Membrane-based process for the recovery of lactic acid and glycerol from a "corn thin stillage" stream

• US 5,250,182 A
• Filed: 07/13/1992
• Issued: 10/05/1993
• Est. Priority Date: 07/13/1992
• Status: Expired due to Fees

• Current Assignee: New Energy Company of Indiana Limited
• Original Assignee: Zenon Environmental Incorporated (Veolia Environnement SA)
• Inventors: Bento, John M. A., Fleming, Hubert L.
• Primary Examiner(s): SPEAR JR, FRANK
• Application Number:
  US07/912,320
• Time in Patent Office: 449 Days
• Field of Search: 210/641, 210/651, 210/652, 210/259, 426/656
• US Class Current: 210/641
• CPC Class Codes: B01D 61/025 Reverse osmosis; Hyperfiltration
• CPC Class Codes: B01D 61/027 Nanofiltration
• CPC Class Codes: B01D 61/145 Ultrafiltration
• CPC Class Codes: B01D 61/147 Microfiltration
• CPC Class Codes: B01D 61/58 Multistep processes
• CPC Class Codes: C12F 3/10 from distillery slops
• CPC Class Codes: C12P 7/06 Ethanol, i.e. non-beverage
• CPC Class Codes: Y02E 50/10 Biofuels, e.g. bio-diesel

Abstract

"Thin stillage", discharged from a centrifuge in which relatively large >10 μm insoluble solids in an ethanol stillbottoms stream are separated from "whole stillage", is separated in a step-wise membrane separation process to recover lactic acid and glycerol, together. In each step, the permeate recovery is at least 50%. In a first step, an ultrafiltration (UF) membrane means produces a UF permeate stream in which not only essentially all the insoluble portion of said thin stillage >0.0.05 μm is removed as UF concentrate, but also at least 50% of solubles having a molecular weight >2×10⁵ Daltons, including dissolved proteins in said thin stillage. In a second step to which the UF permeate is fed, a nanofiltration (NF) membrane produces a NF permeate with a rejection of less than 30% of both the lactic acid and the glycerol, preferably less than 25%. Essentially all molecules larger than lactic acid or glycerol are removed in the NF concentrate. In a third step, to which the NF permeate is fed, a reverse osmosis (RO) membrane means produces demineralized RO water which contains essentially no lactic acid and glycerol, because these are rejected in the RO concentrate. Use of the membrane separation process in the production of ethanol based on the dry-milling of corn, eliminates the use of a conventional evaporator.

Claims

1. A two-step membrane recovery process for recovering lactic acid and glycerol, together, from thin stillage obtained from the distillation of beer produced in a fermentation zone, said process comprising,

(1) in a first membrane recovery step,

(a) flowing said thin stillage essentially free from insoluble suspended solids larger than about 10 μ

m, in cross-flow, to an ultrafiltration (UF) zone, at a temperature in the range from about 30°

0 C.-100°

C. and at a pressure in the range from 1 atm to 10 atm, said UF zone having at least one module containing a UF membrane having a pore size smaller than 0.1 μ

m, sufficient to remove suspended solids >

0.1 μ

m and `heavies` in the range from 1000-200,000 Daltons; and

,

(b) withdrawing an ultrafiltered permeate (UF permeate) and an ultrafiltered concentrate (UF concentrate) from said UF zone with recovery of UF permeate being at least 50% in said UF zone;

said UF permeate containing essentially all `lights` consisting of soluble solids having a molecular weight <

1000 Daltons, said solids being present in said thin stillage;

said UF concentrate containing essentially all solid insoluble particulates >

0.1 μ

m and essentially all `heavies` consisting of soluble solids having a molecular weight >

1000 Daltons; and

,

(2) in a second membrane recovery step,

(a) flowing said UF permeate at a temperature in the range from 30°

0 C.-100°

C. and at a pressure in the range from 5 atm to 40 atm, in cross-flow, to a nanofiltration (NF) zone having at least one module with a NF membrane permeable to non-ionized molecules having a molecular weight <

200 Daltons; and

,

(b) withdrawing a nanofiltered permeate (NF permeate) and a nanofiltered concentrate (NF concentrate) from said NF zone with recovery of NF permeate being at least 50% in said NF zone;

said NF permeate containing a major proportion by weight of lactic acid and glycerol present in said UF permeate, said NF permeate being essentially free of dissolved solids having a molecular weight >

200 Daltons;

said NF concentrate containing essentially all soluble solids having a molecular weight >

200 Daltons; and

,

(3) recovering said UF concentrate and said NF concentrate;

whereby no UF permeate or NF permeate is flowed to an evaporation zone, and the operation and maintenance of an evaporator for producing syrup from thin stillage is obviated.

