US20210040131A1 - Decolorization of concentrated rhamnolipid composition - Google Patents
Decolorization of concentrated rhamnolipid composition Download PDFInfo
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- US20210040131A1 US20210040131A1 US17/079,162 US202017079162A US2021040131A1 US 20210040131 A1 US20210040131 A1 US 20210040131A1 US 202017079162 A US202017079162 A US 202017079162A US 2021040131 A1 US2021040131 A1 US 2021040131A1
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- 239000000203 mixture Substances 0.000 title claims abstract description 19
- FCBUKWWQSZQDDI-UHFFFAOYSA-N rhamnolipid Chemical compound CCCCCCCC(CC(O)=O)OC(=O)CC(CCCCCCC)OC1OC(C)C(O)C(O)C1OC1C(O)C(O)C(O)C(C)O1 FCBUKWWQSZQDDI-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000004042 decolorization Methods 0.000 title claims description 11
- 238000000034 method Methods 0.000 claims abstract description 35
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical class [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 claims abstract description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 28
- 230000002378 acidificating effect Effects 0.000 claims description 19
- 230000008569 process Effects 0.000 claims description 19
- 239000007791 liquid phase Substances 0.000 claims description 17
- 239000012071 phase Substances 0.000 claims description 9
- 239000002609 medium Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 6
- 239000007790 solid phase Substances 0.000 claims description 6
- 230000001965 increasing effect Effects 0.000 claims description 5
- 238000006386 neutralization reaction Methods 0.000 claims description 4
- 239000012736 aqueous medium Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 239000002351 wastewater Substances 0.000 abstract description 8
- 230000003472 neutralizing effect Effects 0.000 abstract description 2
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 31
- 229940045872 sodium percarbonate Drugs 0.000 description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- 230000003287 optical effect Effects 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 10
- 238000000855 fermentation Methods 0.000 description 9
- 230000004151 fermentation Effects 0.000 description 9
- 229960002163 hydrogen peroxide Drugs 0.000 description 9
- 230000009467 reduction Effects 0.000 description 8
- 239000007858 starting material Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 6
- 238000013019 agitation Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 150000002978 peroxides Chemical class 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 238000003916 acid precipitation Methods 0.000 description 3
- 239000003876 biosurfactant Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- SHZGCJCMOBCMKK-JFNONXLTSA-N L-rhamnopyranose Chemical compound C[C@@H]1OC(O)[C@H](O)[C@H](O)[C@H]1O SHZGCJCMOBCMKK-JFNONXLTSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 235000013379 molasses Nutrition 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- YNCMLFHHXWETLD-UHFFFAOYSA-N pyocyanin Chemical compound CN1C2=CC=CC=C2N=C2C1=CC=CC2=O YNCMLFHHXWETLD-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- SHZGCJCMOBCMKK-UHFFFAOYSA-N D-mannomethylose Natural products CC1OC(O)C(O)C(O)C1O SHZGCJCMOBCMKK-UHFFFAOYSA-N 0.000 description 1
- 229930186217 Glycolipid Natural products 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- PNNNRSAQSRJVSB-UHFFFAOYSA-N L-rhamnose Natural products CC(O)C(O)C(O)C(O)C=O PNNNRSAQSRJVSB-UHFFFAOYSA-N 0.000 description 1
- 241000589517 Pseudomonas aeruginosa Species 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010564 aerobic fermentation Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000843 anti-fungal effect Effects 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- WORJEOGGNQDSOE-UHFFFAOYSA-N chloroform;methanol Chemical compound OC.ClC(Cl)Cl WORJEOGGNQDSOE-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- MFLMBWASGCAJGO-UHFFFAOYSA-L disodium;hydrogen peroxide;carbonate Chemical compound [Na+].[Na+].OO.[O-]C([O-])=O MFLMBWASGCAJGO-UHFFFAOYSA-L 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000008821 health effect Effects 0.000 description 1
- 235000012907 honey Nutrition 0.000 description 1
- -1 hydroxy fatty acids Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000424 optical density measurement Methods 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229940121125 oxy clean Drugs 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
- C07H1/06—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
- C07H15/02—Acyclic radicals, not substituted by cyclic structures
- C07H15/04—Acyclic radicals, not substituted by cyclic structures attached to an oxygen atom of the saccharide radical
- C07H15/06—Acyclic radicals, not substituted by cyclic structures attached to an oxygen atom of the saccharide radical being a hydroxyalkyl group esterified by a fatty acid
-
- B01F17/0021—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
- C07H15/02—Acyclic radicals, not substituted by cyclic structures
- C07H15/04—Acyclic radicals, not substituted by cyclic structures attached to an oxygen atom of the saccharide radical
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/38—Alcohols, e.g. oxidation products of paraffins
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/001—Refining fats or fatty oils by a combination of two or more of the means hereafter
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/02—Refining fats or fatty oils by chemical reaction
- C11B3/04—Refining fats or fatty oils by chemical reaction with acids
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/662—Carbohydrates or derivatives
Definitions
- a method for decolorizing and optionally neutralizing a rhamnolipid composition comprising treating said composition with a percarbonate salt as well as the decolorized and optionally neutralized composition obtainable therefrom. Also provided is a method for improving the quality of the liquid phase generated (also referred to as the aqueous layer or wastewater) which contains a variety of organic and/or inorganic substances during from fermentation during said decolorization process.
