Chevron U.s.a. Inc.

Dennis Dykstra

Alexander E Kuperman

Theodorus Maesen

Soy Uckung

Darren P Fong

Theodorus Ludovicus Michael Maesen

Ping Wang

Ibrahim J Uckung

Darren Fong

In a process for forming a bulk hydroprocessing catalyst by sulfiding a catalyst precursor made in a co-precipitation reaction, up to 60% of the metal precursor feeds do not react to form catalyst precursor and end up in the supernatant as metal residuals. In the present disclosure, the metals can be recovered in a chemical precipitation step, wherein the supernatant is mixed with at least one of an acid, a sulfide-containing compound, a base, and combinations thereof to precipitate at least 50% of metal ions in at least one of the metal residuals, wherein the precipitation is carried out at a pre-select pH. The precipitate is isolated and recovered, yielding an effluent stream. The precipitate and/or the effluent stream can be further treated to form at least a metal precursor feed which can be used in the co-precipitation reaction. The process generates an effluent to waste treatment containing less than 50 ppm metals.

Hydroconversion multi-metallic catalyst and method for making thereof

In a process for forming a bulk hydroprocessing catalyst by sulfiding a catalyst precursor made in a co-precipitation reaction, up to 60% of the metal precursor feeds end up in the supernatant. The metals can be recovered via any of chemical precipitation, ion exchange, electro-coagulation, and combinations thereof to generate an effluent stream containing less than 50 mole % of metal ions in at least one of the metal residuals, and for at least one of the metal residuals recovered as a metal precursor feed for use in the co-precipitation reaction. In one embodiment, the resin functions as an anion exchange resin with an acidic supernatant to recover Group VIB metal residuals, and a cation exchange resin with a basic supernatant to recover Promoter metal residuals. An effluent stream from the process to waste treatment contains less than 50 ppm metals.

In a process for forming a bulk hydroprocessing catalyst by sulfiding a catalyst precursor made in a co-precipitation reaction, up to 60% of the metal precursor feeds do not react to form catalyst precursor and end up in the supernatant. In the present disclosure, the metals can be recovered in an electro-coagulation reactor, wherein portion of the metal residuals in the supernatant reacts with the electrodes to form a slurry containing insoluble metal compounds. The insoluble metal compounds are isolated and recovered, forming an effluent stream. The insoluble metal compounds and/or the effluent stream can be further treated to form at least a metal precursor feed which can be used in the co-precipitation reaction.

In a process for forming a bulk hydroprocessing catalyst by sulfiding a catalyst precursor made in a co-precipitation reaction, up to 60% of the metal precursor feeds do not react to form catalyst precursor and end up in the supernatant. In the present disclosure, the metals can be recovered via any of chemical precipitation, ion exchange, electro-coagulation, and combinations thereof to generate an effluent stream containing less than 50 mole % of metal ions in at least one of the metal residuals, and for at least one of the metal residuals is recovered as a metal precursor feed, which can be recycled for use in the co-precipitation reaction. An effluent stream from the process to waste treatment contains less than 50 ppm metal ions.

In a process for forming a bulk hydroprocessing catalyst by sulfiding a catalyst precursor made in a co-precipitation reaction, up to 60% of metal ions in at least one of the metal precursor feeds do not react to form catalyst precursor and end up in the supernatant as metal residuals. In the present disclosure, the metals can be recovered via ion-exchange, wherein an exchange resin is provided for a portion of the metal ions in the supernatant to be exchanged and bound onto the resin. The previously resin-bound metals can be subsequently recovered, or the effluent stream for the exchange resin column can also be recovered, forming at least a metal precursor feed which can be used in the co-precipitation reaction.

In a process for forming a bulk hydroprocessing catalyst by sulfiding a catalyst precursor in a co-precipitation reaction, up to 60% of the metal precursor feeds do not react to form catalyst precursor and stay in the supernatant. In one embodiment, at least a precipitant is added to the product mixture at a molar ratio of precipitant to metal residuals in the supernatant ranging from 1.5:1 to 20:1 to precipitate at least 50 mole % of metal ions in the residuals forming additional catalyst precursor. The remaining metal residuals can be recovered via any of chemical precipitation, ion exchange, electro-coagulation, and combinations thereof to generate an effluent stream containing less than 50 mole % of at least one of the metal residuals. In one embodiment, at least one of the metal residuals is recovered and recycled for use as a metal precursor feed in the co-precipitation reaction.

The invention relates to a bulk multi-metallic catalyst for hydrotreating heavy oil feeds and to a method for preparing the catalyst. The bulk multi-metallic catalyst is prepared by sulfiding a catalyst precursor having a poorly crystalline structure with disordered stacking layers, with a type IV adsorption-desorption isotherms of nitrogen with a hysteresis starting point value of about 0.35, for a sulfided catalyst that will facilitate the reactant's and product's diffusion in catalytic applications. In another embodiment, the precursor is characterized as having a type H3 hysteresis loop. In a third embodiment, the hysteresis loop is characterized as having a well developed plateau above P/Pof about 0.55. The mesapores of the precursor can be adjustable or tunable.

