초록 ▼

Oxidative dehydrogenation of paraffins to olefins provides a lower energy route to produce olefins. Oxidative dehydrogenation processes may be integrated with a number of processes in a chemical plant such as polymerization processes, manufacture of glycols, and carboxylic acids and esters. Addition

Oxidative dehydrogenation of paraffins to olefins provides a lower energy route to produce olefins. Oxidative dehydrogenation processes may be integrated with a number of processes in a chemical plant such as polymerization processes, manufacture of glycols, and carboxylic acids and esters. Additionally, oxidative dehydrogenation processes can be integrated with the back end separation process of a conventional steam cracker to increase capacity at reduced cost.

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1. A chemical complex comprising one or more unit operations selected from the group consisting of a high pressure polyethylene unit, a gas phase polyethylene unit, a slurry phase polyethylene unit, a solution phase polyethylene unit, an acetic acid unit, a vinyl acetate unit, an ethylene epoxide un

1. A chemical complex comprising one or more unit operations selected from the group consisting of a high pressure polyethylene unit, a gas phase polyethylene unit, a slurry phase polyethylene unit, a solution phase polyethylene unit, an acetic acid unit, a vinyl acetate unit, an ethylene epoxide unit, an ethylene glycol unit, an ethanol unit, an ethylene halide unit, an ethanol dehydrogenation unit, and an acetic acid dehydrogenation unit; and a steam cracker feeding at least one of a C2 cryogenic distillation tower and a hydrogenation unit to remove acetylene, the improvement consisting of integrating an oxidative dehydrogenation unit for the oxidative dehydrogenation of ethane in a mixed stream of ethylene and ethane;wherein the product stream from the cracker is heated and fed to parallel hydrogenation units to produce a stream having less than 1 ppm acetylene, and passed through a knock out drum and split so that at least a portion of the resulting stream passes through an oxidative dehydrogenation unit to increase the ethylene content thereof, and returned to the product stream having less than 1 ppm of acetylene and the combined stream is dried for further processing;wherein the oxidative dehydrogenation of ethane to ethylene is conducted at a temperature from 250° C. to 600° C., a pressure from 0.5 to 100 psi (3.4 to 689.5 kPa) and has a productivity of not less than 1000 g of olefin per kg of catalyst per hour in the presence of a catalyst selected from the group consisting of:i) catalysts of the formula NixAaBbDdOe whereinx is a number from 0.1 to 0.9, preferably from 0.3 to 0.9, most preferably from 0.5 to 0.85, most preferably 0.6 to 0.8;a is a number from 0.04 to 0.9;b is a number from 0 to 0.5;d is a number from 0 to 0.5;e is a number to satisfy the valence state of the catalyst;A is selected from the group consisting Ti, Ta, V, Nb, Hf, W, Y, Zn, Zr, Si and Al or mixtures thereof;B is selected from the group consisting of La, Ce, Pr, Nd, Sm, Sb, Sn, Bi, Pb, Tl, In, Te, Cr, Mn, Mo, Fe, Co, Cu, Ru, Rh, Pd, Pt, Ag, Cd, Os, Ir, Au, Hg, and mixtures thereof;D is selected from the group consisting of Ca, K, Mg, Li, Na, Sr, Ba, Cs, and Rb and mixtures thereof; andO is oxygen;ii) catalysts of the formula MOfXgYhOi whereinX is selected from the group consisting of Ba, Ca, Cr, Mn, Nb, Ta, Ti, Te, V, W and mixtures thereof;Y is selected from the group consisting of Bi, Ce, Co, Cu, Fe, K, Mg, V, Ni, P, Pb, Sb, Si, Sn, Ti, U, and mixtures thereof;f=1;g is 0 to 2;h=0 to 2, with the proviso that the total value of h for Co, Ni, Fe and mixtures thereof is less than 0.5;i is a number to satisfy the valence state of the catalyst;iii) catalysts of the formula VxMoyNbzTemMenOp wherein Me is a metal selected from the group consisting of Ta, Ti, W, Hf, Zr, Sb and