ADDITIVE FOR BIOETHANOL FERMENTATION PROCESS AND METHOD FOR PRODUCING BIOETHANOL

Abstract

There is provided an additive for a bioethanol fermentation process comprising a polyoxyalkylene compound (A) having a Griffin's HLB value in the range of 0 to 6, a polyoxyalkylene polyol (B) and a base oil (C) that is liquid at 25° C. The compound (A) is preferably a mixture of a compound represented by a general formula (1) and a compound represented by a general formula (2). In the formula, R.sup.1 and R.sup.3 represent alkyl or alkenyl, R.sup.2 and R.sup.4 represent a hydrogen atom or a monovalent organic group, AO represents oxyalkylene having a carbon number of 3 to 18, a reaction residue of glycidol, a reaction residue of an alkyl glycidyl ether or a reaction residue of an alkenyl glycidyl ether, EO represents oxyethylene, m and n are 1 to 100, and p is 3 to 10.

R.sup.1O-(AO).sub.m—R.sup.2  (1)

R.sup.3O-(AO).sub.n-(EO).sub.p—R.sup.4  (2)

Claims

1. An additive for a bioethanol fermentation process comprising a polyoxyalkylene compound (A) having a Griffin's HLB value in the range of 0 to 6, a polyoxyalkylene polyol (B) and a base oil (C) that is liquid at 25° C.

2. The additive according to claim 1, wherein the polyoxyalkylene compound (A) is a mixture of a polyoxyalkylene compound (A1) represented by a general formula (1) and a polyoxyalkylene compound (A2) represented by a general formula (2):
R.sup.1O-(AO).sub.m—R.sup.2  (1)
R.sup.3O-(AO).sub.n-(EO).sub.p—R.sup.4  (2) wherein R.sup.1 and R.sup.3 represent an alkyl group or alkenyl group having a carbon number of 4 to 28, R.sup.2 and R.sup.4 represent a hydrogen atom or a monovalent organic group having a carbon number of 1 to 24, AO represents an oxyalkylene group having a carbon number of 3 to 18, a reaction residue of glycidol, a reaction residue of an alkyl glycidyl ether having a carbon number of 4 to 21 or a reaction residue of alkenyl glycidyl ether having a carbon number of 5 to 21, EO represents an oxyethylene group, m and n are an integer of 1 to 100, and p is an integer of 3 to 10.

3. The additive according to claim 1, wherein the polyoxyalkylene polyol (B) is at least one selected from the group consisting of a polyoxypropylene polyol (B1) represented by a general formula (3), a polyoxyethylene polyoxypropylene polyol (B2) represented by a general formula (4), a polyoxyethylene polyoxypropylene polyol (B3) represented by a general formula (5), a polyoxyethylene polyoxypropylene polyol (B4) represented by a general formula (6), and a polyoxyethylene polyoxypropylene polyol (B5) represented by a general formula (7);
R.sup.5—[—(PO).sub.q—H].sub.r  (3)
R.sup.6-[-(EO).sub.s—(PO).sub.q—H].sub.r  (4)
R.sup.7—[—(PO).sub.q-(EO).sub.s—H].sub.r  (5)
R.sup.8-[-(EO).sub.s—(PO).sub.q-(EO).sub.t—H].sub.r  (6)
R.sup.9—[—(PO).sub.q-(EO).sub.s—(PO).sub.z—H].sub.r  (7) wherein R.sup.5, R.sup.6, R.sup.7, R.sup.8 and R.sup.9 are a hydroxyl group or a reaction residue of an active hydrogen compound having a carbon number of 1 to 25, PO is an oxypropylene group, EO is an oxyethylene group, q, s, t and z are an integer of 1 to 100, and r is an integer of 1 to 10; and the oxyethylene group and the oxypropylene group in the general formulae (4), (5), (6) and (7) are bound in a block form.

4. The additive according to claim 1, wherein the base oil (C) that is liquid at 25° C. is at least one selected from the group consisting of a hydrocarbon oil (C1), a glycerin fatty acid ester (C2) a monoalcohol fatty acid ester (C3) and a silicone (C4).

