Process for producing propylene and aromatics from butenes by metathesis and aromatization
The invention is for a process for producing propylene and hexene (along with ethylene, pentenes, product butenes, heptenes and octenes) by metathesis from butenes (iso-, 1- and cis and trans 2-) and pentenes and then aromatizing the hexenes (along with higher olefins, such as heptenes and octenes) to benzene (along with toluene, xylenes, ethylbenzene and styrene). Since the desired products of the metathesis reaction are propylene and hexene, the feed to the metathesis reaction has a molar ratio for 1-butene:2-butene which favors production of propylene and 3-hexene with the concentration of hexenes and higher olefins in the metathesis product being up to 30 mole %. An isomerization reactor may be used to obtain the desired molar ratio of 1-butene:2-butene for the feed composition into the metathesis reactor. After the metathesis reaction, of hexene and higher olefins are separated for aromatization to benzene and other aromatics.
1. A process for producing propylene and aromatics comprising:
a) reacting in a metathesis reactor a hydrocarbon feed mixture comprising 1-butene, 2-butane and, optionally, isobutene in the presence of a metathesis catalyst at conditions to produce a product comprising ethylene, propylene, product butenes, pentenes, hexenes and higher olefins;
b1) separating from the product and recycling to the metathesis reactor the pentenes, the butenes, and optionally, the ethylene;
b2) separating the propylene from the product;
b3) separating the hexenes and higher olefins from the product; and
c) reacting the hexenes and higher olefins to aromatics in the presence of an aromatization catalyst, wherein the aromatization catalyst is Pt/CsGeZSM-5, Pt/KGeZSM-5 or Pt/KZSM-5,
wherein in step a) the molar ratio of 1-butene:2-butene in the hydrocarbon feed is in the range of from about 1:6 to about 6:1.
2. The process of claim 1 wherein the metathesis catalyst is WO 3 on SiO 2 , MoO 3 on Al 2 O 3 or Re 2 O 7 on Al 2 O 3 .
3. The process of claim 1 wherein the aromatization catalyst is Pt/CsGeZSM-5.
4. The process of claim 1 wherein the concentration of hexenes and higher olefins is up to 30%.
5. The process of claim 1 wherein the hydrocarbon feed mixture additionally comprises pentenes.
6. The process of claim 1 wherein the molar ratio of 1-butene:2-butene in the hydrocarbon feed is about 2:1.
7. The process of claim 1 wherein the hydrocarbon feed comprises a level of non-diene impurities, contaminants and poisons of no more than 100 ppm.
8. The process of claim 7 wherein the impurities, contaminants and poisons are acetylenic compounds, polar molecules, oxygenates, sulfur compounds, nitrogen compounds or combinations thereof.
9. The process of claim 8 wherein the polar molecule is water.
10. The process of claim 1 wherein metathesis is carried out at a temperature in the range of from about 25° C. to about 400° C. and a pressure in the range of from about 0 psig to about 500 psig.
11. The process of claim 1 wherein aromatization is carried out at a liquid hourly space velocity in the range between 0.1 and 100 h −1 , at a temperature in the range between 200 and 600° C. and at a pressure in the range between 1 and 315 psia.
12. The process of claim 1 wherein, after the butenes are recycled to the hydrocarbon feed, the hydrocarbon feed is isomerized to a 1-butene:2-butene molar ratio in the range of from about 1:6 to about 6:1 prior to being introduced into the metathesis reactor.
13. The process of claim 1 wherein the butenes are isomerized prior to being recycled to the hydrocarbon feed and the hydrocarbon feed has a 1-butene:2-butene molar ratio in the range of from about 1:6 to about 6:1 prior to being introduced into the metathesis reactor.
14. The process of claim 1 wherein the propylene:hexenes molar ratio in step a) is about 2:1.
15. The process of claim 1 wherein the propylene:hexenes molar ratio in the product is in the range of from about 1:1 to about 3:1.
16. The process of claim 1 wherein the concentration of hexenes in the product is about three to about twenty mole %.
17. A process for producing propylene and aromatics comprising:
a) reacting in a metathesis reactor a hydrocarbon feed mixture comprising 1-butene, 2-butene and, optionally, isobutene in the presence of a metathesis catalyst at conditions to produce a product comprising ethylene, propylene, product butenes, pentenes, hexenes and higher olefins;
b1) separating from the product and recycling to the metathesis reactor the pentenes, the butenes, and optionally, the ethylene;
b2) separating the propylene from the product; b3) separating the hexenes and higher olefins from the product; and
c) reacting the hexenes and higher olefins to aromatics in the presence of an aromatization catalyst, wherein the aromatization catalyst is Pt/CsGeZSM-5, Pt/KGeZSM-5 or Pt/KZSM-5,wherein greater than or equal to 86% aromatic selectivity is achieved;
wherein in step a) the molar ratio of 1-butene:2-butene in the hydrocarbon feed is in the range of from about 1:6 to about 6:1.
18. A process for producing propylene and aromatics comprising:
a) reacting in a metathesis reactor a hydrocarbon feed mixture comprising 1-butene, 2-butane and, optionally, isobutene in the presence of a metathesis catalyst at conditions to produce a product comprising ethylene, propylene, product butenes, pentenes, hexenes and higher olefins;
b1) separating from the product and recycling to the metathesis reactor the pentenes, the butenes, and optionally, the ethylene;
b2) separating the propylene from the product; b3) separating the hexenes and higher olefins from the product; and
c) reacting 3-hexene and higher olefins to aromatics in the presence of an aromatization catalyst, wherein the aromatization catalyst is Pt/CsGeZSM-5, Pt/KGeZSM-5 or Pt/KZSM-5,
wherein in step a) the molar ratio of 1-butene:2-butene in the hydrocarbon feed is in the range of from about 1:6 to about 6:1.