Methods, systems and devices for simultaneous production of lactic acid and propylene glycol from glycerol

Patent metadata

Field	Value
Publication number	US-9447011-B2
Application number	US-201314646670-A
Country	US
Kind code	B2
Filing date	Nov 21, 2013
Priority date	Nov 21, 2012
Publication date	Sep 20, 2016
Grant date	Sep 20, 2016

Abstract

Methods, processes and systems for using solid catalysts to simultaneously produce lactic acid and propylene glycol from glycerol are provide, as are methods, processes and systems of converting glycerol use heterogeneous catalytic agents. Different combinations of catalysts and reaction conditions provide tunable ranges for the yields of lactic acid and propylene glycol. The conversion methods, processes and systems are not reliant on external hydrogen. Applications to crude glycerol, including that co-produced during biodiesel production, are also described.

First claim

What is claimed is:

1. A method of converting glycerol to lactic acid and propylene glycol, the method comprising:
providing liquid glycerol;
providing a heterogeneous catalyst, wherein the heterogeneous catalyst comprises a base ingredient and a dehydrogenation ingredient, wherein the base ingredient comprises an alkaline earth metal oxide selected from the group consisting of magnesium oxide (MgO), calcium oxide (CaO), and strontium oxide (SrO); and
reacting the liquid glycerol with the heterogeneous catalyst,
whereby glycerol is simultaneously converted to a product comprising lactic acid and propylene glycol.

2. The method of claim 1 , wherein the dehydrogenation ingredient comprises a metal catalyst.

3. The method of claim 2 , wherein the metal catalyst is selected from the group consisting of copper (Cu), cuprous oxide (Cu 2 O), copper oxide (CuO), copper chromite (Cu 2 Cr 2 O 5 ), barium promoted copper chromite (Ba—Cu 2 Cr 2 O 5 ) and copper ore.

4. The method of claim 1 , wherein the base ingredient and dehydrogenation ingredient of the heterogeneous catalyst are mixed or wherein the dehydrogenation ingredient is supported on the base ingredient.

5. The method of claim 4 , wherein the heterogeneous catalyst mixture comprises CaO and Cu 2 O.

6. The method of claim 4 , wherein the base supported dehydrogenation ingredient comprises Cu 2 O supported on CaO.

7. The method of claim 1 , wherein the glycerol is concentrated glycerol.

8. The method of claim 1 , wherein the glycerol is crude glycerol, wherein the crude glycerol comprises about 75% to about 85% glycerol and about 5% to about 15% water, wherein the crude glycerol has a pH of about 6 to about 7.

9. The method of claim 1 , wherein the dehydrogenation ingredient is recoverable and can be recycled in the method of converting glycerol to lactic acid and/or propylene glycol.

10. The method of claim 1 , wherein the source of glycerol is biodiesel production.

11. The method of claim 1 , wherein the molar ratio of the dehydrogenation ingredient to glycerol ranges from about 0.02 to about 0.10 and wherein the molar ratio of the base ingredient to glycerol ranges from about 0.2 to about 0.8.

12. The method of claim 1 , further comprising regenerating spent catalyst.

13. A method of converting glycerol to lactic acid and propylene glycol, the method comprising:
providing a glycerol stock;
providing a heterogeneous catalyst, wherein the heterogeneous catalyst comprises a base ingredient and a dehydrogenation ingredient;
reacting the glycerol stock with the heterogeneous catalyst;
cooling and washing the products of the reaction, wherein the products comprise lactate salt, glycerol and propylene glycol;
treating the lactate salt with sulfuric acid solution to form free lactic acid and a sulfate salt;
separating the propylene glycol from the remaining products, whereby glycerol is converted to a lactic acid and propylene glycol; and
regenerating spent catalyst, wherein the spent catalyst comprises Ca(OH) 2 and Cu, wherein the regeneration comprises a calcination process, wherein the regenerated catalyst comprise CaO and CuO.

14. The method of claim 13 , further comprising a two-phase distillation process to separate glycerol and propylene glycol.

15. The method of claim 13 , wherein glycerol remaining after the reaction is recycled a glycerol stock in the method of converting glycerol to lactic acid and propylene glycol.

16. The method of claim 13 , wherein the dehydrogenation ingredient comprises a metal catalyst, and wherein the base ingredient comprises an alkaline earth metal.

17. A glycerol conversion system, comprising:
a reactor for reacting stock glycerol with a heterogeneous catalyst, wherein the heterogeneous catalyst comprises a base ingredient and a dehydrogenation ingredient;
a rotary vacuum filter for cooling and washing the products of the reaction in the reactor, optionally wherein a filtrate containing calcium lactate, glycerol and propylene glycol is separated from a filter cake containing Cu and Ca(OH) 2 ;
a crystallizer for filtering out calcium lactate from the filtrate, wherein the calcium lactate is treated with sulfuric acid solution to form lactic acid;
a distillation tower for concentrating lactic acid; and
a series of separation towers for separating glycerol and propylene glycol from the filtrate.

18. The system of claim 17 , further comprising a furnace for calcinating Cu and Ca(OH) 2 in the filter cake to thereby form CuO and CaO, wherein CuO and CaO are recycled and used in the reactor as the dehydrogenation ingredient and base ingredient, respectively.

19. The system of claim 17 , further comprising storage containers for storing the produced lactic acid and propylene glycol.

20. The method of claim 1 , wherein the simultaneous production of lactic acid and propylene glycol utilizes hydrogen generated in situ during the conversion of glycerol such that an external hydrogen supply is not needed.

21. The method of claim 13 , wherein the simultaneous production of lactic acid and propylene glycol utilizes hydrogen generated in situ during the conversion of glycerol such that an external hydrogen supply is not needed.

22. The method of claim 1 , wherein the base ingredient comprises an alkaline earth metal oxide selected from the group consisting of calcium oxide (CaO) and strontium oxide (SrO).

23. The method of claim 1 , wherein the yield of lactic acid is about 50 to 70 mol %, wherein the yield of propylene glycol is about 17 to 30 mol %, and the glycerol conversion of about 87 to 95 mol %.

24. The method of claim 13 , wherein the yield of lactic acid is about 50 to 70 mol %, wherein the yield of propylene glycol is about 17 to 30 mol %, and the glycerol conversion of about 87 to 95 mol %.

25. The method of claim 12 , wherein the spent catalyst comprises Ca(OH) 2 and Cu, wherein the regeneration comprises a calcination process, wherein the regenerated catalyst comprise CaO and CuO.

Assignees

• Univ Tennessee Res Found

Inventors

• Ye Xiaofei Philip
• Liu Lu

Classifications

• B01J23/78

  with alkali- or alkaline earth metals · CPC title

• B01J19/24

  Stationary reactors without moving elements inside (B01J19/08, B01J19/26 take precedence; with stationary particles B01J8/02) · CPC title

• C07C29/00

  Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring · CPC title

• B01J2219/24

  Stationary reactors without moving elements inside · CPC title

• C07C51/00 Primary

  Preparation of carboxylic acids or their salts, halides or anhydrides (of acids by hydrolysis of oils, fats or waxes C11C) · CPC title