SELECTIVE CATALYSTS HAVING HIGH TEMPERATURE ALUMINA SUPPORTS FOR NAPHTHA HYDRODESULFURIZATION

The present invention refers to the following steps (iii) to (i) produced by including method of, a catalyst suitable for the HDS of naphtha relates to: alumina precursor (i) about 800 °C hot heating the heated material at more than and, which phase forms alumina, said high temperature cobalt salt (a) alumina, (b) molybdenum salts and (c) at least one organic additive aqueous solution impregnated impregnated high temperature, which phase forms alumina wherein, the high temperature alumina alumina relative to the total weight of the weight of less than about 50% gamma, eta and alumina content lower, about 100 Å to about 1000 Å of an intermediate pore diameter and about 40 m²/g to about 200 m²/g has a surface area of a, step ; (ii) said impregnated high temperature alumina at a temperature of less than about 200 °C is dried, drying the impregnated high temperature alumina to form a catalyst precursor ; (iii) said and is dried, impregnated high temperature alumina catalyst precursor by sulfide to a sulfide as phase[...][...][...] as a step in HDS catalyst, the HDS catalyst or the catalyst precursor sulfide in HDS prior to or which is not calcined, step.

In one aspect a preferred embodiment, HDS a catalyst precursor a catalyst support body, wherein said component comprises from about 1 weight % to about 8 weight % cobalt, and a catalyst support body, wherein said component comprises from about 6% to about 20 weight % of weight and comprising at [...] material and a molybdenum. Said HDS catalyst a delta alumina, theta alumina and kappa in addition to alumina other high temperature, such as alumina, alpha-alumina can further.

Another embodiment (iv) to (i) the following steps aspect a method of preparing a catalyst including HDS relates to: alumina precursor (i) about 800 °C heating the heated material at more than, which phase forms alumina a hot; high temperature (ii) cobalt salt (a) alumina, (b) molybdenum salts and (c) at least one organic additive impregnated impregnated aqueous solution, which phase forms alumina wherein high temperature, the high temperature alumina alumina relative to the total weight of the weight of less than about 50% gamma, eta and alumina content lower, about 100 Å to about 1000 Å of an intermediate pore diameter and about 40 m²/g to about 200 m²/g has a surface area of a, step ; (iii) said impregnated high temperature alumina at a temperature of less than about 200 °C is dried, drying the impregnated high temperature alumina to form a catalyst precursor ; (iv) said and is dried, impregnated high temperature alumina catalyst precursor a of forming the HDS by sulfide to a sulfide, [...] , the HDS catalyst or the catalyst precursor sulfide in HDS prior to or which is not calcined, step.

Another embodiment including a (iii) to (i) the following steps aspect, based on the weight of naphtha about 5 weight % or more olefin content relates to HDS method of naphtha: HDS catalyst (i) said naphtha HDS conditions contacting the wherein, the alumina precursor catalyst is said about 800 °C hot heating the heated material at more than and, which phase forms alumina, said high temperature cobalt salt (a) alumina, (b) molybdenum salts and (c) at least one organic additive impregnated impregnated aqueous solution, which phase forms alumina wherein high temperature, the high temperature alumina alumina relative to the total weight of the weight of less than about 50% gamma, eta and alumina content lower, about 100 Å to about 1000 Å of an intermediate pore diameter and about 40 m²/g to about 200 m²/g has a surface area of a, step ; (ii) said impregnated high temperature alumina at a temperature of less than about 200 °C been dried so drying ㏊ high temperature and to be used for medicines for high temperature alumina to form a catalyst precursor ; (iii) said and is dried, impregnated high temperature alumina catalyst precursor by sulfide to a sulfide of forming the wherein HDS, the HDS catalyst or the catalyst precursor sulfide in HDS prior to or which is not calcined, step.

Said HDS catalyst in the case of being employed for HDS of naphtha, naphtha feed of high HDS as maintain olefin saturation exhibits improved selectivity.

