DE10321607A1 - Biomass production, for use as fuel, involves fermentation and distillation and/or separation, and includes removal of soluble, globular sticky proteins - Google Patents

Abstract

Production of bioalcohol from biomass (especially rye and wheat straw waste) by fermentation and distillation and/or separation includes (in addition to removal of particulate sticky proteins) the removal of soluble, globular sticky proteins (SGSP's) in the biomass.

Description

The The invention relates to a method for producing bioalcohol from biomass, especially rye and wheat sludge Fermentation and Distillation and / or separation as well as the separation of particulate adhesive proteins.

The fermentation of biomass is under the aspect of the future planned addition of Bio alcohol to fuel economically of great importance. With the large-scale Production of bioalcohol prepares the presence of adhesive proteins, especially gluten, problems with downstream thermal Separation of the fermented alcohol. These proteins lead due to their very sticky Properties of deposits in distillation plants, resulting in shorter maintenance intervals leads. So far, these proteins have mostly been centrifuged or other separators. By sedimentation, regardless of whether forced in a centrifugal field or self-adjusting in clarifiers however, only those portions of the adhesive proteins accessible in the form of suspensions or in particle form. Physically dissolved globular proteins remain in the prepared ones Schlämpen. These proteins settle in the subsequent thermal separation on heat exchanger surfaces and lead at a significant additional Maintenance.

The The invention has for its object an improved method for the production of bioalcohols from biomass, especially rye and Weizenschlämpen, through fermentation and distillation and / or separation and the separation of particulate adhesive proteins provide with the above disadvantages avoided become.

The object is achieved according to the invention in that soluble globular adhesive proteins, which preferably have molecular weights greater than or equal to 10,000 daltons, are separated off in advance of the alcohol separation, in particular by denaturation and also by membrane techniques. A combination of the two methods is particularly efficient. By denaturing disruptive adhesive proteins, which can be achieved very efficiently in the heat by means of Lewis acids, preferably Fe ³⁺ salts, particularly preferably FeCl ₃ , particulate proteins are obtained which are easy to separate by means of micro or ultrafiltration membranes. The addition of bases in such a solution leads to a precipitation of the dissolved proteins, so that a simple filtration or clarification can be sufficient for the separation.

However, nanofiltration membranes or membranes whose separation area is in the area of reverse osmosis are particularly efficient, since these membranes can be used for further very advantageous processing of the process liquids to be fermented or already fermented. This will be explained in the following exemplary embodiments. In the first exemplary embodiment, after the biomass has been mashed in and the particulate and / or suspended adhesive proteins have been separated off by appropriate classic separator technology or their enzymatic cleavage, a Lewis acid, preferably Fe ³⁺ salts, particularly preferably FeCl _{3, is} added and the mash is added Temperatures of 70 to 100 ° C heated. In this process, the globular proteins denature. Higher temperatures accelerate the process. These proteins are completely precipitated by adding bases. The proteins thus precipitated can be separated off by clarification, centrifugation or filtration. Enzymes are then added to liquefy and saccharify the mash. After the fermentation process, the yeasts are separated and the alcohol can be separated in a thermal separation step. The adhesive proteins can also be precipitated after the fermentation, in which case the denatured proteins are separated off together with the yeasts.

In a second advantageous embodiment, after the biomass has been mashed in, the particulate or suspended adhesive proteins are separated or enzymatically cleaved. The mash obtained is then mixed with a Lewis acid, preferably Fe ³⁺ salts, particularly preferably FeCl ₃ , and heated as described in Example 1. After the addition of bases, the precipitated proteins are also removed as described in Example 1. The denaturing and removal of the proteins can also take place at another point during the process, for example after saccharification. The dissolved proteins can also be retained without prior denaturation on a membrane with a molecular weight cut off (MWCO) of less than 10,000 Daltons, albeit at lower flows.

After adding enzymes, the mash is liquefied and saccharified. The strength of the mash is broken down to 96 to 100% to mono- and disaccharides. The sugar solution thus obtained is transferred to a working container which is coupled to a nanofiltration unit. By adding water to this working container, the glucose contained there is discharged enriched via the nanofiltration membrane. The permeate from the nanofiltration, which is now very rich in glucose, is then subjected to reverse osmosis, which results in a concentration of the glucose. The concentrates of reverse osmosis, which contain these concentrated glucose, who which is then fed to the fermentation. The permeate of reverse osmosis is water and is returned to nanofiltration, which creates an internal water cycle. These permeates can also be used to mash the grain. Since the concentrates from the reverse osmosis give a very pure glucose solution, the fermentation to alcohol can be simplified because there are no more contaminants. The same applies to the downstream thermal separation stages for separating the bioalcohol produced.