- the surface-acting agents or surfactants play an essential role in an industrial application especially personal cares and household cleaning products due to their ability to foam, clean, disperse, emulsify and lower surface tensions.
- Most surfactants available in the market are chemically derived from petroleum. Therefore, the demand of biosurfactants has been significantly increased due to their eco-friendly properties (i.e., biodegradability and biocompatibility) [1].
- Rhamnolipids are one of the most investigated and well known biosurfactants since they have high biodegradability, low toxicity, high foaming and the ability to be synthesized from renewable feedstock [2-4].
- Rhamnolipids are interface-active glycolipids containing carbohydrates (rhamnose) and aliphatic acids (hydroxy fatty acids).
- RLs consist of one (monorhamnosylipids or mono-rhamnolipids) or two rhamnose units (dirhamnosylipids or di-rhamnolipids) and one or two (predominantly two) 3-hydroxy fatty acid residues.
- Several industrial applications include detergents and cleaners, antifungal [5, 6], cosmetics, bioremediation and enhanced oil recovery (EOR) [7].
- the production of rhamnolipids includes an aerobic fermentation of bacteria predominately Pseudomonas aeruginosa with various carbon and nitrogen sources such as vegetable oil, crude glycerol, molasses, soap stock [8, 9].
- the RL concentration is typically in the range of 1-50 g/L depending upon types of feedstock, fermentation condition and fermentation process [10-12]. Since the RL concentration obtained from the fermentation is very low, separation and purification are required afterwards to produce concentrated RL product (i.e., 30-90%RL concentration). The most common separation process starts with an acid precipitation. By adjusting the fermentation broth pH to 2-3 making the rhamnolipids insoluble in the aqueous solution and thus, precipitate out.
- a solvent extraction with ethyl acetate, hexane, chloroform-methanol and/orbutanol [13, 14] is also performed to further purify rhamnolipids from aqueous layer which is discarded. After stripping the solvent out [15], a concentrated viscous brownish-to-black oily rhamnolipid liquid is obtained.
- the concentration of rhamnolipids with 90% or less contains dark brown color [16, 17].
- the brownish-to-black color of concentrated rhamnolipids is possible due to the pigment, pyocyanin, produced by P. aeruginosa during fermentation [18-20].
- the dark color of the concentrated rhamnolipids appears to be an issue when being used as a biosurfactant for personal care and household cleaning products.
- the aqueous layer is sent to a wastewater treatment plant since it contains a variety of inorganic and organic substances unconsumed during fermentation.
- the most commonly measured quality of wastewater is the biochemical oxygen demand (BOD).
- BOD biochemical oxygen demand
- TSS total suspended solid
- an organic solvent-free process for obtaining a neutralized and decolorized composition comprising one or more rhamnolipids (RLs) comprising: (a) providing an aqueous medium comprising at least one rhamnolipid; (b) treating said medium provided with acid to obtain an acidic medium comprising a solid, liquid and oily phase; (c) removing at least the liquid phase from said acidic medium of (b) to obtain an acidic solid phase and optionally acidic oily phase and (d) treating said acidic solid phase and optionally acidic oily phase obtained in (c) with a composition comprising a percarbonate salt in an amount effective to neutralize and decolorize said acidic solid phase and optionally said acidic oil phase of step (c) to obtain said neutralized and decolorized composition.
