IP Library › Granted Patent US 12,264,208
Granted Patent B2
US 12,264,208 · App. 18/829,679 · Granted Apr 1, 2025

Processes for converting C4 feeds to isobutylene, polyisobutylene, or derivatives thereof

Inventors: Clyde Edward Baxter, Jr. (League City, TX); Mark W. Roll (Boerne, TX); Billy W. Waycaster (Cypress, TX)
Assignee: NTP Tec, LLC
C08F10/10C07C5/2767
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Quick Facts
Patent No.
US 12,264,208
App. No.
18/829,679
Granted
Apr 1, 2025
Kind
B2
Abstract

Embodiments described herein generally relate to new processes for converting C4 feeds to isobutylene. In an embodiment is provided a process for forming isobutylene that includes hydroisomerizing 1,3-butadiene present in a C4 feed to form a hydroisomerization product effluent comprising isobutylene and 2-butene; and forming an isobutylene feed by separating the isobutylene from the hydroisomerization product effluent. Embodiments of the present disclosure also generally relate to new processes for converting C4 feeds to polyisobutylene. In an embodiment is provided a process that includes hydroisomerizing a C4 feed comprising 1,3-butadiene in a hydroisomerization reactor to form a hydroisomerization product effluent comprising isobutylene and 2-butene; separating the isobutylene from the hydroisomerization product effluent to form a first isobutylene-containing feed; forming a reaction mixture comprising a polymerization catalyst and the first isobutylene-containing feed; and reacting the reaction mixture, in a polymerization reactor, to form a polymerization product effluent comprising polyisobutylene.

Claims (47)

1. A process for forming isobutylene, the process comprising:

(a) hydroisomerizing, in a hydroisomerization unit, 1,3-butadiene present in a feed to a hydroisomerization product effluent comprising 2-butene, the hydroisomerizing the 1,3-butadiene comprising converting at least a portion of the 1,3-butadiene to the 2-butene;

(b) isomerizing at least a portion of the 2-butene present in the hydroisomerization product effluent to form an isomerization product effluent comprising 1-butene, 2-butene, and isobutylene, the isomerization product effluent having a higher concentration of isobutylene than the concentration of isobutylene in the hydroisomerization product effluent;

(c) combining the isomerization product effluent with the feed to form a mixture; and

(d) hydroisomerizing the mixture in the hydroisomerization unit.

2. The process of claim 1 , wherein:

the mixture formed at (c) comprises 1-butene; and

the hydroisomerizing the mixture at (d) comprises forming 2-butene from the 1-butene present in the mixture.

3. The process of claim 1 , wherein, after (c), the process further comprises:

separating at least a portion of the isobutylene from the mixture.

4. The process of claim 1 , wherein the feed comprising the 1,3-butadiene comprises greater than 3 wt % of the 1,3-butadiene based on a total wt % of the feed.

5. The process of claim 1 , wherein the feed comprising the 1,3-butadiene comprises an effluent from a steam cracker, a catalytic cracker, or combinations thereof.

6. The process of claim 1 , wherein the feed comprising the 1,3-butadiene is free of isobutylene.

7. A process for forming polyisobutylene, the process comprising:

(a) hydroisomerizing, in a hydroisomerization unit, 1,3-butadiene present in a feed to a hydroisomerization product effluent comprising 2-butene, the hydroisomerizing the 1,3-butadiene comprising converting at least a portion of the 1,3-butadiene to the 2-butene;

(b) isomerizing at least a portion of the 2-butene present in the hydroisomerization product effluent to form an isomerization product effluent comprising 1-butene, 2-butene, and isobutylene, the isomerization product effluent having a higher concentration of isobutylene than the concentration of isobutylene in the hydroisomerization product effluent;

(c) combining the isomerization product effluent with the feed to form a mixture;

(d) hydroisomerizing the mixture in the hydroisomerization unit to form a hydroisomerized mixture; and

(e) reacting a reaction mixture comprising at least a portion of the isobutylene present in the hydroisomerized mixture formed at (d) and a polymerization catalyst to form a first polymerization product effluent comprising polyisobutylene (PIB).