5. The additive according to claim 1 further comprising at least one hydrophobic compound (D) selected from the group consisting of hydrophobic silica (D1), hydrophobic amide (D2), hydrophobic wax (D3), hydrophobic synthetic resin (D4) and hydrophobic metallic soap (D5).

6. The additive according to claim 1, wherein the content of the polyoxyalkylene compound (A) is 1 to 69% by weight, the content of the polyoxyalkylene polyol (B) is 1 to 63% by weight and the content of the base oil (C) that is liquid at 25° C. is 30 to 90, based on the total weight of the polyoxyalkylene compound (A), the polyoxyalkylene polyol (B) and the base oil (C) that is liquid at 25° C.

7. The additive according to claim 2, wherein the content of the polyoxyalkylene compound (A1) represented by the general formula (1) is 0.1 to 90% by weight, and the content of the polyoxyalkylene compound (A2) represented by the general formula (2) is 10 to 99.9% by weight, based on the weight of the polyoxyalkylene compound (A).

8. The additive according to claim 5, wherein the content of the hydrophobic compound (D) is 2 to 30% by weight based on the total weight of the polyoxyalkylene compound (A), the polyoxyalkylene polyol (B) and the base oil (C) that is liquid at 25° C.

9. A method for producing bioethanol in which at least one selected from the group consisting of saccharide raw materials, starch raw materials and wooden (or cellulose) raw materials is used as a raw material, the method comprising: a fermentation step of fermenting the raw material by adding the additive as defined in claim 1 to a fermentation liquid.

Description

EXAMPLES

[0097] Hereinbelow, the present invention will be described further in detail with reference to examples, but the present invention is not limited thereto. Unless otherwise indicated, parts mean parts by weight, and % means % by weight.

[0098] The Polyoxyalkylene compound (A), the polyoxyalkylene polyol (B), the base oil (C) that is liquid at 25° C. and the hydrophobic compound (D) used Examples, are shown below.

<Polyoxyalkylene Compound (A)>

[0099] Polyoxyalkylene compounds (a11 to a16, a21 to a27) synthesized by known methods are shown in Tables 1 to 2. In the tables, PO represents oxypropylene, EO represents oxyethylene, and BO represents oxybutylene (the same is applied also hereinafter).

TABLE-US-00001 TABLE 1 R.sup.1O—(AO).sub.m—R.sup.2 (1) R.sup.1 (AO).sub.m R.sup.2 HLB a11 Butyl (PO).sub.60 Lignoceryl 0 a12 Cetyl (PO).sub.14 Hydrogen atom 0 a13 Montanyl (BO).sub.1 Methyl 0 a14 Myristyl (PO).sub.14 Hydrogen atom 0 a15 Butyl (PO).sub.100 Hydrogen atom 0 a16 Cetyl (PO).sub.3 Hydrogen atom 0

TABLE-US-00002 TABLE 2 R.sup.3O—(AO).sub.n—(EO).sub.P—R.sup.4 (2) R.sup.3 (AO).sub.n p R.sup.4 HLB a21 Montanyl (PO).sub.10 10 Ethyl 6 a22 Cetyl (PO).sub.14 6 Hydrogen atom 4 a23 Butyl (PO).sub.100 3 Methyl 0.4 a24 Myristyl (PO).sub.14 4 Hydrogen atom 2.9 a25 Cetyl (BO).sub.1 3 Lignoceryl 3.3 a26 Myristyl (PO).sub.3 3 Hydrogen atom 5.1 a27 Butyl (PO).sub.60 7 Hydrogen atom 1.6

<Polyoxyalkylene Polyol (B)>

[0100] Polyoxyalkylene polyols (b31 to b37, b41 to b43, b51 to b53, b61 to b67, and b71 to b73) synthesized by known methods are shown in Tables 1 to 3.