In a further advantageous embodiment, the particulate and / or suspended protein substances are removed as in exemplary embodiments 1 and 2. Then, by adding enzymes, the mash is liquefied and saccharified. This is then fermented. The alcohol-containing fermentation broths obtained are mixed with Lewis acids, preferably Fe ³⁺ salts, particularly preferably FeCl ₃ , and heated, with the result that the globular dissolved adhesive proteins are denatured. These can be separated together with the yeasts still present in the broths. These fermentation broths are then fed to a working container which is coupled to a nanofiltration unit and / or reverse osmosis unit, which has low ethanol retention. By adding water, ethanol is flushed out of the fermentation broth through these membranes. The permeate obtained in the first membrane unit is concentrated in a downstream membrane unit with high ethanol retention. The permeates obtained are used to rinse the alcohol out of the first membrane unit, so that an internal water cycle results. The concentrates of the second membrane unit show only small amounts of foreign matter, so that the subsequent step for the thermal separation of the alcohol can be carried out with very pure feed solutions, as a result of which downtimes are minimized by the necessary cleaning work in the separation stages.

Further Details and features of the present invention may be the the following description of the figures. The illustrated embodiments serve for explanation and are not restrictive.

In 1 it is shown that the biomass to be fermented, preferably wheat and / or rye ( 1 ) with water ( 2 ) for mashing ( 3 ) is given. Then the separation takes place ( 4 ) the particulate adhesive proteins using decanters and / or separators ( 5 ) instead of. Following the separation of the particulate adhesive proteins, denaturation and precipitation ( 8th ) of the dissolved globular proteins. Lewis acids and bases are used and the solution is heated ( 7 ). In the next step ( 9 ) the precipitated proteins are separated. After adding enzymes ( 11 ), liquefaction ( 12 ) and the addition of further enzymes ( 13 ) and saccharification ( 14 ) a 20% sugar solution ( 15 ) obtained, which is fermented in the subsequent step. From the alcohol-containing mash obtained in this way ( 17 ) the yeast and biomass are separated ( 18 and 18a ). The alkaline solution ( 19 ) the distillation ( 20 ) fed. As a result of the distillation, a distillation residue is obtained ( 21 ) and ethanol 86% ( 22 ).

In 2 it is shown that after the mashing in ( 3 ) the biomass prefers wheat and / or rye ( 1 ) with water ( 2 ) the particulate adhesive proteins using decanters and / or separators ( 5 ) separated. With the addition of Lewis acids, bases and by heating ( 7 ) the mash the denatured globular adhesive proteins are denatured and precipitated ( 8th ). Enzymes are added ( 11 ) to liquefy ( 12 ) and the addition of enzymes ( 13 ) for saccharification ( 14 ). The 20% glucose solution ( 29 ) is placed in a working container ( 23 ) transferred. The glucose and reduced disaccharides are then separated from the water using nanofiltration ( 25 ) and by means of reverse osmosis ( 26 ) concentrated. The water obtained as permeate in nanofiltration and reverse osmosis ( 27 ) is a partial stream ( 28 ) returned to the process. The 20% glucose solution ( 29 ) the fermentation ( 16 ) fed. The alcoholic solution obtained ( 17 ) after the yeast and biomass separation ( 18 and 18a ) distilled ( 20 ). The distillation becomes a distillation residue ( 21 ) and ethanol 86% ( 22 ) receive.

In 3 it is shown that after the mashing in ( 3 ) the biomass ( 1 ) with water ( 2 ), followed by the separation of particulate adhesive proteins ( 4 ) using decanters or separators ( 5 ), the mash with enzymes ( 11 ) to liquefy ( 12 ) and enzymes ( 13 ) for saccharification ( 14 ) is moved. The 20% solution thus obtained ( 15 ) the fermentation ( 16 ) fed. The alcoholic solution with X% alcohol obtained is heated with Lewis acids and bases ( 7 ). Then the yeast and biomass are separated ( 18 and 18a ). After transfer to a work container ( 23 ) and addition of water ( 2 ) the solution is subjected to nanofiltration and reverse osmosis ( 24 and 26 ). In another resersosmosis with high ethanol retention ( 32 ) a water-alcohol mixture with XY% ( 31 ) received, which is returned to the working container. As a concentrate of reverse osmosis, an alcoholic solution with X + Y% ( 33 ) obtained in a subsequent distillation ( 20 ) is processed. Ethanol 86% is obtained as product ( 22 ).

