components (calculated as oxides) making up at least 50 wt. % of the catalyst, wherein the molar ratio between the metal components satisfies the following formula: (Group VIB+Group V):(Group VIII)=0.5-2:1. This catalyst has been found to show a high activity in sulfur removal in combination with good aromatics removal properties.

Abstract: The present invention relates to a process of reducing sulfur- or nitrogen-containing compounds and also producing oxygenates, which can be used as an excellent octane booster in the reformulated gasoline and as a cetane booster for the future oxygenated diesel in a one-pot reaction.

Abstract: The present invention relates to a compressed metal oxide composition particle comprised of metal oxide and an organic binder, with the binder preferably being a water insoluble cellulose composition. The present invention also relates to a method for forming a compressed metal oxide composition particle, with the preferred method including compressing a metal oxide and binder mixture to form compressed metal oxide composition particles having a final particle size of between about 0.1 mm and about 200 mm.

Abstract: A process to reduce the acidity of acidic crude oils for preventing corrosion during processing of the crude oils, including transferring through pipe lines, tanker ships and tank vehicles. Crude oil having substantial amount of organic acid, in particular, naphthenic acid compounds is contacted with supercritical water and a catalyst for deacidification. A treated crude oil product has lower amounts of organic acid compounds than the original crude oil.

Abstract: A continuous process for upgrading sour crude oil by treating the sour crude oil in a two step process that includes a hydro-demetallization section and a hydro-desulfurization section, both of which are constructed in a permutable fashion so as to optimize the operating conditions and catalyst lifespan to produce a high value crude oil having low sulfur and low organometallic impurities.

Abstract: Compositions and processes are disclosed for removing sulfur and sulfur compounds from hydrocarbon fuel feedstocks. The feedstock is contacted with a regenerable sorbent such as a compound of the formula TixCeyO2 where 0<x/y?1 and where 0<x?1 and 0<y?1 capable of selectively adsorbing sulfur compounds present in the hydrocarbon feedstock at about 0° C. to about 100° C. such as at about 25° C.

Abstract: A method and apparatus for removing sulfur from a hydrocarbon-containing fluid stream wherein desulfurization is enhanced by improving the contacting of the hydrocarbon-containing fluid stream and sulfur-sorbing solid particulates in a fluidized bed reactor.

Abstract: Processes and systems associated with hydrodynamic cavitation-catalyzed oxidation of sulfur-containing substances in a fluid are described. In one example method, carbonaceous fluid is combined with at least one oxidant to form a mixture and then the mixture is flowed through at least one local constriction in a flow-through chamber at a sufficient pressure and flow rate to create hydrodynamic cavitation in the flowing mixture having a power density of between about 3,600 kWatts/cm2 and about 56,000 kWatts/cm2 measured at the surface of the local constriction normal to the direction of fluid flow. The creation of hydrodynamic cavitation in the flowing mixture initiates one or more chemical reactions that, at least in part, oxidize at least some of the sulfur-containing substances in the carbonaceous fluid.

Abstract: A desulfurization system is operated in a manner which optimizes sulfur removal and octane retention. When the desulfurization reactor is operated at a specific ratio of total pressure to hydrogen partial pressure (PT/PH) and/or within a specific temperature range, optimum sulfur removal and octane retention are realized. The desulfurization reactor can be maintained at these optimized operating conditions by automatically adjusting one or more operating parameters of the desulfurization reactor in order to maintain a substantially constant hydrogen partial pressure (PH) in the reactor. Maintaining a relatively constant hydrogen partial pressure (PH) in the desulfurization reactor helps ensure a relatively consistent degree of desulfurization.

Abstract: Disclosed is a process which reduces the sulfur and/or nitrogen content of a distillate feedstock to produce a refinery transportation fuel or blending components for refinery transportation fuel, by contacting the feedstock with an oxygen-containing gas in an 5 oxidation/adsorption zone at oxidation conditions in the presence of an oxidation catalyst comprising a titanium-containing composition whereby the sulfur species are converted to sulfones and/or sulfoxides which are adsorbed onto the titanium-containing composition.

Abstract: A catalyst for hydrotreating a hydrocarbon feed has been developed. The catalyst comprises a metal phosphide and promoter metal component as the catalytic component. At least a portion of the metal promoter component is deposited on the metal phosphide. The metal phosphide/promoter metal component combination is dispersed on a refractive inorganic oxide support. An example of this catalyst is where the metal phosphide is nickel phosphide, the promoter metal is molybdenum and the support is alumina. Methods of preparing the catalyst and hydrotreating processes using the catalyst are also described.

Abstract: Propane and/or butanes are separated from a hydrocarbon feedstock contaminated with alkyl mercaptans by fractional distillation at such a pressure that the separated overheads stream containing said propane and/or butanes is at a temperature in the range 50 to 100° C. Sufficient oxygen is introduced into the hydrocarbon feedstock to oxidise the mercaptans therein and the resultant mixture is subjected to the fractional distillation in a column including at least one bed of a catalyst capable, under the prevailing conditions, of oxidising the mercaptans to higher boiling point sulphur compounds. These higher boiling point sulphur compounds are separated as part of the liquid phase from the distillation.

Abstract: An adsorbent composition comprising a nanostructured titanium oxide material of the formula TiO2-, where 0?×?1 with nanotubular and/or nanofibrilar morphology, high oxygen deficiency, having an orthorhombic JT crystalline phase described by at least one of the space groups 59 Pmmn, 63 Amma, 71Immm or 63 Bmmb, and comprising between 0 and 20 weight percent of a transition metal oxide is used for the selective adsorption of nitrogen compounds and/or sulfur compounds from light and intermediate petroleum fractions.

