Process and system for making cyclopentadiene and/or dicyclopentadiene

Patent metadata

Field	Value
Publication number	US-9896396-B2
Application number	US-201615288354-A
Country	US
Kind code	B2
Filing date	Oct 7, 2016
Priority date	Nov 4, 2015
Publication date	Feb 20, 2018
Grant date	Feb 20, 2018

Abstract

Processes and systems for making cyclopentadiene and/or dicyclopentadiene include converting acyclic C5 hydrocarbon(s) into CPD in a first reactor to obtain a first reactor hydrocarbon effluent, which is processed in an eductor to obtain an eductor effluent at higher total pressure than atmospheric pressure, separating the eductor effluent in a separator such as compression train to obtain a C5-rich fraction comprising CPD, dimerizing the C5-rich fraction in a second reactor to obtain a product effluent comprising DCPD, which is separated to obtain a DCPD-rich fraction. Multiple-stage of dimerization and separation steps can be optionally used to obtain multiple DCPD-rich fractions of various degrees of purity and quantity. C5-rich fractions from various stages of the process may be recycled to the first reactor, or converted into mogas components after selective hydrogenation. C5-rich fractions and mogas components may be optionally separated to produce value-adding chemicals.

First claim

What is claimed is:

1. A process for making cyclopentadiene (CPD) and/or dicyclopentadiene (DCPD), the process comprising:
(I) feeding a C5 feedstock comprising at least one acyclic C5 hydrocarbon into a first reactor;
(II) contacting the at least one acyclic C5 hydrocarbon with a catalyst under conversion conditions to obtain a first reactor hydrocarbon effluent from an outlet of the first reactor comprising: C5 components including CPD and acyclic diolefins; light components including hydrogen and C1-C4 hydrocarbons; one-ring aromatics; and multiple-ring aromatics;
(III) feeding at least a portion of the first reactor hydrocarbon effluent to a suction chamber of an eductor;
(IV) injecting a stream of a motive fluid through a nozzle into the suction chamber;
(V) obtaining an eductor effluent from an exit of the eductor comprising the motive fluid and CPD;
wherein:
the overall pressure of the first reactor effluent at the outlet of the first reactor is lower than the overall pressure of the eductor effluent at the exit of the eductor; and
the temperature of the first reactor effluent at the outlet of the first reactor is higher than the temperature of the eductor effluent at the exit of the eductor.

2. The process of claim 1 , further comprising:
(VI) separating at least a portion of the eductor effluent in a first separation sub-system to obtain (i) a first light components-rich fraction including H2 and C1-C4 hydrocarbons; (ii) a first C5-rich fraction; and (iii) a first multiple-ring aromatics-rich fraction.

3. The process of claim 1 , wherein:
the first reactor hydrocarbon effluent comprises CPD at a concentration of C(CPD)1 wt % and acyclic diolefins at a total concentration of C(ADO)1 wt %, both based on the total weight of C5s in the first reactor hydrocarbon effluent; and
C(CPD)1/C(ADO)1≧1.5.

4. The process of claim 1 , wherein:
the first reactor effluent at the outlet of the first reactor has an overall pressure in the range from 20 to 100 kilopascal and/or a temperature in the range from 500° C. to 800° C.

5. The process of claim 4 , wherein:
the eductor effluent at the exit of the eductor has an overall pressure in the range from 100 kilopascal to 400 kilopascal and/or a temperature in the range from 30° C. to 700° C.

6. The process of claim 4 , wherein:
the stream of the motive fluid when entering the suction chamber has an overall pressure in the range from 100 to 10,000 kilopascal and/or a temperature in the range from 30° C. to 700° C.

7. The process of claim 1 , wherein:
the eductor is operated under eductor conditions including at least one of: (i) a compression ratio in the range from 1 to 20; (ii) an entrainment ratio in the range from 0.05 to 3, and (iii) an expansion ratio in the range from 5 to 100.

8. The process of claim 1 , wherein the motive fluid comprises at least one of: C1-C5 hydrocarbons, benzene, mono or multiple alkyl benzenes, mono or multiple alkyl naphthalenes, water, and mixtures thereof.

9. The process of claim 1 , wherein the motive fluid is essentially free of materials capable of undergoing Diels-Alder condensation reactions with CPD.

10. The process of claim 1 , wherein hydrogen is co-fed into the first reactor, and the molar ratio of the hydrogen and the C5 feed fed into the first reactor is in a range from 0.1 to 3.0.