1

Biomass / wheat, rye

2

water

3

maceration

4

separation particulate Adhesive proteins

5

Decanters / separators

6

particulate adhesive proteins

7

Lewis acids / heating / bases

8th

Denaturation / precipitation

9

separation the felled proteins

10

felled, denatured proteins

11

enzymes

12

liquefaction

13

enzyme

14

saccharification

15

sugar solution

16

fermentation

17

alcohol

18

Yeast- and biomass separation

18a

Yeast- and biomass

19

alkaline solution

20

distillation

21

distillation residue

22

ethanol 86%

23

working container

24

nanofiltration

25

glucoses and reduced disaccarides

26

reverse osmosis

27

Permeate / water

28

partial flow

29

glucose 20%

30

alcohol X%

31

permeate Water / alcohol (X - Y)%

32

reverse osmosis with big Ethanol support

33

concentrate Alcohol (X + Y)%

Claims (16)

Process for the production of bioalcohols from biomass, in particular rye and wheat slurries, by fermentation and distillation and / or separation, and the separation of particulate adhesive proteins, characterized in that the soluble, globular adhesive proteins contained in the biomass are separated. Method according to claim 1, characterized in that the soluble globular Adhesive proteins be denatured before separation. Method according to claim 2, characterized in that the soluble globular Adhesive proteins using Lewis acids be denatured. Process according to claim 3, characterized in that the Lewis acid used is Fe ³⁺ salts. Process according to claim 4, characterized in that the Fe ³⁺ salt used is FeCl ₃ . Procedure according to a of claims 3 to 5, characterized in that the denatured protein substances precipitated by bases and be separated. Procedure according to a or more of the claims 1 to 6, characterized in that for the separation of the particular felled Protein nanofiltration and / or membrane filtration and / or osmotic and / or reversosmotic processes be used. Procedure according to a or more of the claims 1 to 7, characterized in that the alcohol obtained by means of Concentrated osmotic or reverse osmotic processes. Method according to one or more of claims 7 to 8, characterized in that the as Permeate water is returned to the process cycle. Procedure according to a or more of the claims 1 to 6, characterized in that it is used in the Biomass around rye and / or Weizenschlämpen acts as an adhesive protein Contain gluten. Procedure according to a or more of the claims 1 to 10, characterized by the following process stages: a) Maceration of the biomass, b) separation of the particulate and / or suspended adhesive proteins by separator technology and / or enzymatic cleavage, c) Addition of a Lewis acid, d) warming the mash at 70 to 100 ° C, e) Add bases to precipitate the denatured protein substances, f) Separation of the felled proteins by means of clarification and / or centrifuging and / or filtering, g) addition of Enzymes, especially yeasts, for liquefaction and saccharification, H) Separation of the yeasts after fermentation, i) Separation of the Alcohol using thermal processes. Method according to claim 11, characterized in that the Denaturation, precipitation and separation of the adhesive protein only after fermentation takes place. Method according to one or more of claims 1 to 10, characterized by the following process stages: a) mashing in of the biomass, b) separation of the particulate and / or suspended ten adhesive proteins by separator technology and / or enzymatic cleavage, c) addition of a Lewis acid, d) heating of the mash to 70 to 100 ° C, e) addition of bases to precipitate the denatured proteins, f) separation of the precipitated proteins by clarification and / or centrifuging and / or filtering, g) adding enzymes, in particular yeasts, for liquefaction and saccharification, h) transferring the sugar solution obtained into a working container which is coupled to a nanofiltration unit, i) adding water, j) removing the sugar over the nanofiltration membrane, k) supplying the sugar-containing permeate obtained to a reverse osmosis for water separation, l) enzymatic fermentation of the concentrated sugar solution m) recycling the water obtained in step k) into the process cycle, n) thermal separation of the alcohol Method according to claim 1, characterized in that the soluble globular Adhesive proteins be separated by membrane filtration, the used Membrane a molecular weight cut off (MWCO) less than 10,000 Daltons has. Procedure according to a or more of the claims 1 to 10, characterized by the following process stages: a) Maceration of the biomass, b) separation of the particulate and / or suspended adhesive proteins, c) Adding enzymes, especially yeasts, for liquefaction and saccharification, d) addition of a Lewis acid, e) heating the Mash at 70 to 100 ° C, f) Add bases to precipitate the denatured protein substances, G) Separation of the felled proteins by means of clarification and / or centrifuging and / or filtering, h) separation the yeast after fermentation, i) transfer of the solution into a working container and subsequent Nanofiltration and / or reverse osmosis, these low retention for alcohols, j) Add water to rinse out of alcohols over the membranes described in i), k) Transfer of the alcoholic permeate into a membrane filtration unit with high retention for alcohols, l) enrichment alcohol by separating water, m) thermal separation of alcohol. Claim according to claim 15, characterized in that the obtained in the filtration and / or the osmotic process Water in the process cycle is returned.