Abstract: A method for desulfurizing a hydrocarbon stream (10) containing heterocyclic sulfur compounds, which process comprises contacting the heterocyclic sulfur compounds in the gas phase (60) in the presence of oxygen (70) with a supported metal oxide catalyst, or with a bulk metal oxide catalyst (600) to convert at least a portion of the heterocyclic sulfur compounds to oxygenated products as well as sulfur-deficient hydrocarbons and separately recovering the oxygenated products separately from a hydrocarbon stream with substantially reduced sulfur.

Abstract: The present invention relates to a novel process for refining the liquefied petroleum gas (LPG) in a commercial scale. The process comprises: sequentially performing fine desulfurization and mercaptan conversion of the LPG after alcohol amine treatment through desulfurizer and catalyst set in fixed bed reactor in the absence of alkali, wherein, during the fine desulfurization, the resultants of reaction between hydrogen sulfide in the LPG and Fe—Ca oxides or their hydrates adhered on the desulfurizer, and during the mercaptan conversion, the mercaptan in the LPG reacts with the residual trace amount of air in the LPG under the action of the catalyst to produce the disulfides; letting the formed disulfides along with the LPG flow out of the fixed bed reactor; rectifying the LPG after the mercaptan conversion to obtain the refined LPG products, with further rectification to obtain the valuable disulfide products.

Abstract: A process for the autocatalytic production of organic hydroperoxides and ultra low sulfur diesel boiling range hydrocarbons is disclosed. The organic hydroperoxides react with sulfur compounds to produce sulfones, and the sulfones can be removed from the diesel boiling range hydrocarbons to provide ultra low sulfur diesel.

Abstract: The present invention is directed to the removal of nitrogen and sulfur containing impurities from high molecular weight petroleum feedstock obtained from fluid cracking catalyst or distillation zone of a petroleum treatment plant. The present process comprises first treating C12 and higher hydrocarbon petroleum feedstock having nitrogen and sulfur containing compounds therein with a porous, particulate adsorbent comprising a silica matrix having an effective amount of metal atoms therein to cause the adsorbent to have Lewis acidity of at least 500 ?mol/g and then treating the resultant feedstock to catalytic hydrodesulfurization to produce a hydrocarbon fuel having low sulfur and nitrogen content.

Abstract: A composition comprising a metal oxide and a promoter, wherein at least a portion of the promoter is present as a reduced valence promoter, and methods of preparing such composition are disclosed. The thus-obtained composition is employed in a desulfurization zone to remove sulfur from a hydrocarbon stream.

Abstract: The present invention is directed to the removal of nitrogen and sulfur containing impurities from high molecular weight petroleum feedstock obtained from fluid cracking catalyst or distillation zone of a petroleum treatment plant. The present process comprises first treating C12 and higher hydrocarbon petroleum feedstock having nitrogen and sulfur containing compounds therein with a porous, particulate adsorbent comprising a silica matrix having an effective amount of metal atoms therein to cause the adsorbent to have Lewis acidity of at least 500 ?mol/g and then treating the resultant feedstock to catalytic hydrodesulfurization to produce a hydrocarbon fuel having low sulfur and nitrogen content.

Abstract: The sulfur content of liquid cracking products, especially the cracked gasoline, of the catalytic cracking process is reduced by the use of a sulfur reduction catalyst composition comprising a porous molecular sieve which contains a metal in an oxidation state above zero within the interior of the pore structure of the sieve as well as a cerium component which enhances the stability and sulfur reduction activity of the catalyst. The molecular sieve is normally a faujasite such as USY. The primary sulfur reduction component is normally a metal of Period 3 of the Periodic Table, preferably vanadium. The sulfur reduction catalyst may be used in the form of a separate particle additive or as a component of an integrated cracking/sulfur reduction catalyst.

Abstract: The invention relates to: a process for the desulphurization of feed streams comprising: supplying a hot process stream to a lead catalyst bed (8) comprising a first sulphur-removing catalyst and a second sulphur-removing catalyst under conditions whereby sulphur is removed from the process stream by the first sulphur-removing catalyst and said second sulphur-removing catalyst does not effectively remove sulphur from the stream at the operating temperature of the lead catalyst bed for the duration of the bed's life; collecting a hot partially sulphur-depleted stream from the lead catalyst bed and cooling said stream; passing said cooled stream through a lag catalyst bed (11) comprising the first sulphur-removing catalyst and the second sulphur-removing catalyst under conditions whereby sulphur is removed from the process stream by the second sulphur-removing catalyst and said first sulphur-removing catalyst removes sulphur less efficiently from the stream at the operating temperature of the lag catalyst bed;

Abstract: The sulfur content of liquid cracking products, especially the cracked gasoline, of the catalytic cracking process is reduced by the use of a sulfur reduction additive comprising a porous molecular sieve which contains a metal in an oxidation state above zero within the interior of the pore structure of the sieve. The molecular sieve is normally a large pore size zeolite such as USY or zeolite beta or an intermediate pore size zeolite such as ZSM-5. The metal is normally a metal of Period 4 of the Periodic Table, preferably zinc or vanadium. The sulfur reduction catalyst may be used in the form of a separate particle additive or as a component of an integrated cracking/sulfur reduction catalyst.

Abstract: The object of the present invention is a process for the elimination of sulphur compounds from the gasoline fraction, characterized in that it comprises carrying out an oxidation reaction of said sulphur compounds using at least one organic-inorganic composite as a catalyst which comprises at least: Si, Ti and silicon linked to carbon and using organic or inorganic hydro-peroxides as oxidating agents. According to the process for the present invention, said organic or inorganic composite is obtained by means of a process that comprises a sililation stage during synthesis or by means of a process that comprises a post-synthesis sililation stage.