8. The process of claim 7 , wherein, after (c), the process further comprises:

separating the isobutylene from the mixture to form a first isobutylene-containing feed.

9. The process of claim 8 , further comprising:

polymerizing isobutylene present in the first isobutylene-containing feed to form a second polymerization product effluent comprising PIB.

10. The process of claim 7 , wherein:

the mixture formed at (c) comprises 1-butene; and

the hydroisomerizing the mixture at (d) comprises forming 2-butene from the 1-butene present in the mixture.

11. The process of claim 7 , further comprising:

removing unreacted isobutylene from the first polymerization product effluent; and

polymerizing the unreacted isobutylene.

12. The process of claim 7 , further comprising:

removing isobutylene oligomer byproducts from the first polymerization product effluent;

cracking the isobutylene oligomer byproducts to form a second isobutylene-containing feed; and

polymerizing isobutylene present in the second isobutylene-containing feed.

13. The process of claim 7 , further comprising:

oligomerizing isobutylene present in the isomerization product effluent to form an oligomerization effluent comprising isobutylene oligomers;

cracking the isobutylene oligomers to form a third isobutylene-containing feed; and

polymerizing isobutylene present in the third isobutylene-containing feed to PIB.

14. The process of claim 13 , wherein, prior to the cracking the isobutylene oligomers to form the third isobutylene-containing feed, the process further comprises:

separating normal butylenes from the oligomerization effluent.

15. The process of claim 7 , wherein the polymerization catalyst comprises a solid polymerization catalyst.

16. The process of claim 15 , further comprising:

separating the solid polymerization catalyst from the first polymerization product effluent;

regenerating polymerization catalyst from the separated solid polymerization catalyst; and

polymerizing isobutylene with the regenerated polymerization catalyst.

17. The process of claim 7 , wherein the feed comprising the 1,3-butadiene comprises greater than 3 wt % of the 1,3-butadiene based on a total wt % of the feed.

18. The process of claim 7 , wherein the feed comprising the 1,3-butadiene comprises an effluent from a steam cracker, a catalytic cracker, or combinations thereof.