- RLs rhamnolipids
- compositions comprising a neutralized and decolorized solution obtainable therefrom.
- the neutralization and decolorization step occurs at a temperature of between about 30-80° C. for at least about 30 minutes and in a more particular embodiment, to about 1 week.
- the composition used in step (d) to decolorize and neutralize may further comprises a second base, e.g., NaOH.
- percarbonate salt is present in a concentration of about 0.5-3% w/w equivalent hydrogen peroxide concentration (EHPC).
- a method for increasing the quality of the liquid phase obtained in step (b) comprising treating said liquid phase with an amount of percarbonate salt effective to increase said quality of the liquid phase.
- the quality of the liquid phase may be determined by measuring the biochemical oxygen demand (BOD) and/or total suspended solid (TSS).
- BOD biochemical oxygen demand
- TSS total suspended solid
- a method of reducing the BOD and/or TSS of at least about 25% in the liquid phase comprising treating said liquid phase with a composition comprising a percarbonate salt in an amount effective to reduce BOD and/or TSS of at least about 25% in said liquid phase.
- BOD and/or TSS is reduced at least about 30%, more particularly at least about 40%, even more particularly at least about 45%, yet even more particularly about 50%, yet even more particularly at least about 55% and even yet more particularly at least about 60%, wherein percarbonate salt is present at a concentration of about 0.2% to about 0.8% w/w EHPC.
- FIG. 1 schematically shows an overall process producing color reduced concentrated clarified broth (CR-CCB) with sodium percarbonate treated acid-form concentrated clarified broth (ACCB).
- FIG. 2 schematically shows the reaction scheme used in Example 2 of U.S. application Ser. No. 14/992,995, filed Jan. 11, 2016 (published as US20160272667).
- FIG. 3 shows a comparison of the color of the samples with sodium percarbonate addition at 0.75, 1, 1.25, 1.5, 2, 2.5 and 3% w/w EHPC (from left to right). Pictures were taken at 30 min of heating at 60° C. and 250 rpm.
- FIG. 4 shows a comparison of the color of the samples with sodium percarbonate addition at 0.75, 1, 1.25, 1.5, 2, 2.5 and 3% w/w EHPC (from left to right). Pictures were taken at 3 hours of heating at 60° C., 250 rpm.
- FIG. 5 shows the color of CCB obtained from Example 2 of US20160272667 (0% w/w EHPC, 1 st left) vs. the color of CR-CCB obtained from sodium percarbonate addition at 2, 2.5 and 3%EHPC after heating at 60° C., 250 rpm for 30 min (from 2 nd left to right).
- FIG. 6 shows the optical density of CCB sample (0% w/w EHPC) and CR-CCB with various sodium percarbonate concentrations (2-3% w/w EHPC) after heating at 60° C. for 3 hours.
- FIG. 7 shows the optical density of CCB sample (0% w/w EHPC) and CR-CCB with various sodium percarbonate concentrations (1-2.5% w/w EHPC) after heating at 45° C. for 4 hours.
- FIG. 8 shows the %reduction in optical density (color) of CR-CCB samples with 1-2.5% w/w EHPC compared to no sodium percarbonate addition (0% w/w EHPC) after heating at 45° C. for 4 hours.
- the starting material is an acidic rhamnolipid slurry (the solid rhamnolipid containing phases) obtained from the precipitation of rhamnolipid out of clarified broth at about pH 2.1 as described in U.S. application Ser No. 14/992,995, filed Jan. 11, 2016 (published as US20160272667).
- the sodium percarbonate is added into the acidic rhamnolipid slurry at about 2-3% w/w equivalent hydrogen peroxide concentration (EHPC).
- Additional base such as NaOH can be used at about 0.5-1.5% w/w to bring the pH neutral if needed.
- Heating the solution at about 40-60° C. for 30 min. to several hours can speed up the decolorization process. After heating, the color of the concentrated rhamnolipids is lightened from black color like molasses to light brown or dark yellow color like honey. There is no loss of rhamnolipid concentration as a result of heating the solution.
- Example 3 Further provided as set forth in Example 3 is a process to increasing (alternatively referred to as enhancing) the quality of the liquid phase obtained.
- the increase in the quality of the liquid phase may be determined by BOD and/or TSS and/or OD measurements between about OD400 to about OD800.
