Catalytic activation and oligomerization of isopentane-enriched mixtures

Patent metadata

Field	Value
Publication number	US-10745328-B2
Application number	US-201916364764-A
Country	US
Kind code	B2
Filing date	Mar 26, 2019
Priority date	Mar 27, 2018
Publication date	Aug 18, 2020
Grant date	Aug 18, 2020

Abstract

The present disclosure relates generally to processes and systems for producing liquid transportation fuels by converting a feed stream that comprises both isopentane and n-pentane, and optionally, some C6+ hydrocarbons. Isopentane and smaller hydrocarbons are separated to form a first fraction while n-pentane and larger components of the feed stock form a second fraction. Each fraction is then catalytically-activated in a separate reaction zone with a separate catalyst, where the conditions maintained in each zone maximize the conversion of each fraction to olefins and aromatics, while minimizing the production of C1-C4 light paraffins. In certain embodiments, the first fraction is activated at a lower temperature than the second fraction. Certain embodiments additionally comprise mixing at least a portion of the two effluents and contacting with an oligomerization catalyst to provide enhanced yields of aliphatic hydrocarbons that possess the characteristics of a blend component of a liquid transportation fuel or other value-added chemical products.

First claim

We claim:

1. A method for converting a feedstock comprising pentanes to produce a liquid transportation fuel or a blend component thereof, comprising:
a. providing a hydrocarbon feed stream comprising at least 50 wt. % pentanes, including both n-pentane and isopentane, wherein the hydrocarbon feed stream further comprises less than 10 wt. % of hydrocarbons containing four or fewer carbons;
b. at least partially separating various constituents in the hydrocarbon feed stream according to each constituent's characteristic vapor pressure, to produce:
i. a first fraction comprising at least 80% of the isopentane present in the feed stream, and at least 90% of hydrocarbons present in the feed stream that are characterized by a vapor pressure equal to or greater than the vapor pressure of isopentane;
ii. a second fraction that comprises at least 80% of the n-pentane present in the feed stream and at least 90% of any hydrocarbons containing six or more carbons that were in the feed stream;

c. contacting the first fraction with a first activation catalyst at conditions comprising a first temperature and first pressure that facilitate conversion of at least a portion of the first fraction by the first activation catalyst to a first effluent comprising C2-C5 olefins and aromatics;
d. contacting at least a portion of the second fraction with a second activation catalyst at a second temperature and second pressure that facilitate conversion of at least a portion of the second fraction by the second catalyst to produce a second effluent comprising C2-C5 olefins and aromatics, wherein the first temperature is lower than the second temperature;
e. combining at least a portion of the first effluent and the second effluent to produce a mixed effluent and contacting at least a portion of the mixed effluent with an oligomerization catalyst at conditions of temperature and pressure that facilitate the conversion of the mixed effluent to produce an oligomerization effluent comprising an increased wt. % of C6-C9 aliphatic hydrocarbons relative to the mixed effluent, wherein the contacting converts a portion of the mixed effluent to a liquid hydrocarbon product that comprises the liquid transportation fuel.

2. The method of claim 1 , further comprising splitting the oligomerization effluent into a condensable liquid hydrocarbons comprising at least 80 wt. % hydrocarbons that contain at least five carbons, and a light hydrocarbons fraction comprising at least 80 wt. % hydrocarbons that contain four or fewer carbons.

3. The method of claim 2 , further comprising separating the condensable liquid hydrocarbons to produce an aliphatic hydrocarbon fraction comprising aliphatic hydrocarbons containing from six to nine carbon atoms, and a recycle fraction comprising alkanes and olefins containing from four to six carbon atoms, wherein the aliphatic hydrocarbon fraction meets government specifications for use as a blend component of a liquid transportation fuel.

4. The method of claim 1 , wherein the feed stream comprises less than 5 wt. % of hydrocarbons containing four or fewer carbon atoms.

5. The method of claim 1 , wherein the feed stream comprises at least 60 wt. % pentanes.

6. The method of claim 1 , wherein the first temperature is at least 25° C. lower than second temperature.

7. The method of claim 1 , wherein the first temperature is at least 50° C. lower than second temperature.

8. The method of claim 1 , wherein the weight hourly space velocity of the first fraction through the first reactor is higher than the weight hourly space velocity of the second fraction through the second reactor.

9. The method of claim 1 , wherein the first catalyst differs from the second catalyst in at least one of chemical composition and structural composition.

10. The method of claim 1 , wherein the contacting of the mixed effluent with the oligomerization catalyst converts at least 50 wt. % of the mixed effluent to the liquid hydrocarbon product.

11. The method of claim 10 , wherein adding the diluent alters the specificity of at least one of the first activation catalyst and the second activation catalyst to increase the production of olefins, decrease the production of aromatics, or combinations thereof, thereby increasing the ratio of olefins to aromatics in the mixed effluent.

12. The method of claim 10 , wherein the diluent is added in an amount that is effective to provide an olefins to aromatics ratio in the range of 0.5 to 2.0 in the mixed effluent.

13. The method of claim 10 , wherein the diluent is added in an amount that is effective to provide an olefins to aromatics ratio in the range of 0.5 to 1.0 in the mixed effluent.

14. The method of claim 10 , wherein the diluent is selected from methane, ethane, propane, butanes, benzene, toluene, xylenes, alkyl- or dialkyl-benzenes, naphthenes, C2-C5 olefins, and combinations thereof.

15. The method of claim 1 , wherein a portion of the second fraction is not contacted with the second catalyst and is combined with the liquid hydrocarbon product of e).

16. The method of claim 1 , further comprising adding a diluent to at least one of: the first fraction prior to the contacting of c) and the second fraction prior to the contacting of d), wherein the diluent is characterized as less likely to react with the first catalyst than molecules present in the first fraction at the conditions of temperature and pressure that are maintained in the first reactor, and/or wherein the diluent is characterized as less likely to react with the second catalyst than molecules present in the second fraction at the conditions of temperature and pressure that are maintained in the second reactor.

17. The method of claim 1 , further comprising adding a diluent to at least one of: the first fraction prior to the contacting of c) and the second fraction prior to the contacting of d), wherein the diluent is does not react catalytically with the first activation catalyst at the conditions of temperature and pressure that are maintained in the first reactor, and/or wherein the diluent does not react catalytically with the second activation catalyst at the conditions of temperature and pressure that are maintained in the second reactor.

Assignees

• Phillips 66 Co

Inventors

• Baldridge Anthony O
• Mcdaniel Neal D
• Suttil James A
• Kundu Soumen
• Yao Jianhua
• Randolph Bruce B
• Sardashti Maziar
• Lusk Steven E
• Walston Jr Robert M

Classifications

• Y02P20/52

  using catalysts, e.g. selective catalysts · CPC title

• C10G2300/1081

  Alkanes · CPC title

• C07C4/10

  from acyclic hydrocarbons · CPC title

• C07C5/327

  Formation of non-aromatic carbon-to-carbon double bonds only · CPC title

• C07C4/06

  Catalytic processes {(C07C4/025 takes precedence)} · CPC title