2. The process of claim 1 wherein said pore size of said UF membrane is no greater than 0.05 μ

m so as to remove suspended insoluble solid particles >

0.05 μ

m;

said thin stillage to said UF zone is at a pressure in the range from 1-5 atm;

said NF membrane in said NF zone is permeable to molecules <

150 Daltons;

said UF permeate to said NF zone is at a pressure in the range from 10-25 atm;

said NF permeate contains at least 70% by weight of said lactic acid and glycerol present in said UF permeate; and

said UF concentrate and NF concentrate are recovered by flowing to a solids-concentration zone.

3. The process of claim 1, including a third membrane recovery step, comprising,

(a) flowing said NF permeate at a temperature in the range from about 30°

0 C.-60°

C. and at a pressure in the range from 25 atm to 70 atm, to a reverse osmosis (RO) zone containing at least one RO membrane permeable to molecules having a molecular weight <

50 Daltons; and

,

(b) withdrawing a RO permeate and a RO concentrate with recovery of said RO permeate being at least 50% in said RO zone;

whereby said RO concentrate contains about 90% of lactic acid and glycerol present in said NF permeate, and said RO permeate is demineralized water essentially free of dissolved solids; and

,

recirculating said RO permeate for reuse.

4. In a process for the production of industrial ethanol by dry-milling corn, fermenting a saccharified corn meal in a fermentation zone to produce a beer, distilling said beer to produce said ethanol and whole stillage, and centrifuging said whole stillage to obtain a separation of wet cake and thin stillage containing lactic acid and glycerol, the improvement comprising,

flowing said thin stillage to a membrane separation zone comprising at least two filtration zones, an ultrafiltration (UF) zone and a nanofiltration (NF) zone, each zone providing a permeate recovery of at least 50%, including,

flowing said thin stillage to said UF zone provided with a UF membrane having a sufficiently small pore size to reject a major portion by weight of dissolved solids having a molecular weight >

2×

10⁵ Daltons and essentially all suspended solids >

0.05 μ

m, so as to obtain an ultrafiltered permeate (UF permeate) essentially free of suspended solids >

0.05 μ

m, and an ultrafiltered concentrate (UF concentrate) containing solids having a nominal diameter >

0.05 μ

m;

flowing said UF permeate to said NF zone provided with a semipermeable membrane effective to reject dissolved solids having a molecular weight >

200 Daltons in a nanofiltered concentrate (NF concentrate);

recovering a nanofiltered permeate (NF permeate) containing a major portion by weight of said lactic acid and glycerol present in said thin stillage; and

, recovering said UF concentrate and said NF concentrate.

5. The process of claim 4 comprising, in addition,

flowing said UF concentrate and said NF concentrate to a drying zone;

and,

drying said UF and NF concentrates to a moisture content less than 5%.

6. The process of claim 4 comprising, in addition,

(a) flowing said NF permeate at a temperature in the range from 30°

0 C.-60°

C. and at a pressure in the range from 25 atm to 70 atm, to a reverse osmosis (RO) zone containing a RO membrane permeable to molecules having a molecular weight <

50 Daltons;

(b) withdrawing a RO permeate and a RO concentrate with recovery of said RO permeate being at least 50% through said RO zone;

whereby said RO concentrate contains at least 90% of lactic acid and glycerol present in said NF permeate, and said RO permeate is water essentially free of dissolved solids; and

,

(c) flowing said RO permeate for reuse.