- the process described here can be used in any fermentation product that is dark in color due to pigments produced by microorganisms.
- Example 1 Color Removal of Acid-Form Concentrated Clarified Broth (ACCB) with Sodium Percarbonate Addition at 0.75-3% w/w Equivalent Hydrogen Peroxide Concentration (EHPC) at 60° C.
- ACCB Acid-Form Concentrated Clarified Broth
- EHPC Equivalent Hydrogen Peroxide Concentration
- the starting material of this process is an acid-form concentrated clarified broth (ACCB) obtained from the precipitation of rhamnolipid out of clarified broth (CB) at pH 2.1 before neutralization step as described in US20160272667.
- ACCB acid-form concentrated clarified broth
- the pH of the starting material, ACCB is around 2.1.
- Sodium percarbonate having a chemical formula of Na 2 CO 3 .1.5H 2 O 2 is added to ACCB at 0.75-3% w/w equivalent hydrogen peroxide concentration (EHPC).
- EHPC equivalent hydrogen peroxide concentration
- FIGS. 3 and 4 A reduction in color of the samples with sodium percarbonate addition are shown in FIGS. 3 and 4 .
- Sodium hydroxide (NaOH) is added to the samples with sodium percarbonate addition less than 2% EHPC in order to bring the pH ⁇ 7.
- the amount of sodium percarbonate and NaOH added to the samples are shown in Table 1 along with the concentration of residue H 2 O 2 in the samples after 4 hours of heating at 60° C.
- the quantity of light absorbance or optical density (OD) of samples is measured at various wavelengths using a GENESYSTM 20 Visible Spectrophotometers (Thermo Scientific) in order to compare the concentration of light-absorbing constituent in the medium samples. Based on Beer's and Lambert's Laws, the higher the OD, the darker the sample.
- FIG. 6 clearly shows that the CCB sample designated as 0% EHPC (the 1 st left sample in FIG. 5 ) has the highest OD than the other samples with sodium percarbonate addition.
- the OD appears to be in the same range as those reduced color concentrated clarified broth (CR-CCB). This suggests that the color of the CR-CCB is relatively about the same darkest as 20% CCB.
- the starting material ACCB for this example is taken from the same batch/source and thus, the variation of the material is zero.
- Example 2 Color Removal of Acid-Form Concentrated Clarified Broth (ACCB) with Sodium Percarbonate Addition at 1%-2.5% w/w equivalent Hydrogen Peroxide Concentration (EHPC) at 45° C.
- ACCB Acid-Form Concentrated Clarified Broth
- EHPC Hydrogen Peroxide Concentration
- the starting material of this process is an acid-form concentrated clarified broth (ACCB) as described in Example 1.
- ACCB acid-form concentrated clarified broth
- EHPC equivalent hydrogen peroxide concentration
- NaOH sodium hydroxide
- the samples are then heated at 45° C. in non-baffle flasks with agitation at 350 rpm using MaxQTM 8000 Stackable Orbital Shakers (Thermo Scientific) to ensure consistency of the agitation speed and temperatures of all samples.
- the degree of darkness of the samples is quantified with a GENESYSTM 20 Visible Spectrophotometers (Thermo Scientific) to measure the optical density (OD) of the samples at various wavelengths. The lower the OD value, the lighter the sample color.
- the optical density of the samples is shown in FIG. 7 .
- the darkness color of the sample reduced with increasing the concentration of sodium percarbonate addition so as the OD value.
- the % reduction in optical density or color of the samples is also calculated against the sample without sodium percarbonate (0% w/w EHPC) and plotted in FIG. 8 which clearly supports this invention.
- Example 3 Color Removal and Wastewater Quality Enhancement of the Aqueous Layer Waste Stream from Non-Organic Solvent Rhamnolipid Concentrated Process by Acid Precipitation Described in US20160272667 with Sodium Percarbonate Addition
- the aqueous (water) layer obtained from acid precipitation step of clarified broth (CB) to obtain concentrated rhamnolipid products described in Examples 2-6 of US20160272667 is considered a wastewater from this process which is a starting material for this example.
- Sodium percarbonate is added into this acidic wastewater stream at 0.25%, 0.5% and 0.75% w/w EHPC.
