Diene-selective hydrogenation of metathesis derived olefins and unsaturated esters
View Patent ↗Methods are provided for refining natural oil feedstocks and partially hydrogenating polyunsaturated olefins and polyunsaturated esters. The methods comprise reacting the feedstock in the presence of a metathesis catalyst under conditions sufficient to form a metathesized product comprising olefins and esters. In certain embodiments, the methods further comprise separating the polyunsaturated olefins from the polyunsaturated esters in the metathesized product. In certain embodiments, the methods further comprise partially hydrogenating the polyunsaturated olefins in the presence of a hydrogenation catalyst, wherein at least a portion of the polyunsaturated olefins are converted to monounsaturated olefins. In other embodiments, the methods further comprise partially hydrogenating the polyunsaturated esters in the presence of a hydrogenation catalyst, wherein at least a portion of the polyunsaturated esters are converted to monounsaturated esters.
1. A method of forming monounsaturated olefins, comprising:
providing a feedstock comprising polyunsaturated olefins, wherein the polyunsaturated olefins are formed by a process comprising reacting a natural oil in the presence of a metathesis catalyst; and
partially hydrogenating the polyunsaturated olefins in the presence of a hydrogenation catalyst for 30-180 minutes at a temperature between 150° C. and 250° C. with a hydrogen gas pressure between 50 psig and 500 psig to form a product comprising monounsaturated olefins,
wherein the hydrogenation catalyst is provided in an amount between 0.01-1.0 wt % of the polyunsaturated olefins, wherein the partially hydrogenating step has a conversion rate of at least 85% and a selectivity of at least 90%;
wherein the conversion rate refers to the difference between the weight of polyunsaturated olefins in the feedstock and the weight of polyunsaturated olefins in the product as a percentage proportion of the weight of polyunsaturated olefins in the feedstock; and
wherein the selectivity refers to the weight of monounsaturated olefins formed as a percentage proportion of the total weight of monounsaturated olefins and saturated paraffins formed.
2. The method of claim 1 , wherein the feedstock is treated prior to the hydrogenating step under conditions sufficient to diminish catalyst poisons in the feedstock,
wherein the feedstock is treated with one or more of the following: heat, molecular sieves, alumina, silica gel, montmorillonite clay, fuller's earth, bleaching clay, diatomaceous earth, zeolites, kaolin, activated metals, acid anhydrides, activated carbon, soda ash, metal hydrides, metal sulfates, metal halides, metal carbonates, metal silicates, phosphorous pentoxide, metal aluminum hydrides, alkyl aluminum hydrides, metal borohydrides, organometallic reagents, and palladium on carbon catalysts.
3. The method of claim 1 , wherein the hydrogenation catalyst comprises a metal selected from the group consisting of nickel, copper, palladium, platinum, molybdenum, iron, ruthenium, osmium, rhodium, iridium, and combinations thereof.
4. The method of claim 1 , wherein the conversion rate is at least 90% and the selectivity is at least 95%.
5. The method of claim 1 , wherein the conversion rate is at least 95% and the selectivity is at least 99%.
6. The method of claim 1 , wherein the hydrogenation catalyst has been recycled prior to the hydrogenating step.