11. The process of claim 1 , further comprising recycling at least a portion of the hydrogen in the first light components-rich fraction into the first reactor.

12. The process of claim 2 , further comprising:
(VII) separating at least a portion of the first light components-rich fraction by using one or more of a pressure swing process, a rapid cycle pressure swing adsorption process, a cryogenic process, a thermal swing adsorption process, and a membrane separation process to obtain at least one of the following:
(i) a hydrogen-rich stream comprising at least 95 mol % of hydrogen;
(ii) a methane-rich stream; and
(iii) a C2-C4-rich stream.

13. The process of claim 12 , wherein at least a portion of the methane-rich stream and/or the C2-C4 rich stream is used as at least a portion of the motive fluid.

14. The process of claim 2 , further comprising:
(VIII) supplying at least a portion of the first C5-rich fraction into a second reactor operating under a first set of dimerization conditions;
(IX) obtaining a second reactor effluent from in the second reactor comprising CPD and DCPD; and
(X) separating at least a portion of the second reactor effluent to obtain a first DCPD-rich fraction comprising DCPD and a second C5-rich fraction.

15. The process of claim 2 , wherein step (VI) comprises at least one of the following:
(VIa) cooling the eductor effluent;
(VIb) increasing the total pressure of the eductor effluent;
(VIc) washing at least a portion of the eductor effluent with a wash oil;
(VId) removing light components from the eductor effluent;
(VIe) removing C6+ components from the eductor effluent; and
(VIf) removing at least a portion of the motive fluid.

16. The process of claim 2 , wherein step (VI) comprises washing the eductor effluent with a wash oil comprising at least one of: cylcohexane; monoalkyl, dialkyl, and trialkyl cyclohexanes; benzene; monoalkyl, dialkyl, and trialkyl benzenes; monoalkyl, dialkyl, trialkyl, and tetraalkyl naphthalenes; other alkylated multiple-ring aromatics, and mixtures and combinations thereof.

17. The process of claim 2 , wherein step (VI) comprises removing C4 and lighter components from the eductor effluent using a compression train with inter-stage cooling and vapor/liquid separation.

18. The process of claim 2 , further comprising:
(XI) feeding at least a portion of the second C5-rich fraction into a third reactor operating under a second set of dimerization conditions;
(XII) obtaining a third reactor effluent from the third reactor comprising CPD and DCPD; and
(XIII) separating at least a portion of the third reactor effluent to obtain a second DCPD-rich fraction and a third C5-rich fraction.

19. The process of claim 18 , further comprising:
(XIV) feeding at least a portion of the third C5-rich fraction into a fourth reactor operating under a third set of dimerization conditions;
(XV) obtaining a fourth reactor effluent comprising CPD and DCPD; and
(XVI) separating at least a portion of the fourth reactor effluent to obtain a third DCPD-rich fraction and a fourth C5-rich fraction.

20. The process of claim 2 , further comprising:
(XVII) recycling, directly or indirectly, at least a portion of at least one of the first C5-rich fraction, the second C5-rich fraction, the third C5-rich fraction, and the fourth C5-rich fraction, if produced, to the first reactor.

21. The process of claim 2 , further comprising:
(XVIII) selectively hydrogenating at least a portion of at least one of the first C5-rich fraction, the second C5-rich fraction, the third C5-rich fraction, and the fourth C5-rich fraction, if produced, to obtain a mogas component feed; and
(XIX) forming a motor gas blend from the mogas component feed.

22. The process of claim 21 , wherein the mogas component feedstock is essentially free of dienes.

23. The process of claim 2 , comprising:
(XX) separating at least a portion of at least one of the first C5-rich fraction, the second C5-rich fraction, the third C5-rich fraction, and the fourth C5-rich fraction, if produced, to obtain a C6-rich fraction and a fifth C5-rich fraction depleted in C6+

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Iaccino Larry L
• Leung Kevin C P

Classifications

• C07C2603/68

  Dicyclopentadienes; Hydrogenated dicyclopentadienes · CPC title

• C07C2103/68

  Chemistry & Metallurgy · mapped topic

• C01B2203/043

  Regenerative adsorption process in two or more beds, one for adsorption, the other for regeneration · CPC title

• C01B2203/1064

  Platinum group metal catalysts · CPC title

• C07C2101/10

  Chemistry & Metallurgy · mapped topic