19. The process of claim 7 , wherein the feed comprising the 1,3-butadiene is free of isobutylene.

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Oct 17, 2024
From: BAXTER, CLYDE EDWARD, JR.; ROLL, MARK W.; WAYCASTER, BILLY W.
To: NTP TEC, LLC
Reel/Frame 068932/0282 →
Continuity (5)
Continuation 18661249 · May 10, 2024
Provisional Application 63630397 · Jan 31, 2024
Provisional Application 63629098 · Sep 20, 2023
Provisional Application 63577757 · May 19, 2023
Related Publication 20240425624A1 · Dec 26, 2024
References Cited (110)
US 1885060A · Hoffmann et al. · 1932 [cited by applicant]
US 2404788A · Burk et al. · 1946 [cited by applicant]
US 2484384A · Levine et al. · 1949 [cited by applicant]
US 2552692A · Schulze et al. · 1951 [cited by applicant]
US 2677002A · Yahnke et al. · 1954 [cited by applicant]
US 2721889A · O'Young et al. · 1955 [cited by applicant]
US 2766312A · Serniuk et al. · 1956 [cited by applicant]
US 2804411A · Anderson et al. · 1957 [cited by applicant]
US 2804491A · May et al. · 1957 [cited by applicant]
US 2957930A · Jackson et al. · 1960 [cited by applicant]
US 2976338A · Thomas · 1961 [cited by applicant]
US 3068301A · Hervert et al. · 1962 [cited by applicant]
US 3114785A · Hervert et al. · 1963 [cited by applicant]
US 3119884A · Allen et al. · 1964 [cited by applicant]
US 3131156A · Grace · 1964 [cited by applicant]
US 3131320A · Shinada et al. · 1964 [cited by applicant]
US 4152499A · Boerzel et al. · 1979 [cited by applicant]
US 4256913A · Jung et al. · 1981 [cited by applicant]
US 4306105A · Abernathy et al. · 1981 [cited by applicant]
US 4400565A · Darden et al. · 1983 [cited by applicant]
US 4407731A · Imai · 1983 [cited by applicant]
US 4409410A · Cosyns · 1983 [cited by examiner]
US 4427791A · Miale et al. · 1984 [cited by applicant]
US 4427797A · Smith · 1984 [cited by applicant]
US 4427941A · Riedesel, Jr. et al. · 1984 [cited by applicant]
US 4429177A · Morganson et al. · 1984 [cited by applicant]
US 4533651A · Masters et al. · 1985 [cited by applicant]
US 4558168A · Gussow et al. · 1985 [cited by applicant]
US 4605808A · Samson · 1986 [cited by applicant]
US 4707731A · Ghazey · 1987 [cited by applicant]
US 4915255A · Curtis · 1990 [cited by applicant]
US 4918255A · Chou et al. · 1990 [cited by applicant]
US 4935577A · Huss, Jr. et al. · 1990 [cited by applicant]
US 5068487A · Theriot · 1991 [cited by applicant]
US 5068490A · Eaton · 1991 [cited by applicant]
US 5191044A · Rath et al. · 1993 [cited by applicant]
US 5268520A · Karn et al. · 1993 [cited by applicant]
US 5286823A · Rath · 1994 [cited by applicant]
US 5294578A · Ho et al. · 1994 [cited by applicant]
US 5300701A · Cherpeck · 1994 [cited by applicant]
US 5326920A · Ho et al. · 1994 [cited by applicant]
US 5326923A · Cooper et al. · 1994 [cited by applicant]
US 5408018A · Rath · 1995 [cited by applicant]
US 5408108A · Nakamura et al. · 1995 [cited by applicant]
US 5510560A · O'Young et al. · 1996 [cited by applicant]
US 5646332A · Cusumano et al. · 1997 [cited by applicant]
US 5663470A · Chen et al. · 1997 [cited by applicant]
US 5710225A · Johnson et al. · 1998 [cited by applicant]
US 5770539A · Chen et al. · 1998 [cited by applicant]
US 5789335A · Chen et al. · 1998 [cited by applicant]
US 5877365A · Chodorge · 1999 [cited by examiner]
US 5910550A · Rath · 1999 [cited by applicant]
US 5945575A · Sigwart et al. · 1999 [cited by applicant]
US 5962604A · Rath · 1999 [cited by applicant]
US 6207115B1 · Chodorge et al. · 2001 [cited by applicant]
US 6294578B1 · Arimoto et al. · 2001 [cited by applicant]
US 6384054B1 · Woosley et al. · 2002 [cited by applicant]
US 6384154B1 · Sigwart et al. · 2002 [cited by applicant]
US 6433238B1 · Di Girolamo et al. · 2002 [cited by applicant]
US 6441110B1 · Sigwart et al. · 2002 [cited by applicant]
US 6525149B1 · Baxter, Jr. et al. · 2003 [cited by applicant]