- the samples After 1 hour of gentle agitation at 60° C., the samples are removed from heat and let to cool to room temperatures during 1-2 hours. Afterwards, the samples are subjected to optical density (OD) measurement and biological oxygen demand (BOD) and total suspended solid (TSS) analysis.
- OD optical density
- BOD biological oxygen demand
- TSS total suspended solid
- the optical density (OD) of the samples is measured with a GENESYSTM 20 Visible Spectrophotometers (Thermo Scientific). BOD and TSS are performed based on Standard Methods for the Examination of Water and Wastewater (available form www.standardmethods.org) 5210B and 2540, respectively).
- the % optical density at various wavelength (nm), %BOD and %TSS reductions of the samples are shown in Table 2. It clearly shows that treating the aqueous waste stream with sodium percarbonate at 0.5% w/w EHPC gives rise to the highest reduction of BOD and TSS while the most reduction in color is observed with 0.75% w/w EHPC sample at the studied wavelengths (400-800 nm). The color of the aqueous layer is reduced with the addition of sodium percarbonate from brown to yellow.
- OD 400 indicates optical density of samples at 400 nm.
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Abstract
Provided is a method for decolorizing and optionally neutralizing a rhamnolipid composition comprising treating said composition with a percarbonate salt as well as the decolorized and optionally neutralized composition obtainable therefrom. Also provided is a method for improving the quality of wastewater generated during said method.
Description
- Provided is a method for decolorizing and optionally neutralizing a rhamnolipid composition comprising treating said composition with a percarbonate salt as well as the decolorized and optionally neutralized composition obtainable therefrom. Also provided is a method for improving the quality of the liquid phase generated (also referred to as the aqueous layer or wastewater) which contains a variety of organic and/or inorganic substances during from fermentation during said decolorization process.
- The surface-acting agents or surfactants play an essential role in an industrial application especially personal cares and household cleaning products due to their ability to foam, clean, disperse, emulsify and lower surface tensions. Most surfactants available in the market are chemically derived from petroleum. Therefore, the demand of biosurfactants has been significantly increased due to their eco-friendly properties (i.e., biodegradability and biocompatibility) [1].
- Rhamnolipids (RLs) are one of the most investigated and well known biosurfactants since they have high biodegradability, low toxicity, high foaming and the ability to be synthesized from renewable feedstock [2-4]. Rhamnolipids are interface-active glycolipids containing carbohydrates (rhamnose) and aliphatic acids (hydroxy fatty acids). RLs consist of one (monorhamnosylipids or mono-rhamnolipids) or two rhamnose units (dirhamnosylipids or di-rhamnolipids) and one or two (predominantly two) 3-hydroxy fatty acid residues. Several industrial applications include detergents and cleaners, antifungal [5, 6], cosmetics, bioremediation and enhanced oil recovery (EOR) [7].
- The production of rhamnolipids includes an aerobic fermentation of bacteria predominately Pseudomonas aeruginosa with various carbon and nitrogen sources such as vegetable oil, crude glycerol, molasses, soap stock [8, 9]. The RL concentration is typically in the range of 1-50 g/L depending upon types of feedstock, fermentation condition and fermentation process [10-12]. Since the RL concentration obtained from the fermentation is very low, separation and purification are required afterwards to produce concentrated RL product (i.e., 30-90%RL concentration). The most common separation process starts with an acid precipitation. By adjusting the fermentation broth pH to 2-3 making the rhamnolipids insoluble in the aqueous solution and thus, precipitate out. A solvent extraction with ethyl acetate, hexane, chloroform-methanol and/orbutanol [13, 14] is also performed to further purify rhamnolipids from aqueous layer which is discarded. After stripping the solvent out [15], a concentrated viscous brownish-to-black oily rhamnolipid liquid is obtained.
- However, only a small quantity of rhamnolipids is available on the market at high price. It is very hard to find the availability online without submitting a request order form. Among those listed for sale, the concentration of rhamnolipids with 90% or less contains dark brown color [16, 17]. The brownish-to-black color of concentrated rhamnolipids is possible due to the pigment, pyocyanin, produced by P. aeruginosa during fermentation [18-20]. The dark color of the concentrated rhamnolipids appears to be an issue when being used as a biosurfactant for personal care and household cleaning products. The current possible route to remove this color is to purify the concentrated rhamnolipids further using a thin layer chromatography (TLC) to remove color. However, the process is costly and time consuming which is unnecessary to do so for the personal cares and household cleaning application since the concentration of rhamnolipids used in these products is very low (less than 5%).
