IP Library Granted Patent US 9,353,025
Granted Patent B2
US 9,353,025 · App. 14/799,808 · Granted May 31, 2016

Process for selective removal of acetylenes from gaseous streams

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Quick Facts
Patent No.
US 9,353,025
App. No.
14/799,808
Granted
May 31, 2016
Kind
B2
Abstract

The present discloses a process and catalyst therefor to selectively remove acetylenes from gaseous streams in the vapor phase. The process is particularly suitable for high yield recovery of olefinic hydrocarbons from gaseous streams in refinery processes.

Claims (15)

1. A vapor phase process for selective removal of at least 80 mole % of acetylenic impurities from an input gaseous stream wherein said input stream comprises C1 to C9 unsaturated hydrocarbon monoolefins, diolefins and acetylenic impurities wherein said process comprises contacting said input stream in the vapor phase at a temperature in the range of 250° C. (480° F.) to 900° C. (1650° F.) with a solid zinc-free catalyst, said catalyst having the following metals only: Ni, Fe, alkali metal, and optionally alkaline earth element(s) wherein said Ni is present in an amount of 0.25-20 wt % on a dry basis of said catalyst and Fe is present in an amount of 30-75 wt % on a dry basis of said catalyst; and thereafter recovering an output stream wherein said output stream retains at least 95 mole % of said C1 to C9 unsaturated hydrocarbon monoolefins and diolefins but lacks at least 80 mole % of said acetylenic impurities.

2. The process of claim 1 , wherein said process selectively removes at least 95 mol % of said acetylenic impurities.

3. The process of claim 1 , wherein said selectively removed acetylenic impurities are vinyl acetylene.

4. The process of claim 1 , wherein said temperature ranges from 480° C. (900° F.) to 650° C. (1200° F.).

5. The process of claim 1 , wherein said catalyst is in a reaction zone at a pressure of from 0.014 to 2.1 MPa (2-300 psia).

6. The process of claim 1 , wherein Ba is present in about 1-20 wt % on dry basis of said catalyst, Ni is present in about 1-15 wt % on dry basis of said catalyst, Na is present in about 0.5-30 wt % on dry basis of said catalyst, with the remainder of catalytic metal being Fe.

7. The process of claim 1 , wherein said Ba is present in about 5-8 wt % on dry basis of said catalyst, Ni is present in about 7-9 wt % on dry basis of said catalyst, Na is present in about 10-14 wt % on dry basis of said catalyst, with the remainder being Fe.

8. The process of claim 1 , wherein said catalyst is prepared from barium carbonate, nickel carbonate, sodium hydroxide and iron oxide.

9. The process of claim 1 , wherein said input stream contains about 1-2 mole % acetylenic impurities and said output stream contains less than 0.02 mole % acetylenic impurities.

10. The process of claim 1 , wherein said output stream retains more than about 98 mole % of said C1 to C9 unsaturated hydrocarbon monoolefins and diolefins.

11. The process of claim 1 , additionally comprising the step of regenerating the catalyst after use.

12. The process of claim 11 , wherein said regeneration comprises controlled oxidation with air or steam in the absence of hydrocarbon.

13. A zinc-free catalyst for selective removal of acetylenic impurities from a hydrocarbon stream, said catalyst having the following metals, only: Ni, Fe, alkali metal, and optionally alkaline earth element(s) wherein said Ni is present in an amount of 0.25-20 wt % on a dry basis of said catalyst, Fe is present in an amount of 30-75 wt % on a dry basis of said catalyst.

14. The zinc-free catalyst of claim 13 , wherein Ba is present in 1-20 wt % on dry basis of said catalyst, Ni is present in 1-10 wt % on dry basis of said catalyst, Na is present in 0.5-30 wt % on dry basis of said catalyst, with the remainder of catalytic metal being Fe.

15. The zinc-free catalyst of claim 13 , wherein Ba is present in 5-8 wt % on dry basis of said catalyst, Ni is present in 7-9 wt % on dry basis of said catalyst, Na is present in 10-14 wt % on dry basis of said catalyst, with the remainder of catalytic metal being Fe.