Terms "naphtha" has, and a major component of petrol using hydrocarbons with a medium boiler while referring to light fractions while ordinarily used to, terms "FCC naphtha" comprises a fluid catalysis is publicly known well to made by a procedure in which with a desired channel and. refers to naphtha. Naphtha having a medium boiler 10 °C about in the atmospheric pressure (i.e., generally C₅ made from) to about 232 °C (50F to 450F), preferably about 21 °C to about 221 °C (430F to 70F) is naphtha with a boiling point. FCC process without hydrogen added fabrication of naphtha polyolefin and aromatic compounds having a relatively high concentration of. producing naphtha. Other naphtha e.g., steam cracking naphtha and to be relatively coker naphtha and comprising at a high concentration of the olefins in the vaporized oil. A naphtha olefin typically based on the weight of naphtha about 5 weight % or more and about 60% hereinafter, preferably about 5 weight % to about 40 weight % of olefin content; based on the weight of naphtha about 300 ppmw to about 7000 ppmw of sulfur content in the; and about based on the weight of naphtha has a nitrogen content of 500 ppmw to about 5 ppmw. Polyolefin is a open chain olefin, cyclic olefin, as dienes and olefins chains comprising hydrocarbon and the annular. Polyolefin and the aromatic compound is because the high octane component, naphtha hydrocracking typically a hydrogen a naphtha olefin is higher than the side directions in order to octane vehicle studies and exhibits. In olefin content is naphtha olefin but, typically in good, they are other compounds, in particular sulfur-containing compound, and a nitrogen-containing compounds can also include a.

Selective catalytic

The lowest degree olefin saturation sulfur to olefins from a catalyst for selectively removing a support material temperature alumina produced with the aid of side.. High temperature, high surface area alumina (about 40 m²/g to about 200 m²/g) and large pore alumina and down. Alpha alumina other on alumina (phase), are connected to the hot e.g., about 1000 °C to about 1200 °C when heated sufficiently to a temperature above its melting point a semiconductor layer is formed on the most stable high temperature alumina. different. Therefore, alumina precursor e.g., boehmite (boehmite) or [...] cordierite and method for scanning video coefficients bidirectionally (psuedoboehmite) (AlO (OH)) (bayerite) or [...] site (gibbsite) (Al (OH)₃) be gradually heated until a hot the on alumina switched onto through alpha. The start of [...] , normally acceptable associated with an increase temperature comprises adding a phase transition the following equal: boehmite → gamma alumina surface portion focuses of alumina/→ delta alumina/kainate alumina → alpha alumina. The start of [...] , temperature associated with an increase phase transition the following equal: → positive photosensitive anionic site [...] alumina → kappa alumina → alpha alumina. Bi with light the start of, temperature associated with an increase phase transition the following equal: bi cordierite → eta alumina → theta alumina → alpha alumina. Establishing an optical fiber at a side, alpha alumina processing based on the determined gamma properties, positive photosensitive anionic, eta, delta, kappa and theta and heating alumina other materials such as different final on.. As used in the present specification, high temperature alumina theta alumina, delta alumina, kappa alumina and alpha alumina, and only small amounts of gamma on alumina, alumina or eta on kainate on alumina with an alumina mixture thereof. mixture by the addition of an initiator. Gamma alumina, an alumina total of positive photosensitive anionic alumina and eta alumina based on the weight of less than about 50 weight %, preferably about less than 30 weight %, more preferably, at least 20% less than weight. In one aspect a embodiment, an alumina alumina high temperature about relative to the total weight of the 50 weight % or more, preferably about 70 weight % or more, more preferably, at least 80 weight % or more theta alumina, kappa alumina, delta alumina and alpha alumina containing one or more of..

The present invention according to a precursor e.g. high temperature alumina, gamma alumina, bi cordierite, about 800 °C [...] sites and/or boehmite by heating the heated material at more than can be produced. Furthermore, starter temperature used is a function of heating time properties and on and, on a desired time a controlled to achieve. Therefore, preferably alumina high temperature mainly theta alumina, kappa alumina and alpha alumina made of is a mixture, more preferably mainly theta alumina and alpha alumina is a mixture made up of a. "Mainly" addition, the height of particular constituent in a product weight of components or mixture exceeds about 50% of the weight of the dosage form which implies that the.. Rubber steam treatment the alumina also used for forming. genes of interest. For example, about 1000 °C and from about 95% humidity in surface steaming the alumina precursor time 1 pure theta material generated. High temperature alumina having properties that are the resist layer is a, conventional method including high temperature alumina other manufacturing method can be using a liquid crystal display displays.

Alumina phase allocated to respective X-ray diffraction is measured. Variety of are an essential and peak intensity is measured by-space d is a characteristic X-ray diffraction pattern individually indicate the.. Therefore, X-ray diffraction high temperature alumina are to be produced to ensure that the can be used.