- After separating rhamnolipids out, the aqueous layer is sent to a wastewater treatment plant since it contains a variety of inorganic and organic substances unconsumed during fermentation. The most commonly measured quality of wastewater is the biochemical oxygen demand (BOD). The higher the BOD, the higher organic maters in water thus, required more oxygen to break down those compounds which means a higher operating cost for the water treatment. The measurement for the total suspended solid (TSS) is also used to qualify the quality of the wastewater since they cause problem to aquatic life.
- Provided is an organic solvent-free process for obtaining a neutralized and decolorized composition comprising one or more rhamnolipids (RLs) comprising: (a) providing an aqueous medium comprising at least one rhamnolipid; (b) treating said medium provided with acid to obtain an acidic medium comprising a solid, liquid and oily phase; (c) removing at least the liquid phase from said acidic medium of (b) to obtain an acidic solid phase and optionally acidic oily phase and (d) treating said acidic solid phase and optionally acidic oily phase obtained in (c) with a composition comprising a percarbonate salt in an amount effective to neutralize and decolorize said acidic solid phase and optionally said acidic oil phase of step (c) to obtain said neutralized and decolorized composition. Also provided is a composition comprising a neutralized and decolorized solution obtainable therefrom. In a particular embodiment, the neutralization and decolorization step occurs at a temperature of between about 30-80° C. for at least about 30 minutes and in a more particular embodiment, to about 1 week. In a particular embodiment, the composition used in step (d) to decolorize and neutralize may further comprises a second base, e.g., NaOH. In a particular embodiment, percarbonate salt is present in a concentration of about 0.5-3% w/w equivalent hydrogen peroxide concentration (EHPC).
- Also provided is a method for increasing the quality of the liquid phase obtained in step (b) comprising treating said liquid phase with an amount of percarbonate salt effective to increase said quality of the liquid phase. The quality of the liquid phase may be determined by measuring the biochemical oxygen demand (BOD) and/or total suspended solid (TSS). In a particular embodiment, provided is a method of reducing the BOD and/or TSS of at least about 25% in the liquid phase comprising treating said liquid phase with a composition comprising a percarbonate salt in an amount effective to reduce BOD and/or TSS of at least about 25% in said liquid phase. In a more particular embodiment, BOD and/or TSS is reduced at least about 30%, more particularly at least about 40%, even more particularly at least about 45%, yet even more particularly about 50%, yet even more particularly at least about 55% and even yet more particularly at least about 60%, wherein percarbonate salt is present at a concentration of about 0.2% to about 0.8% w/w EHPC.
- Where a range of values are provided, it is understood that each intervening value, to the tenth of the unit of the lower limit unless the context clearly dictates otherwise, between the upper and lower limit of that range and any other stated or intervening value in that stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included in the smaller ranges and are also encompassed within the invention, subject to any specifically excluded limit in the stated range. Where the stated range includes one or both of the limits, ranges excluding either both of those included limits are also included in the invention.
- Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present invention, the preferred methods and materials are now described.
- All publications and patents cited in this disclosure are incorporated by reference in their entirety. Nothing herein is to be construed as an admission that the invention is not entitled to antedate such disclosure by virtue of prior invention. To the extent the material incorporated by reference contradicts or is inconsistent with this specification, the specification will supersede any such material.
- It must be noted that as used herein and in the appended claims, the singular forms “a,” “and” and “the” include plural references unless the context clearly dictates otherwise.
- Unless otherwise indicated, the term “at least” preceding a series of elements is to be understood to refer to every element in the series. Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the invention described herein. Such equivalents are intended to be encompassed by the present invention. Throughout this specification and the claims which follow, unless the context requires otherwise, the word “comprise”, and variations such as “comprises” and “comprising”, will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integer or step. Thus the terms “comprising”, “including,” “containing”, “having” etc. shall be read expansively or open-ended and without limitation. When used herein, the term “comprising” can be substituted with the term “containing” or sometimes when used herein with the term “having”.