7. The process of claim 6 wherein said UF membrane is an inorganic tubular membrane;

said NF membrane is an organic membrane of spiral wound material;

said NF permeate is flowed to said RO zone at a pressure in the range from 40-60 atm;

said RO membrane is an organic membrane of spiral wound material; and

, recovery of RO water is about 90%.

8. The process of claim 6, comprising flowing said RO water to said fermentation zone.

9. A proteinaceous animal feed obtained from corn thin stillage having a pH in the range from 3 to 5 and containing from 5 to 15% total solids, said thin stillage in turn being obtained from whole stillage after fermentation of beer, said feed being essentially free from lactic acid and glycerol, other organic components of said thin stillage being maintained in said feed having a moisture content of less than 5%, said feed consisting essentially of (i) water-insoluble solids having a primary particle size in the range from >

0.005 μ

m to <

0.1 μ

m, (ii) proteins having a molecular weight >

1000 Daltons, and (iii) fatty acids having a molecular weight >

150 Daltons, wherein each said (i), (ii) and (iii) is present in said corn thin stillage.

10. In a system for producing ethanol from corn, said system including, milling means for milling corn, liquefaction means for liquefying corn meal, saccharification means for saccharifying liquefied corn meal, fermentation means for fermenting saccharified corn meal, distillation means for distilling beer, and centrifuge means for centrifuging stillbottoms to provide corn thin stillage, the improvement comprising, plural membrane separation means, including, ultrafiltration (UF) membrane means in flow communication with said centrifuge means so as to receive thin stillage under sufficient pressure to produce a UF concentrate and a UF permeate, said UF membrane means including at least one tubular UF membrane having a pore size sufficient to remove molecules in the range from 1000-200,000 Daltons;

and,

nanofiltration (NF) membrane means in flow communication with said UF membrane means so as to receive said UF permeate under sufficient pressure to produce a NF concentrate and a NF permeate, said NF membrane means including a semipermeable membrane which effectively rejects molecules having a molecular weight >

200 Daltons;

whereby said NF permeate contains at least 90% of lactic acid and glycerol present in said UF permeate.

11. The system of claim 10 wherein said plural membrane separation means includes, in addition,

reverse osmosis (RO) membrane means in flow communication with said NF membrane means so as to receive said NF permeate under sufficient pressure to produce a RO concentrate and a RO permeate, said RO membrane means including a semipermeable membrane which effectively rejects molecules having a molecular weight >

150 Daltons;

whereby said RO permeate is demineralized water containing essentially no lactic acid or glycerol.

12. A proteinaceous animal feed obtained from corn thin stillage having a pH in the range from 3 to 5 and containing from 5 to 15% total solids, said thin stillage in turn being obtained from whole stillage after fermentation of beer, said feed being produced in a process for the production of industrial ethanol by dry-milling corn, comprising,

fermenting a saccharified corn meal in a fermentation zone to produce a beer, distilling said beer to produce said ethanol and whole stillage, and centrifuging said whole stillage to obtain a separation of wet cake and thin stillage containing lactic acid and glycerol, flowing said thin stillage to a membrane separation zone comprising at least two filtration zones, an ultrafiltration (UF) zone and a nanofiltration (NF) zone, each zone providing a permeate recovery of at least 50%, said UF zone having a UF membrane with a sufficiently small pore size to reject a major portion by weight of dissolved solids having a molecular weight >

2×

10⁵ Daltons and essentially all suspended solids >

0.05 μ

m, so as to obtain an ultrafiltered permeate (UF permeate) essentially free of suspended solids >

0.05 μ

m, and an ultrafiltered concentrate (UF concentrate) containing solids having a nominal diameter >

0.05 μ

m;

flowing said UF permeate to said NF zone having a semipermeable membrane effective to reject dissolved solids having a molecular weight >

200 Daltons in a nanofiltered concentrate (NF concentrate);

recovering a nanofiltered permeate (NF permeate) containing a major portion by weight of said lactic acid and glycerol present in said thin stillage;

recovering said UF concentrate and said NF concentrate;

flowing said UF concentrate and said NF concentrate to a drying zone; and

,

drying said UF and NF concentrates to a moisture content less than 5%.