mixtures thereof; andx is from 0.1 to 3;y is from 0.5 to 1.5;z is from 0.001 to 3;m is from 0.001 to 5;n is from 0 to 2and p is a number to satisfy the valence state of the mixed oxide catalyst;iv) catalysts of the formula MOaVbNbcTeeOn wherein a=1.0; b=0.05 to 1.0, c=0.001 to 1.0, e=0.001 to 0.5, and n is determined by the oxidation states of the other elements; andv) catalysts of the formula MOaVbXcYdZeMfOn wherein X is at least one of Nb and Ta; Y is at least one of Sb and Ni; Z is at least of one of the Te, Ga, Pd, W, Bi and Al; M is at least one of Fe, Co, Cu, Cr, Ti, Ce, Zr, Mn, Pb, Mg, Sn, Pt, Si, La, K, Ag and In; a=1.0 (normalized); b=0.05 to 1.0; c=0.001 to 1.0; d=0.001 to 1.0; e=0.001 to 0.5; and f=0.001 to 0.3; and n is determined by the oxidation states of the other elements. 2. The chemical complex according to claim 1, wherein in said catalysts of the formula(iii) n is 0. 3. The chemical complex according to claim 1, wherein the oxidative dehydrogenation unit has a selectivity of not less than 95% to produce ethylene. 4. The chemical complex according to claim 3, wherein the oxidative dehydrogenation catalyst is supported on an inert porous ceramic membrane selected from oxides of titanium, zirconia, aluminum, magnesium, yttria, lantana, silica and their mixed compositions, to provide from 0.1 to 20 weight % of said catalyst and from 99.9 to 80 weight % of said inert porous ceramic membrane. 5. The chemical complex according to claim 4, wherein the oxidative dehydrogenation unit comprises an outer shell and one or more internal ceramic tubes defining a separate, flow passage for oxygen-containing gas on the interior of said tubes and a passage between the external wall of the reactor and the ceramic tubes defining a flow path for an ethylene-containing gas. 6. The chemical complex according to claim 5, wherein the ceramic tube further comprises an internal steel mesh and an external steel mesh. 7. The chemical complex according to claim 6, wherein the oxidative dehydrogenation of ethane to ethylene is conducted at a temperature from 300° C. to 550° C. 8. The chemical complex according to claim 6, wherein the ethylene halide unit is present and reacts ethylene, optionally in the presence of oxygen with a halide to produced one or more products selected from the group consisting of ethyl chloride, ethylene chloride, ethylene dichloride, ethyl bromide, ethylene bromide and ethylene dibromide. 9. The chemical complex according to claim 6, wherein the acetic acid unit is present and oxidizes one or more of ethane and ethylene from the oxidative dehydrogenation unit, the steam cracker or both to produce acetic acid. 10. The chemical complex according to claim 9, wherein acetic acid from the acetic acid unit is reacted with ethylene to produce vinyl acetate. 11. The chemical complex according to claim 3, wherein the oxidative dehydrogenation catalyst is supported on an inert ceramic support having a surface area from 20 to 5 m2/g selected from oxides of titanium, zirconia, aluminum, magnesium, yttria, lantana, silica and their mixed compositions, to provide from 0.1 to 20 weight % of said catalyst and from 99.9 to 80 weight % of said inert ceramic support. 12. The chemical complex according to claim 11, wherein the ethylene halide unit is present and reacts ethylene, optionally in the presence of oxygen with a halide to produced one or more products selected from the group consisting of ethyl chloride, ethylene chloride, ethylene dichloride, ethyl bromide, ethylene bromide and ethylene dibromide. 13. The chemical complex according to claim 11, wherein the acetic acid unit is present and oxidizes one or more of ethane and ethylene from the oxidative dehydrogenation process, the steam cracker or both to produce acetic acid. 14. The chemical complex according to claim 13, wherein acetic acid from the acetic acid unit is reacted with ethylene to produce vinyl acetate.