Furthermore, high temperature the alumina support (a) cobalt salt, (b) molybdenum salts and (c) at least one organic additive e.g., organic formed by impregnates into the reaction chamber. Alumina support are formed with a non-photosensitivity used to perform any cobalt and molybdenum salt can be a water-soluble salt thereof. A preferred salts include carbonate, nitrate, such as [...]. The amount of salt weight of supported alumina support wherein said component comprises from about 2 weight % to about 8 weight %, preferably about 3 weight % to about 6 weight % of cobalt oxide (CoO) and from about 8 weight % to about 30 weight %, preferably about 10 weight % to about 25% weight oxidation of [...] (MoO₃) will containing.

A cobalt and molybdenum component organic ligand silica support to its inferred it help. organic additive. The organic additive oxygen and/or nitrogen atoms which disposing of mono-, bi-disposing of disposing of and poly-. containing a ligand. The organic additive may [...] (ligands). Organic ligands include one or more of a carboxylic acid, polyol, amino acid, amine, amide, amino alcohol, ketone, ester such as. Examples of organic ligands [...] , quinolinol, salicylic acid, acetic acid, ethylene diamine ethylenedaiminetetra acetic acid (EDTA), cyclohexane diamine (CYDTA) ethylenedaiminetetra acetic acid, alanine, arginine, triethanolamin (TEA), writing two three rolls , histidine, acetylacetonate, guanidine and nitrile with tree acet acid (NTA), citric acid and urea with.

Contact 140° about the alumina support high temperature using angle ASTM method number D4284 state in gap method of measurement determined through a measurement large mercury has high void volume for. Void volume about 0.3 cc/g to about 1.5 cc/g, preferably about 0.5 cc/g to about 1.5 cc/g is. Mercury press intermediate in the pore size according to a measurement using volume about 100 Å to about 1000 Å, is preferably about 150 Å to about 1000 Å. According to a measurement using BET method a the use of nitrogen in a surface area of from about 40 m²/g to 200 m²/g, preferably about 40 m²/g to about 150 m²/g is.

Of which are held in any particular theory but without intending to be, , and greater void diameter weakly dried of the present invention have high temperature the alumina support organic ligands e.g., arginine, when combined and ureas and citric deposit desulfuration feed naphtha HDS while maintaining for activating catalysts determines the desired olefin saturation and exhibits a selectivity catalyst to an to HDS. Organic ligands an alumina support throughout the metal effectively assists in distributing this effective distribution of the present invention that are indicated by the catalyst selectivity increased the pixels include the causes in. estimated.

High temperature the alumina support 1 through group 18 based on IUPAC format group having 2 to 4 of the periodic table group, preferably metal family of 2 and 4. may be doped. Zr examples of these metals, milligram, users can Ti.. For example, literature (The Merck Index, Twelfth Edition, Merck & Co. , Inc. , 1996) reference a.

Catalyst preparation and use

High temperature alumina support typically techniques involve changing one, i.e., hydrogen added design catalysts, synthesis, making and/or utilizing in fields such a publicly known to one skilled in the art or by a sand blast, an cobalt salt and molybdenum salt impregnating a an aqueous solution comprising visitor is checked through a. Organic ligands before an alumina support added to an aqueous solution of salt thereto can be. Alumina support embodiment a impregnating a metal salt containing initial aspect is impregnated by method (incipient wetness method). In method is, a metal salt and an aqueous solution containing organic additive using techniques conventional effective time of the initial containing the admixture support point.

Alumina support initial manner impregnating a metal salt supported using alumina support mixtures impregnating the cobalt salt and an organic ligand, support impregnated with dried and subsequently, drying and a support made from a molybdenum salt solution or organic containing a ligand the initial containing a molybdenum salt solution can be manner impregnated point. Another embodiment in one aspect, cobalt salt subsequent to the molybdenum salt can be the reverse stacking order for impregnating. Another embodiment in one aspect, support cobalt salt and an organic ligand-containing molybdenum salt mixtures initial containing point can through the co-precipitation method. Through the co-precipitation method, is dry-to-the supporting body through the co-precipitation method and. can be repeated process. Another embodiment in one aspect, extruded the alumina support cobalt salt, molybdenum salts and organic ligands can be impregnated with mixture of drying impregnated support is subjected. This processing if desired. can be repeated. In one aspect all said embodiment, a single ligands or may be organic ligand can also be a mixture of ligands.. That have been split from a reaction mixture impregnated alumina support about 50 °C to about 200 °C is heated at a temperature and dried to be a to form a catalyst precursor. May perform well under the vacuum the drying or may be air or inert gas e.g., can be in nitrogen trifluoride.