This invention is directed to a synthesis process for preparing magnesium aluminosilicate clays and to the products of said process. Briefly, a silicon component, an aluminum component, and a magnesium component are combined, under aqueous conditions and at an acidic pH, to form a first reaction mixture and subsequently the pH of the first reaction mixture is adjusted to greater than 7.5 to form a second reaction mixture. The second reaction mixture is allowed to react under conditions sufficient to form the magnesium aluminosilicate clay of the present invention. The invention is also directed to catalyst compositions comprising the magnesium aluminosilicate clays synthesized according to the process of the invention. The resulting magnesium aluminosilicate clay can be used as a catalyst or as a component in catalyst compositions. The invention is further directed to a magnesium aluminosilicate clay with a characteristicSi NMR spectrum and the use of said magnesium aluminosilicate clay in catalyst compositions.

Magnesium aluminosilicate clays&#x2014;synthesis and catalysis

A catalyst precursor for preparing a bulk multi-metallic catalyst upon sulfidation is provided. The precursor has an essentially monomodal pore volume distribution with at least 90% of the pores being macropores, and a total pore volume of at least 0.08 g/cc. The bulk multi-metallic prepared from the precursor is particularly suitable for hydrotreating heavy oil feeds having a boiling point in the range of 343&#xb0; C. (650&#xb0; F.)&#x2014;to 454&#xb0; C. (850&#xb0; F.), an average molecular weight Mn ranging from 300 to 400, and an average molecular diameter ranging from 0.9 nm to 1.7 nm.

A method for preparing a bulk multi-metallic suitable for hydrotreating heavy oil feeds is provided. In the process of preparing the catalyst precursor which is subsequently sulfided to form the bulk catalyst, non-agglomerative drying is employed to keep the catalyst precursor from aggregating/clumping, resulting in a catalyst precursor with optimum porosity with at least 90% of the pores being macropores, and having a total pore volume of at least 0.08 g/cc.

A catalyst and a process for making a catalyst from a precursor composition containing rework materials are disclosed. The catalyst is made by sulfiding a catalyst precursor containing 5-95 wt. % rework material. The catalyst precursor employing rework materials can be a hydroxide or oxide material. Rework can be materials generated in the forming or shaping of the catalyst precursor, or formed upon the breakage or handling of the shaped catalyst precursor. Rework can also be in the form of catalyst precursor feed material to the shaping process, e.g., extrusion process, or catalyst precursor material generated as reject or scrap in the shaping process. In some embodiment, rework may be of the consistency of shapeable dough. In another embodiment, rework is in the form of small pieces or particles, e.g., fines, powder.

A stable catalyst with low volumetric shrinkage and a process for making the stable catalyst with low volumetric shrinkage is disclosed. The catalyst is made by sulfiding a catalyst precursor containing at least a Group VIB metal compound; at least a promoter metal compound selected from Group VIII, Group IIB, Group IIA, Group IVA and combinations thereof, having an oxidation state of either +2 or +4; optionally at least a ligating agent; optionally at least a diluent. In the process of making the catalyst, the catalyst precursor is first shaped then heat treated at a temperature of 50&#xb0; C. to 200&#xb0; C. for about 15 minutes to 12 hours, wherein the catalyst precursor still has a low (less than 12%) volumetric shrinkage after exposure to a temperature of at least 100&#xb0; C. for at least 30 minutes, e.g., in sulfidation or in a hydrotreating reactor.

A method for preparing a bulk multi-metallic suitable for hydrotreating heavy oil feeds is provided. In the process of preparing the catalyst precursor which is subsequently sulfided to form the bulk catalyst, a catalyst precursor filter cake is treated with at least a chelating agent, resulting in a catalyst precursor with optimum porosity with at least 90% of the pores being macropores, and having a total pore volume of at least 0.12 g/cc.

A process for preparing a bulk multi-metallic catalyst for hydrotreating heavy oil feeds is provided. The catalyst is particularly suitable for hydrotreating heavy oil feeds having a boiling point in the range of 343&#xb0; C. (650&#xb0; F.)- to 454&#xb0; C. (850&#xb0; F.), an average molecular weight Mn ranging from 300 to 400, and an average molecular diameter ranging from 0.9 nm to 1.7 nm. The bulk multi-metallic catalyst is prepared by sulfiding a catalyst precursor that has an essentially monomodal pore volume distribution with at least 95% of the pores being macropores, and having a total pore volume of at least 0.08 g/cc.

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Pinole, CA, United States of America

Dennis Dykstra