SIMPLIFIED PROCESS TO PREPARE POLYOLEFINS FROM SATURATED HYDROCARBONS
A simplified process for preparing polyolefins from saturated hydrocarbons is provided. The process involves partial and selective dehydrogenation of a saturated hydrocarbon in the presence of oxygen to form an olefin, unreacted hydrocarbon, and water, and optionally other by-products and oxygen. The water, other by-products (if present), and oxygen (if present) are separated from the olefin and unreacted hydrocarbon. No other separation is performed. The olefin and unreacted hydrocarbon are polymerized in the presence a polymerization catalyst or initiator to make polyolefin. Solid polyolefin is separated from unreacted hydrocarbon, which is recycled to the dehydrogenation reaction.
1 . A process for making polyolefin from an alkane, comprising:
(a) dehydrogenating an alkane in the presence of oxygen to form a dehydrogenation product stream comprising a corresponding alkene, unreacted alkane, and water, and optionally other by-products and oxygen;
(b) separating the water, other by-products (if present), and oxygen (if present) from the dehydrogenation product stream without separating the unreacted alkane to form a separated dehydrogenation product stream comprising alkene and unreacted alkane;
(c) polymerizing the alkene in the separated dehydrogenation product stream in the presence of a polymerization catalyst or initiator and the unreacted alkane to form a polymerization product stream comprising polyolefin, unreacted alkane, and optionally unreacted alkene;
(d) separating the polyolefin from the unreacted alkane and unreacted alkene (if present) in the polymerization product stream; and
(f) recycling of the unreacted alkane and unreacted alkene (if present) to the dehydrogenation step.
2 . The process according to claim 1 , wherein the polyolefin is polyethylene and the alkane is ethane.
3 . The process according to claim 2 , wherein the polyethylene is low density polyethylene, linear low density polyethylene, or high density polyethylene.
4 . The process according to claim 2 , wherein the polymerization step is carried out under high pressure in an autoclave or tubular reactor, or in solution, a slurry, or gas phase, or combinations thereof.
5 . The process according to claim 2 , wherein the polymerization catalyst is a Ziegler-Natta, metallocene, single site, late transition metal, or chromium catalyst, or combinations thereof.
6 . The process according to claim 1 , wherein the polyolefin is an ethylene copolymer.
7 . The process according to claim 1 , wherein the polyolefin is polypropylene, and the alkane is propane.
8 . The process according to claim 7 , wherein the polymerization step is carried out in a slurry, in bulk, or in the gas phase, or combinations thereof.
9 . The process according to claim 7 , wherein the polypropylene is a homopolymer.
10 . The process according to claim 1 , wherein the polymerization step is carried out in the presence of an α-olefin.
11 . The process according to claim 10 , wherein the α-olefin is 1-butene, 1-hexene, 1-octene, 1-dodecene, or combinations thereof.
12 . The process according to claim 1 , further comprising oligomerizing at least a portion of the alkene in the separated dehydrogenation product stream to form a mixture of α-olefins, and polymerizing the alkene in the unoligomerized portion of the separated dehydrogenation product stream with the mixture of α-olefins in the presence of a polymerization catalyst or initiator and the unreacted alkane to form a polymerization product stream comprising polyolefin and unreacted alkane.
13 . The process according to claim 1 , further comprising recovering heat liberated from the dehydrogenation step.
14 . The process according to claim 13 , wherein the heat recovered from the polymerization step is used in the dehydrogenation step.
15 . The process according to claim 7 , wherein the polymerization catalyst is a Ziegler-Natta, metallocene, or single site catalyst, or combinations thereof.