Dried a catalyst precursor metal oxide, metal salts or metal complex conversion of the corresponding mask assembly to a sufficient temperature to time gas gross volume of wherein said component comprises from about 0.1 volume % to about 10 volume % HDS therefor are subjected to treatment with hydrogen sulfide concentration of to form a catalyst. Hydrogen sulfide a catalyst precursor comprises subjecting, is introduced on the a or a catalyst precursor in by sulfide can be produced. In one aspect a embodiment, is combination with diluent agent sulfide. For example, die methyl disulfide can be combination with naphtha diluent. An amount that is less than that of hydrogen sulfide may be used; however is out of the active layer on the basis of the number of can be times. Inert carrier can be present and activate is liquid or gas phase may take place at. Inert carrier examples of nitrogen and light hydrocarbons and to demetallize the e.g., methane :. Inert gas in the presence of, inert gas may be included as a total gas portion of the volume. 700 °C to about 150 °C about temperature, is preferably about 160 °C to about 343 °C. Said temperature kept at a constant which starting at low temperature or may be activated by thereby increasing the temperature during which gradually increases, can be. A total pressure about 5000 psig (34576 kPa), preferably about 0 psig to about 5000 psig (34576 kPa to 101 kPa), more preferably, at least 50 psig to about 2500 psig (17338 kPa to 446 kPa) is. Liquid carrier in the presence of, liquid construction speed (LHSV) about 0.1 hr^-1 to about 12 hr^-1, preferably about 0.1 hr^-1 to about 5 hr^-1 is. LHSV has a continuous manner relative to. However, batch activation may be loaded with performed (batch mode) manner. Total gas speed about 89 m³/m³ to about 890 m³/m³ (500 scf/B to 5000 scf/B) can be.

The same catalyst sulfidation based or other reactant reaction system may take place at. Sulfide with catalysts and the sulfiding agent by contacting a higher than the first voltage and the sulfiding agent liquid or gas phase by using can be caused. Alternatively, catalyst can occur during is sulphided hydrogen sulfide to may be sulfide. When liquid phase sulfiding agent, sulfide and the sulfiding agent catalyst be a carrier liquid and a containing brought into contact. Sulfide a carrier liquid agent can be added to a carrier liquid or. may be sulfide itself. A carrier liquid is preferably untreated hydrocarbon vapor and hydrogenation catalysts are to be contacted with feedstock but may be, any hydrocarbon vapor e.g., mineral (crude) or synthetic source derived from distillate can be. When added to to a carrier liquid agent sulfide, sulfide sulfur-based activation conditions number itself can be the generation of hydrogen in the gas or liquid can be. Examples hydrogen sulfide, carbonyl sulfide, carbon disulfide, sulfide e.g., die methyl sulfide, preparing protected 4 e.g., preparing protected 4 methyl die, and polysulfide e.g., die-t- the pulley clear statement id which will stroll can be mentionned. Some feed e.g., a sulphide sulfide present in the compositions crude feed number can act as aliphatic compounds, aromatic compound and heterocyclic compound including hydrogen sulfide to a capable of generating a wide variety of sulfur-containing species may include a.

Prior to or a sulphide-dried catalytic HDS not calcined in. A dry, that not calcined catalyst about 300 °C, preferably about 200 °C are heated to a temperature above the. no inclusion of. Calcining catalyst formed on, about 60% to about 100% of a dispersing agent prior to or sulfide HDS prior to use of. remaining on a catalyst.

After sulfide, naphtha HDS catalyst conditions. may be brought into contact. Temperature of about 150 °C to 400 °C HDS conditions, about 445 kPa to about 13890 kPa (50 psig to 2000 psig) pressure, about 0.1 to about 12 liquid construction speed, and from about 89 m³/m³ to about 890 m³/m³ (500 scf/B to 5000 scf/B) includes speed gas with hydrogen. After HDS, the desulfurized naphtha a storage or further process e.g., stripping for removing the hydrogen sulfide (stripping) in treated. The desulfurized naphtha other naphtha boiling range-grade hydrocarbon automotive gasoline mixed with. is useful in preparing.

A preferred embodiment embodiment embodiment which is marked as a chemical aspect including aspects is exemplary aspect.

