Process for conversion of lignin to reformulated, partially oxygenated gasoline

• US 6,172,272 B1
• Filed: 08/18/1999
• Issued: 01/09/2001
• Est. Priority Date: 08/21/1998
• Status: Expired due to Term

• Current Assignee: Alliance For Sustainable Energy LLC, University of Utah Research Foundation (State of Utah)
• Original Assignee: University of Utah (State of Utah)
• Inventors: Chornet, Esteban, Zmierczak, Wlodzimierz W., Shabtai, Joseph S.
• Primary Examiner(s): Yildirim, Bekir L.
• Application Number:
  US09/376,864
• Time in Patent Office: 510 Days
• Field of Search: 585/242, 585/240, 585/469, 585/638, 585/639, 208/68, 208/108, 444/47, 444/50, 568/630
• US Class Current: 585/242
• CPC Class Codes: C10G 1/002 in combination with oil conversion- or refining processes
• CPC Class Codes: C10L 1/023 for spark ignition

Abstract

A high-yield process for converting lignin into reformulated, partially oxygenated gasoline compositions of high quality is provided. The process is a two-stage catalytic reaction process that produces a reformulated, partially oxygenated gasoline product with a controlled amount of aromatics. In the first stage of the process, a lignin feed material is subjected to a base-catalyzed depolymerization reaction, followed by a selective hydrocracking reaction which utilizes a superacid catalyst to produce a high oxygen-content depolymerized lignin product mainly composed of alkylated phenols, alkylated alkoxyphenols, and alkylbenzenes. In the second stage of the process, the depolymerized lignin product is subjected to an exhaustive etherification reaction, optionally followed by a partial ring hydrogenation reaction, to produce a reformulated, partially oxygenated/etherified gasoline product, which includes a mixture of substituted phenyl/methyl ethers, cycloalkyl methyl ethers, C₇-C₁₀ alkylbenzenes, C₆-C₁₀ branched and multibranched paraffins, and alkylated and polyalkylated cycloalkanes.

Claims

1. A process for converting lignin into reformulated, partially oxygenated gasoline, comprising the steps of:

(a) providing a lignin material;

(b) subjecting the lignin material to a base-catalyzed depolymerization reaction in the presence of a supercritical alcohol, followed by a selective hydrocracking reaction in the presence of a superacid catalyst to produce a high oxygen-content depolymerized lignin product; and

(c) subjecting the depolymerized lignin product to an etherification reaction to produce a reformulated, partially oxygenated/etherified gasoline product.

2. The process of claim 1, wherein the lignin material is selected from the group consisting of Kraft lignins, organosolve lignins, lignins derived from wood products or waste, lignins derived from agricultural products or waste, lignins derived from municipal waste, and combinations thereof.

3. The process of claim 1, wherein the lignin material includes water or is mixed with water in an amount from about 10 wt-% to about 200 wt-% with respect to the weight of the lignin material.

4. The process of claim 1, wherein the alcohol is methanol or ethanol.

5. The process of claim 1, wherein the depolymerization reaction utilizes a base catalyst selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, cesium hydroxide, and mixtures thereof.

6. The process of claim 5, wherein the base catalyst is dissolved in methanol or ethanol in a concentration from about 2 wt-% to about 10 wt-%.

7. The process of claim 1, wherein the depolymerization reaction utilizes a solid superbase catalyst having a Hammett function value greater than about 26.

8. The process of claim 7, wherein the solid superbase catalyst is selected from the group consisting of high-temperature treated MgO, MgO—

Na₂O, CsX-type zeolite, and combinations thereof.

9. The process of claim 1, wherein the depolymerization reaction is carried out at a temperature from about 230°

C. to about 330°

C.

10. The process of claim 1, wherein the depolymerization reaction time is from about 30 seconds to about 15 minutes.

11. The process of claim 4, wherein the methanol/lignin weight-ratio during the depolymerization reaction is from about 2 to about 7.5.

12. The process of claim 4, wherein the ethanol/lignin weight-ratio during the depolymerization reaction is from about 1 to about 5.

13. The process of claim 1, wherein the superacid catalyst is a platinum-modified catalyst.

14. The process of claim 13, wherein the superacid catalyst is selected from the group consisting of supported or nonsupported Pt/SO₄²⁻

/ZrO₂, Pt/WO₄²⁻

/ZrO₂, Pt/SO₄²⁻

/TiO₂, and combinations thereof.

15. The process of claim 1, wherein the depolymerized lignin product comprises a mixture of compounds belonging to the group consisting of alkylated phenols, alkylated alkoxyphenols, alkybenzenes, and branched paraffins.

16. The process of claim 1, wherein the etherification reaction includes reacting phenolic groups in the depolymerized lignin product at an elevated temperature and pressure with an alcohol in the presence of a superacid catalyst.

17. The process of claim 16, wherein the etherification reaction is carried out at a temperature from about 100°

C. to about 400°

C., and at a pressure from about 100 psig to about 2000 psig.

18. The process of claim 16, wherein the alcohol in the etherification reaction is methanol or ethanol.

19. The process of claim 16, wherein the catalyst in the etherification reaction is a sulfated or tungstated oxide of a metal selected from the group consisting of Zr, W, Mn, Cr, Mo, Cu, Ag, Au, and combinations thereof.

20. The process of claim 16, wherein the catalyst in the etherification reaction comprises a solid superacid selected from the group consisting of SO₄²⁻

/ZrO₂, WO₄²⁻

/ZrO₂, SO₄²⁻

/MnO_x/Al₂O₃, SO₄²⁻

/WO_x/Al₂O₃, and combinations thereof.

21. The process of claim 1, further comprising the step of subjecting a product of the etherification reaction to a partial ring hydrogenation reaction to produce a reformulated, partially oxygenated/etherified gasoline product.

22. The process of claim 21, wherein the hydrogenation reaction is performed at an elevated temperature and pressure in the presence of a catalyst.

23. The process of claim 22, wherein the hydrogenation reaction is carried out at a temperature from about 50°

C. to about 250°

C., and at a hydrogen pressure from about 500 psig to about 2500 psig.

24. The process of claim 22, wherein the catalyst in the hydrogenation reaction is selected from the group consisting of Pt/Al₂O₃, Pd/Al₂O₃, Pt/C, Pd/C, and combinations thereof.

25. The process of claim 21, wherein the hydrogenation reaction is moderated and controlled to produce a partially oxygenated/etherified gasoline product having a concentration of aromatics of about 25 wt-% or less.

26. The process of claim 1, wherein the partially oxygenated/etherified gasoline product comprises a mixture of compounds belonging to the group consisting of substituted phenyl/methyl ethers, cycloalkyl methyl ethers, C₇-C₁₀ alkylbenzenes, C₆-C₁₀ branched and multibranched paraffins, and alkylated and polyalkylated cycloalkanes.