Exxon Research and Engineering Company

Ronald Liotta

Martin Leo Gorbaty

Teh Chung Ho

Viktor Buchholz

Chang S Hsu

William Bartok

Howard Freund

Gerald Dennis Dupre

The instant invention is directed to a process for removing hard sulfurs from hydrocarbon streams by selectively oxidizing hard sulfurs in a hydrotreated stream, under oxidizing conditions in the presence of an effective amount of an oxidizing agent, wherein the oxidizing agent is a peroxometal complex and wherein the hard sulfurs are oxidized into the corresponding sulfoxides and sulfones.

Process for deep desulfurization using combined hydrotreating-oxidation

Disclosed is a one-step ion-exchange method for organically bonding alkali and alkaline-earth metals onto coal. The method comprises contacting the coal, at a temperature from about 20.degree. C. to about 100.degree. C. with, (a) an aqueous solution containing cations of one or more metals selected from the group consisting of alkali and alkaline-earth metals, and (b) an oxidizing gas.

Cation ion exchange of coal

Coal and coal bottoms characterized by having the hydrogens of substantially all of the hydroxyl and carboxyl groups, of the coal and coal bottoms replaced with C.sub.1 to C.sub.20 alkyl or acyl groups.

O-Alkylated/O-acylated coal and coal bottoms

Coal liquids are disclosed wherein the hydrogen of substantially all of the hydroxyl groups of the coal liquids have been replaced with C.sub.1 to C.sub.20 alkyl or acyl groups.

O-Alkylated/O-acylated coal liquids

Disclosed is a method for improving the caking properties of coals by use of quaternary base solutions. Caking properties of various coals can be upgraded for the production of metallurgical grade coke, preferably with a substantially reduced mineral matter content.

Method for producing coke

Disclosed is a method for improving the properties of carbonous materials and products thereof by oxygen-alkylation. The carbonous material is treated with a quaternary base then heated to temperatures from about 100.degree. C. to 400.degree. C.

Oxygen-alkylation of carbonous material and products thereof

Disclosed is a method for comminuting and simultaneously removing mineral matter from coal by first treating the coal with a quaternary base solution, such as tetrabutylammonium hydroxide, then physically separating the mineral matter by any conventional separation technique based on the density differences of two materials.

Demineralization of coal

Highly caking coals are formed by selective oxygen-alkylation or oxygen-acylation of moderately, weakly or non-caking coals, employing a phase transfer reaction which chemically alters phenolic and carboxylic functional substituents. These two very polar functional groups are converted to relatively non-polar ethers and esters, respectively. The O-alkylation or O-acylation is carried out in a binary liquid phase solution (organic and water phases with a solid phase suspended in the medium). A quaternary ammonium or phosphonium salt is reacted with alkali or alkaline earth base to produce the corresponding quaternary ammonium or phosphonium base (an example of a phase transfer reagent). This quaternary base is non-nucleophilic and readily removes the phenolic and carboxylic protons but does little else to the coal structures. After the removal of the weakly acidic protons by the quaternary base, the phenoxides and carboxylates which are produced then undergo O-alkylation or O-acylation. The alkylating or acylating agent comprises a carbon-bearing functional group and a displaceable leaving group. The process of the invention produces caking properties in non-caking subbituminous coals and increases the caking ability of weakly or moderately caking coals. An important aspect of this invention concerns the coal liquids and gases which are produced during coke formation. The pyrolysis which forms the coke of the O-alkylated or O-acylated coal also produces higher quality coal liquids and gases.

Formation of caking coals

Solid, naturally-occurring carbonaceous materials such as coal, lignite, peat and the like are treated by oxygen-alkylation or oxygen-acylation employing a phase transfer reaction under mild conditions. The treated coal may then be liquefied, gasified, pyrolyzed, solubilized or otherwise further processed to obtain useful products therefrom. For example, liquid products derived from coal so treated are more compatible with petroleum products and evidence lower viscosity and boiling range than liquid products not so treated. The solubility of coal bottoms is increased in common organic solvents as compared with coal bottoms derived from untreated coal. The phase transfer reaction chemically alters phenolic and carboxylic functional substituents. These two very polar functional groups are converted to relatively non-polar ethers and esters, respectively. The O-alkylation or O-acylation is carried out in a binary liquid phase solution (organic and water phases with a solid phase suspended in the medium). A quaternary ammonium or phosphonium salt is reacted with alkali metal or alkaline earth metal base to produce the corresponding quaternary ammonium or phosphonium base. This quaternary base is non-nucleophilic and readily removes the phenolic and carboxylic protons but does little else to the coal structures. After the removal of weakly acidic protons by the base, the phenoxides and carboxylates which are produced then undergo O-alkylation or O-acylation.