In the embodiment 1to 5

Organic filler number and 2% HNO₃[...] as 30%-300 (UOP) and after mixing (Avicel) (FMC) cells arbiter 1/20 " extruded through a (quadrilobed die) shaped die pulling out the support useful as been produced with at alumina extrudate. Generated extrudate temperature, time and of partial vaporization by is calcined by using for various conditions of alumina support in the embodiment 1 to 5 have been prepared. Specific calcination conditions, confirming on alumina, N₂ BET by surface area, and Hg enabled to operate close to the loop diameter/volume an antioxidant are depicted in table 1. XRD pattern of calcined alumina support is also 1 is shown in a.. Copper anode by cylinder to have. Strength results scattering angle (2 θ) to been dust. Also the 5 to 2 in the embodiment 2, 3, 4 and 5 for Hg pressed in a more, exhibiting a pore size distribution such that at.

In the embodiment 6

Mixed theta alumina phase alpha alumina and containing a (Norpro SA31132) alumina support commercially in the embodiment 1 to 5 a X-ray diffraction technique such as sensors. Also Figure 6 shows a support is X-ray diffraction pattern of tables, via. Also Figure 7 shows a log-log of pore size distribution such that at. foil. Figure 7 HG press on the basis of a volume more, exhibiting pore size distribution such that at. Mercury press said measured deformations with reference volume 672 Å but medium pore diameter, void the measured medium pore diameter is 209 Å. Said support N₂ BET method in according to a measurement using 62 m²/g of surface area and Hg (ASTM-D4284 method) in according to a measurement using 0.77 cc/g has a void volume. 8.34 g solution impregnated urea and 4.20 g of monohydrate citrate sheath is dissolved in water to a 10 milliliter after monohydrate cobalt bicarbonate 2.13 g (46.2% cobalt) and 6.13 g ammonium [...] nitride, which in turn are dissolved prepare. Initial solution impregnated or by a sand blast, an impregnated containing added to alumina support. Impregnated catalyst without calcination dry in 110 °C and sulfide was used to assess the HDS. Based on the dry weight solids which are impermeable relative to the impregnated 3.9 15.5 weight % weight % of cobalt oxide and oxidation of was containing [...].

In the embodiment 7to 11

In the embodiment 1 to 5 as organic additive alumina support of citric acid and utilizes urea cobalt and molybdenum salt impregnating a visitor is checked through a. Impregnation and drying in the embodiment 6 as described performed for all the. 2 table to the dried catalyst precursor disclosed is of metal.

In the embodiment 12

In the embodiment 6 to 11 to the catalyst obtained therefrom a reference commercially available translations and sulfide to a sulfide precursor CoMo/Al₂ O₃ catalyst (RT-225) with cracked naphtha HDS was in high-throughput methods to test selectivity. Said catalyst precursor with a H₂ and untreated naphtha in a metabolism product of sulfur-based visitor is checked through a sulfide using 3%. For evaluating catalyst of 1408 PPM feed containing sulfur and 46.3% of the olefins in the vaporized oil C₅ -177 ° C (350F) FCC naphtha feed insistence. Catalyst H₂ 274 °C (525F) using in 220 psig and MCFB-48 unit (multi-channel fixed bed -48 reactor) was assessed in. Feed flow rate of desulfurization-thiophene 2-65% to 95% can be regulated to achieve. Product stream (stream) the online GC and the an analyte using a SCD. In the products C₅ olefin content supplying in C₅ olefin content compared to olefin saturation rate (% OSAT) of the bill. % HDS % OSAT and 30 about stream a catalyst that is result of a cement time stable after the n bit parallel data inputted in various HDS conversion (% HDS) olefin saturation been and used to evaluate the (% OSAT) rate.

In the embodiment 12 also Figure 8 shows a used to manufacture a-up of catalyst of an alumina support of an intermediate pore diameter (in the void press Hg) for 90% HDS conversion in C₅ olefin saturation is formed inside the tie. small rate. Intermediate a pore diameter commercially available in 90 Å same catalyst which is the n bit parallel data inputted test conditions in said catalyst 14 weight % of 90% HDS conversion C₅ using the olefin saturation. Commercially formed on alumina low temperature catalyst and said catalyst (in the embodiment 7 and 8 obtained from precursor) when comparison with a, high temperature alumina supported on a catalyst of the present invention exhibits a lower olefin saturation.

In the embodiment 12 also Figure 9 shows a used to manufacture a-up of catalyst of an of alumina support (1/intermediate pore diameter) for 90% HDS conversion in C₅ olefin saturation is formed inside the tie. small rate.

In the embodiment 12 also Figure 10 shows a used to manufacture a-up of catalyst of an the case of alumina support (in gap method of measurement determined through a measurement in Hg) greater than 150 Å over a surface area of the 90% HDS conversion in C₅ olefin saturation is formed inside the tie. small rate.