TABLE-US-00003 TABLE 3 Structural formula b31 HO—[—(PO).sub.30—H].sub.1 b32 HO—[—(PO).sub.34—H].sub.1 b33 (Glyceryl)-[—(PO).sub.16—H].sub.3 b34 (Glyceryl)-[—(PO).sub.2—H].sub.3 b35 (Stearyl)-[—(PO).sub.75—H].sub.1 b36 C.sub.17H.sub.35COO—[—(PO).sub.15—H].sub.1 b37 CH.sub.3CH.sub.2N—[—(PO).sub.3—H].sub.2 b41 (Methyl)-[—(EO).sub.60—(PO).sub.70—H].sub.1 b42 HO—[—(EO).sub.3—(PO).sub.60—H].sub.1 b43 C.sub.2H.sub.5C(═O)N—[—(EO).sub.7—(PO).sub.3—H].sub.2 b51 (Lignoceryl)-[—(PO).sub.3—(EO).sub.3—H].sub.1 b52 HO—[—(PO).sub.60—(EO).sub.60—H].sub.1 b53 CH.sub.3CH.sub.2N—[—(PO).sub.3—(EO).sub.3—H].sub.2 b61 HO—[—(EO).sub.8—(PO).sub.37—(EO).sub.8—H].sub.1 b62 HO—[—(EO).sub.3—(PO).sub.37—(EO).sub.3—H].sub.1 b63 HO—[—(EO).sub.60—(PO).sub.37—(EO).sub.60—H].sub.1 b64 (Glyceryl)-[—(EO).sub.7—(PO).sub.3—(EO).sub.3—H].sub.3 b65 (Stearyl)-[—(EO).sub.7—(PO).sub.60—(EO).sub.3—H].sub.1 b66 C.sub.17H.sub.35COO—[—(EO).sub.2—(PO).sub.8—(EO).sub.2—H].sub.1 b67 CH.sub.3CH.sub.2N—[—(EO).sub.3—(PO).sub.5—(EO).sub.3—H].sub.2 b71 CH.sub.3CH.sub.2N—[—(PO).sub.50—(EO).sub.8—(PO).sub.3—H].sub.2 b72 HO—[—(PO).sub.3—(EO).sub.3—(PO).sub.60—H].sub.1 b73 (Stearyl)-[—(PO).sub.3—(EO).sub.60—(PO).sub.3—H].sub.2
<Base Oil (C) that is Liquid at 25° C.>

[0101] Base oil (c11) that is liquid at 25° C.: Mineral oil, COSMO PURESPIN G, manufactured by Cosmo oil lubricants Co., Ltd.

[0102] Base oil (c12) that is liquid at 25° C.: Mineral oil, COSMO PURESPIN E, manufactured by Cosmo oil lubricants Co., Ltd.

[0103] Base oil (c21) that is liquid at 25° C.: Edible rapeseed oil, manufactured by Nikko seiyu Co., Ltd.

[0104] Base oil (c31) that is liquid at 25° C.: Methyl oleate, EXCEPARL M-OL, manufactured by Kao Corporation, “EXCEPARL” is a registered trademark of this company

[0105] Base oil (c41) that is liquid at 25° C.: Dimethyl silicone oil (kinematic viscosity 50 (mm.sup.2/s, at 25° C.)), KF-96L-5CS, manufactured by Shin-Etsu Chemical Co., Ltd.

[0106] Base oil (c42) that is liquid at 25° C.: Dimethyl silicone oil, (kinematic viscosity 3000 (mm.sup.2/s, 25 C)), KF-96-3,000CS, manufactured by Shin-Etsu Chemical Co., Ltd.

[0107] Base oil (c43) that is liquid at 25° C.: Silicone compound in which, of the methyl groups of dimethylsilicone (number average molecular weight: 1800), four methyl groups per a molecule in average were substituted with a polyoxypropylene (25 mol) oxypropyl group

<Hydrophobic Compound (D)>

[0108] Hydrophobic compound (d1): Hydrophobic silica, Nipsil SS-100, manufactured by Tosoh Silica Corporation

[0109] Hydrophobic compound (d12): Hydrophobic silica, AEROSIL R972, manufactured by Nippon Aerosil Co., Ltd.

[0110] Hydrophobic compound (d13): Hydrophobic silica, SIPERNAT D10, manufactured by Degussa Japan Co., Ltd.