Assignments (20)
SECURITY INTEREST Recorded Dec 16, 2024
From: TPC GROUP LLC
To: JEFFERIES FINANCE LLC, AS AGENT
Reel/Frame 069594/0055 →
RELEASE OF SECURITY INTEREST Recorded Dec 16, 2024
From: GLAS TRUST COMPANY LLC
To: TPC GROUP LLC
Reel/Frame 069602/0182 →
TERMINATION AND RELEASE OF GRANT OF SECURITY INTEREST IN UNITED STATES PATENTS AT REEL/FRAME 060287/0820 Recorded Dec 20, 2022
From: GLAS AMERICAS LLC, AS COLLATERAL AGENT
To: TPC GROUP LLC
Reel/Frame 062171/0674 →
TERMINATION AND RELEASE OF SUPPLEMENTAL GRANT OF SECURITY INTEREST IN UNITED STATES PATENTS AT REEL/FRAME 049949/0024 Recorded Dec 20, 2022
From: U.S. BANK TRUST COMPANY, NATIONAL ASSOCIATION, AS SUCCESSOR COLLATERAL AGENT TO U.S. BANK NATIONAL ASSOCIATION
To: TPC GROUP LLC
Reel/Frame 062171/0658 →
TERMINATION AND RELEASE OF SUPPLEMENTAL GRANT OF SECURITY INTEREST IN UNITED STATES PATENTS AT REEL/FRAME 055119/0158 Recorded Dec 20, 2022
From: U.S. BANK TRUST COMPANY, NATIONAL ASSOCIATION, AS SUCCESSOR COLLATERAL AGENT TO U.S. BANK NATIONAL ASSOCIATION
To: TPC GROUP LLC
Reel/Frame 062171/0666 →
SECURITY INTEREST Recorded Dec 16, 2022
From: TPC GROUP LLC
To: ECLIPSE BUSINESS CAPITAL LLC, AS COLLATERAL AGENT
Reel/Frame 062130/0001 →
SECURITY INTEREST Recorded Dec 16, 2022
From: TPC GROUP LLC
To: GLAS TRUST COMPANY LLC, AS COLLATERAL AGENT
Reel/Frame 062130/0137 →
RELEASE OF SECURITY INTEREST AT REEL/FRAME 60113/0169 Recorded Dec 16, 2022
From: ECLIPSE BUSINESS CAPITAL LLC, AS AGENT
To: TPC GROUP LLC
Reel/Frame 062142/0523 →
RELEASE OF SECURITY INTEREST AT REEL/FRAME 37551/0742 Recorded Jun 8, 2022
From: BANK OF AMERICA, N.A., AS ADMINISTRATIVE AGENT
To: TPC GROUP LLC
Reel/Frame 060392/0859 →
GRANT OF SECURITY INTEREST IN UNITED STATES PATENTS Recorded Jun 6, 2022
From: TPC GROUP LLC
To: GLAS AMERICAS LLC, AS COLLATERAL AGENT
Reel/Frame 060287/0820 →
SECURITY INTEREST Recorded Jun 6, 2022
From: TPC GROUP LLC
To: ECLIPSE BUSINESS CAPITAL LLC, AS AGENT
Reel/Frame 060113/0169 →
SECURITY INTEREST Recorded Feb 2, 2021
From: TPC GROUP LLC
To: U.S. BANK NATIONAL ASSOCIATION, AS AGENT
Reel/Frame 055119/0158 →
TERMINATION AND RELEASE OF SECURITY INTEREST IN UNITED STATES TRADEMARKS AND PATENTS Recorded Aug 6, 2019
From: U.S. BANK NATIONAL ASSOCIATION, AS SUCCESSOR COLLATERAL AGENT TO WELLS FARGO BANK, NATIONAL ASSOCIATION
To: TPC GROUP LLC
Reel/Frame 049970/0219 →
CONFIRMATION OF SUCCESSION OF AGENCY Recorded Aug 5, 2019
From: WELLS FARGO BANK, NATIONAL ASSOCIATION
To: U.S. BANK NATIONAL ASSOCIATION
Reel/Frame 049963/0119 →
SECURITY AGREEMENT Recorded Aug 2, 2019
From: TPC GROUP LLC
To: U.S. BANK NATIONAL ASSOCIATION, AS COLLATERAL AGENT
Reel/Frame 049949/0024 →
TERMINATION AND RELEASE OF SECURITY INTEREST IN INTELLECTUAL PROPERTY Recorded Aug 2, 2019
From: RIVERSTONE CREDIT PARTNERS, L.P.
To: TPC GROUP, LLC
Reel/Frame 049949/0259 →
SECURITY INTEREST Recorded Jan 21, 2016
From: TPC GROUP LLC
To: WELLS FARGO BANK, NATIONAL ASSOCIATION, AS COLLATERAL AGENT
Reel/Frame 037551/0867 →
SECURITY INTEREST Recorded Jan 21, 2016
From: TPC GROUP LLC
To: BANK OF AMERICA, N.A., AS ADMINISTRATIVE AGENT
Reel/Frame 037551/0742 →
SECURITY INTEREST Recorded Jan 15, 2016
From: TPC GROUP LLC
To: RIVERSTONE CREDIT PARTNERS, L.P.
Reel/Frame 037499/0246 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Aug 19, 2015
From: DUFF, JOSEPH; MCFARLAND, CECIL G.
To: TPC GROUP LLC
Reel/Frame 036396/0795 →