US 6562013B1 · Marasco, Jr. · 2003 [cited by applicant]
US 6562913B1 · Baxter, Jr. et al. · 2003 [cited by applicant]
US 6683138B2 · Baxter, Jr. et al. · 2004 [cited by applicant]
US 6686510B2 · Commereuc · 2004 [cited by examiner]
US 6710140B2 · Wettling et al. · 2004 [cited by applicant]
US 6867267B2 · Lewtas et al. · 2005 [cited by applicant]
US 6884858B2 · Baxter, Jr. et al. · 2005 [cited by applicant]
US 6952152B2 · Miya et al. · 2005 [cited by applicant]
US 6992152B2 · Lobue et al. · 2006 [cited by applicant]
US 7411104B2 · Yun et al. · 2008 [cited by applicant]
US 7498396B2 · Baxter, Jr. et al. · 2009 [cited by applicant]
US 8791216B2 · Baxter, Jr. · 2014 [cited by applicant]
US 8816028B2 · Baxter, Jr. · 2014 [cited by applicant]
US 9040645B2 · Baxter, Jr. · 2015 [cited by applicant]
US 9637422B2 · Kim et al. · 2017 [cited by applicant]
US 10202476B2 · Kim et al. · 2019 [cited by applicant]
US 10640590B2 · Baxter, Jr. · 2020 [cited by applicant]
US 11124585B2 · Baxter, Jr. · 2021 [cited by applicant]
US 11174206B2 · Baxter, Jr. · 2021 [cited by applicant]
US 11214637B2 · Baxter, Jr. · 2022 [cited by applicant]
US 11214638B2 · Kim et al. · 2022 [cited by applicant]
US 12116426B1 · Baxter, Jr. · 2024 [cited by examiner]
US 20060235252A1 · Gartside et al. · 2006 [cited by applicant]
US 20060235253A1 · Gartside et al. · 2006 [cited by applicant]
US 20120238716A1 · Baxter, Jr. · 2012 [cited by applicant]
US 20130317189A1 · Baxter, Jr. · 2013 [cited by applicant]
US 20180018808A1 · Punjani et al. · 2018 [cited by applicant]
US 20200002246A1 · Baxter, Jr. · 2020 [cited by examiner]
US 20200199271A1 · Baxter, Jr. · 2020 [cited by applicant]
CA 2866897A1 · 2013 [cited by applicant]
WO 9402243A1 · 1994 [cited by applicant]
WO 9526818A1 · 1995 [cited by applicant]
WO 2000013792A1 · 2000 [cited by applicant]
WO 2016047445A1 · 2016 [cited by applicant]
Lamprecht et al., Hydroisomerization of 1-pentene to isopentane in a Single Reactor, May 12, 2009, vol. 196, pp. 1206-1216, (Year: 2009). [cited by examiner]
Komatsu et al., Dehydroisomerization of butane into isobutene on Pt—Sn intermetallic compounds supported on H-SAPO-11, Journal of Catalysis, 241 (2006), pp. 426-434 (Year: 2006). [cited by examiner]
Wilson, Karen et al., “Synthesis of a Supported Solid Acid BF3 Catalyst”, J. of Chem. Soc., Chem. Commun., 1998, pp. 2135-2136. [cited by applicant]
Canadian Office Action for Application No. CA 3,053,389 dated Sep. 9, 2020. [cited by applicant]
Indian Office Action for Application No. IN 201947036946 dated Oct. 14, 2020. [cited by applicant]
Extended European Search Report dated Jan. 28, 2021 for Application No. 18758114.5. [cited by applicant]
Indian Examination Report dated May 20, 2021 for Application No. 202148004624. [cited by applicant]
Malaysia Office Action dated Sep. 29, 2021 for Application No. PI2019004684. [cited by applicant]
International Search Report and Written Opinion for Application No. PCT/2018/018808. [cited by applicant]
International Search Report and Written Opinion for Application No. PCT/US2019/039869 dated Sep. 9, 2019. [cited by applicant]
Indian Examination Report dated Mar. 29, 2021 for Application No. 202147003975. [cited by applicant]
Chemical Market Analytics by OPIS, a Dow Jones Company, “Special Focus: Crude C4 Market Overview”, Jul. 20, 2023; 13 pages. [cited by applicant]
International Search Report and Written Opinion dated Aug. 12, 2024 for Application No. PCT/US24/28930. [cited by applicant]
Lamprecht et al. ‘Hydroisomerization of 1-Pentene to Isopentane In A Single Reactor’, Chemical Engineering Communications, May 12, 2009 (May 12, 2009), vol. 196, pp. 1206-1216; p. 1209. [cited by applicant]
Komatsu et al. ‘Dehydroisomerization of butane into isobutene on Pt—Sn intermetallic compounds supported on H-SAPO-11’, Journal of Catalysis, Jun. 21, 2006 (Jun. 21, 2006), vol. 241, pp. 426-434; p. 426. [cited by applicant]