[0111] Hydrophobic compound (d14): Hydrophobic silica, Nipsil G-0251, manufactured by Tosoh Silica Corporation

[0112] Hydrophobic compound (d21): Ethylene bisoleylamide, ALFLOW AD-281F, manufactured by NOF Corporation

[0113] Hydrophobic compound (d23): Stearylamide, Amide AP-1, manufactured by Nippon Kasei Chemical Co., Ltd.

[0114] Hydrophobic compound (d24): Hexamethylene bisstearylamide, ITOHWAX J-630, manufactured by Itoh Oil Chemicals Co., Ltd.

[0115] Hydrophobic compound (d31): Micrcrystalline wax, Hi-Mic-2095, manufactured by Nippon Seiro Co., Ltd.

[0116] Hydrophobic compound (d32): Fischer-Tropsch wax, FT-105, manufactured by Nippon Seiro Co., Ltd.

[0117] Hydrophobic compound (d33): Oxidized polyethylene wax, Epolene E-10, manufactured by Eastman Chemical Company

[0118] Hydrophobic compound (d34): Alcohol-modified wax, OX-3405, manufactured by Nippon Seiro Co., Ltd.

[0119] Hydrophobic compound (d35): Carnauba wax, Carnauba Wax No. 1, manufactured by S. Kato & Co.

[0120] Hydrophobic compound (d41): Synthetic resin, product prepared in accordance with Example 1 of JP-A-2009-7506 {copolymer having as constitutional units (styrene)/(acrylonitrile)/(divinylbenzene)/(reactive dispersant obtained by jointing a propylene oxide adduct of glycerol and 2-hydroxymethyl methacrylate with tolylene diisocyanate (TDI))/(polyoxyalkylene ether prepared by adding propylene oxide to allyl alcohol) (particle diameter: 0.7 μm)}

[0121] Hydrophobic compound (d51): Aluminum stearate, SA-1500, manufactured by Sakai Chemical Industry Co., Ltd.

Example 1

[0122] The polyoxyalkylene compound (a11) [6.3 parts] and the polyoxyalkylene compound (a21) [0.7 parts] were uniformly mixed by stirring at 30° C. for 30 minutes by a blade-type stirrer, then the polyoxyalkylene polyol (b31) [63 parts] and the base oil (c11) that is liquid at 25° C. [30 parts] were added to this mixture, and the mixture was uniformly mixed by stirring at 30° C. for 1 hour to obtain an additive (1) for a bioethanol fermentation process of the present invention.

Examples 2 to 27

[0123] The same procedures were carried out as in Example 1, except for changing the polyoxyalkylene compound (a11) [6.3 parts], the polyoxyalkylene compound (a21) [0.7 parts], the polyoxyalkylene polyol (b31) [63 parts] and the base oil (c11) that is liquid at 25° C. [30 parts] to the polyoxyalkylene compounds, polyoxyalkylene polyols and base oils that is liquid at 25° C. (the type and the number of parts) shown in Table 4 to obtain the additives (2) to (27) for a bioethanol fermentation process of the present invention. As well, in Examples 2 and 6 to 19, hydrophobic compounds (the type and the number of parts) shown in Table 4 is added together with polyoxyalkylene polyols and base oils that is liquid at 25° C.