Pretreatment of solid, naturally-occurring carbonaceous material

Coal liquids are rendered compatible with petroleum liquids by selective oxygen alkylation or oxygen acylation of weakly acidic protons such as phenolic and carboxylic functionalities by means of a phase transfer reaction. Phenolic and carboxylic functional substituents, which are very polar, are converted to relatively non-polar ethers and esters, respectively. The O-alkylation or O-acylation is carried out in a binary liquid phase solution (organic/water). A quaternary ammonium or phosphonium salt is reacted with alkali or alkaline earth base (caustic) to produce the corresponding quaternary ammonium or phosphonium base (an example of a phase transfer reagent). This quaternary base is non-nucleophilic and readily removes the phenolic and carboxylic protons, but does little else to the coal liquid molecules. After the removal of the weakly acidic protons by the quaternary base, the phenoxides and carboxylates which are produced then undergo O-alkylation or O-acylation. The alkylating or acylating agent comprises a carbon-bearing functionality and a displaceable leaving group. The O-alkylation or O-acylation reduces hydrogen bonding and therefore polarity, thereby rendering coal liquids more compatible with petroleum liquids.

Treatment of coal liquids

Treatment of weakly acidic protons in coal by oxygen-alkylation or oxygen-acylation employing a phase transfer reaction under mild conditions increases the yield, lowers the viscosity and boiling ranges of coal liquefaction distillates and renders these coal liquids more compatible with petroleum liquids. The process also improves the compatibility with petroleum liquids of the coal liquefaction bottoms and their solubility in common organic solvents. The phase transfer reaction chemically alters phenolic and carboxylic functional substituents. These two very polar functional groups are converted to relatively non-polar ethers and esters, respectively. The O-alkylation or O-acylation is carried out in a binary liquid phase solution (organic and water phases with a solid phase suspended in the medium). A quaternary ammonium or phosphonium salt is reacted with alkali or alkaline earth base (caustic) to produce the corresponding quaternary ammonium or phosphonium base (an example of a phase transfer reagent). This quaternary base is non-nucleophilic and readily removes the phenolic and carboxylic protons, but does little else to the coal structures. After the removal of the weakly acidic protons by the quaternary base, the phenoxides and carboxylates which are produced then under O-alkylation or O-acylation. The alkylating or acylating agent comprises a carbon-bearing functional group and a displaceable leaving group.

Treatment of coal to increase yields and improve physical

Increased solubility of heavy fractions of coal (e.g., coal liquefaction bottoms and coal solubilization bottoms) is obtained by oxygen-alkylation or oxygen-acylation of weakly acidic protons such as phenolic and carboxylic functionalities by means of a phase transfer reaction. Phenolic and carboxylic functional substituents, which are very polar, are converted to relatively nonpolar ethers and esters, respectively. The O-alkylation or O-acylation is carried out in a binary liquid phase solution (organic and water phases with a solid phase suspended in the medium). A quaternary ammonium or phosphonium salt is reacted with alkali or alkaline earth base to produce the corresponding quaternary ammonium or phosphonium base (an example of a phase transfer reagent). This quaternary base is non-nucleophilic and readily removes the phenolic and carboxylic protons but does little else to the coal structures. After the removal of the weakly acidic protons by the quaternary base, the phenoxides and carboxylates which are produced then undergo O-alkylation or O-acylation. The alkylating or acylating agent comprises a carbon-bearing functionality and a displaceable leaving group. The O-alkylation or O-acylation reduces hydrogen bonding and polarity, thereby rendering heavy coal fractions more soluble in common organic solvents and petroleum liquids.

Growing community of inventors

Clark, NJ, United States of America

Ronald Liotta