TABLE-US-00004 TABLE 4 Polyoxyalkylene compound (A) Polyoxyalkylene Base oil (C) that Hydrophobic (A1) (A2) polyol (B) is liquid at 25° C. compound (D) Number Number Number Number Number Type of parts Type of parts Type of parts Type of parts Type of parts Examples  1 a11 6.3 a21 0.7 b31 63 c11 30 — —  2 a12 17.5 a22 17.5 b32 15 c12 50 d12 5  3 a13 0.63 a23 62.37 b33 7 c21 30 — —  4 a11 35 — — b41 15 c31 50 — —  5 — — a21 21 b51 9 c41 70 — —  6 a12 10.5 a22 10.5 b61 9 c42 70 d13 2  7 a13 3.5 a23 3.5 b71 3 c43 90 d14 20  8 a14 3.5 a24 3.5 b32 3 c41 90 d21 30  9 a15 1.5 a25 3 b32 25.5 c11 70 d22 5 10 a16 17.85 a26 3.15 b33 9 c12 70 d23 5 11 a11 17.5 a27 17.5 b33 21 c11 50 d24 5 12 a11 17.5 a21 17.5 b34 15 c12 50 d31 5 13 a12 17.5 a22 17.5 b35 15 c11 50 d32 5 14 a13 17.5 a23 17.5 b36 15 c12 50 d33 5 15 a14 17.5 a24 17.5 b37 15 c11 50 d34 5 16 a11 17.5 a21 17.5 b42 15 c12 50 d35 5 17 a12 17.5 a22 17.5 b43 15 c11 50 d41 5 18 a13 17.5 a23 17.5 b52 15 c12 50 d51 5 19 a14 17.5 a24 17.5 b53 15 c11 50 d11 4 20 a11 62.1 a21 6.9 b64 1 c12 30 — — 21 a12 0.07 a22 68.93 b65 1 c11 30 — — 22 a13 0.8 a23 0.2 b66 63 c12 36 — — 23 a14 0.05 a24 0.95 b67 9 c11 90 — — 24 a11 32 a21 8 b72 10 c12 50 — — 25 a12 2 a22 38 b73 6 c11 54 — — 26 a13 4.8 a23 1.2 b62 40 c12 54 — — 27 a14 0.3 a24 5.7 b63 24 c11 70 — —

[0124] Using the additives for a bioethanol fermentation process obtained in Examples 1 to 27, the production efficiency test was carried out as follows, and the results are shown in Table 5. As a blank, the result of testing without using the additive for a bioethanol fermentation process is also shown in Table 5.

<Production Efficiency Test>

[0125] Since the production efficiency of bioethanol fermentation in laboratory levels cannot be compared, the following accelerated test was performed.

[0126] 100 mL of a bioethanol fermentation liquid created by diluting 200 parts of commercially available sugar cane molasses (purchased from MARUKYO NOSAN CO., LTD) with 800 parts of ion-exchanged water and 1 g of a dry yeast (SUPER CAMELLIA, a dried fungus body of Saccharomyces cerevisiae, purchased from Nisshin seifun Group Inc., “SUPER CAMELLIA” is a registered trademark of Nisshin seifun Group Inc.) were put in a glass graduated cylinder with an inner diameter of 50 mm×height of 350 mm, 30 μL of a measurement sample (additive for a bioethanol fermentation process) was added with a microsyringe, and a diffuser stone was inserted into the bottom of the liquid, then carbon dioxide gas was bubbled at 500 mL/min. The volume (mL) of the bioethanol fermentation liquid after 10 minutes was read, and the production efficiency (%) was calculated from the following equation. The smaller the value, the size of the fermenter to be used in the production can be reduced, and the production efficiency is improved.

Production efficiency(9)=(Volume of bioethanol fermentation liquid after 10 minutes)/100

TABLE-US-00005 TABLE 5 HLB of polyoxyalkylene Production compound (A) efficiency (%) Example 1 0 and 6 180 2 0 and 4 150 3 0 and 0.4 190 4 0 330 5 6 260 6 0 and 4 180 7 0 and 0.4 160 8 0 and 2.9 190 9 0 and 3.3 190 10 0 and 5.1 200 11 0 and 1.6 180 12 0 and 6 190 13 0 and 4 170 14 0 and 0.4 150 15 0 and 2.9 180 16 0 and 6 160 17 0 and 4 150 18 0 and 0.4 170 19 0 and 2.9 190 20 0 and 6 240 21 0 and 4 230 22 0 and 0.4 200 23 0 and 2.9 210 24 0 and 6 170 25 0 and 4 180 26 0 and 0.4 160 27 0 and 2.9 150 Blank —  600<

[0127] The additive for a bioethanol fermentation process of the present invention had extremely good production efficiency, as compared to those not using the additive for a bioethanol fermentation process (blank).

INDUSTRIAL APPLICABILITY

[0128] The additive for a bioethanol fermentation process of the present invention is suitable as an additive for improving the production efficiency of bioethanol.