-
FIG. 1 schematically shows an overall process producing color reduced concentrated clarified broth (CR-CCB) with sodium percarbonate treated acid-form concentrated clarified broth (ACCB). -
FIG. 2 schematically shows the reaction scheme used in Example 2 of U.S. application Ser. No. 14/992,995, filed Jan. 11, 2016 (published as US20160272667). -
FIG. 3 shows a comparison of the color of the samples with sodium percarbonate addition at 0.75, 1, 1.25, 1.5, 2, 2.5 and 3% w/w EHPC (from left to right). Pictures were taken at 30 min of heating at 60° C. and 250 rpm. -
FIG. 4 shows a comparison of the color of the samples with sodium percarbonate addition at 0.75, 1, 1.25, 1.5, 2, 2.5 and 3% w/w EHPC (from left to right). Pictures were taken at 3 hours of heating at 60° C., 250 rpm. -
FIG. 5 shows the color of CCB obtained from Example 2 of US20160272667 (0% w/w EHPC, 1st left) vs. the color of CR-CCB obtained from sodium percarbonate addition at 2, 2.5 and 3%EHPC after heating at 60° C., 250 rpm for 30 min (from 2nd left to right). -
FIG. 6 shows the optical density of CCB sample (0% w/w EHPC) and CR-CCB with various sodium percarbonate concentrations (2-3% w/w EHPC) after heating at 60° C. for 3 hours. -
FIG. 7 shows the optical density of CCB sample (0% w/w EHPC) and CR-CCB with various sodium percarbonate concentrations (1-2.5% w/w EHPC) after heating at 45° C. for 4 hours. -
FIG. 8 shows the %reduction in optical density (color) of CR-CCB samples with 1-2.5% w/w EHPC compared to no sodium percarbonate addition (0% w/w EHPC) after heating at 45° C. for 4 hours. - Provided is a process to reduce color of concentrated rhamnolipid solution (30-90%) using a sodium percarbonate (Na2CO3×1.5 H2O2). The starting material is an acidic rhamnolipid slurry (the solid rhamnolipid containing phases) obtained from the precipitation of rhamnolipid out of clarified broth at about pH 2.1 as described in U.S. application Ser No. 14/992,995, filed Jan. 11, 2016 (published as US20160272667). The sodium percarbonate is added into the acidic rhamnolipid slurry at about 2-3% w/w equivalent hydrogen peroxide concentration (EHPC). Additional base such as NaOH can be used at about 0.5-1.5% w/w to bring the pH neutral if needed. Heating the solution at about 40-60° C. for 30 min. to several hours can speed up the decolorization process. After heating, the color of the concentrated rhamnolipids is lightened from black color like molasses to light brown or dark yellow color like honey. There is no loss of rhamnolipid concentration as a result of heating the solution.
- Further provided as set forth in Example 3 is a process to increasing (alternatively referred to as enhancing) the quality of the liquid phase obtained. The increase in the quality of the liquid phase may be determined by BOD and/or TSS and/or OD measurements between about OD400 to about OD800.
- Although US20160272667 discloses the decolorization of the rhamnolipids obtained from an organic solvent-free process with peroxide treatment using hydrogen peroxide (H2O2) or organic peroxide (peroxyacetic acid) or inorganic peroxide (sodium peroxide), the peroxides disclosed may have a high risk of flammability, health and reactivity based on the degree of hazard listed on NAFA 704 [21]. Unlike the abovementioned chemicals, sodium percarbonate is an eco-friendly chemical that has been used in the household word wide commercially named as “Oxyclean” [22]. The advantages of using a sodium percarbonate as a decoloring agent over the peroxides are:
-
- 1. Safer to transport since the sodium percarbonate is a soda ash with hydrogen peroxide combined in the stable white powder form;
- 2. The decolorization with sodium percarbonate takes place simultaneously with the neutralization step and thus, the process is shorter as compared to the decolorization step described in US20160272667;
- 3. The working volume is significantly reduced compared to US20160272667 since the starting material is the concentrated rhamnolipid solution not the aqueous medium (e.g., fermentation medium or broth) and thus, only a small volume being treated;
- 4. The process is significantly shorter. The process is done within 1 hour compared to 48 hours.
- The process described here can be used in any fermentation product that is dark in color due to pigments produced by microorganisms.
- The starting material of this process is an acid-form concentrated clarified broth (ACCB) obtained from the precipitation of rhamnolipid out of clarified broth (CB) at pH 2.1 before neutralization step as described in US20160272667.
- The pH of the starting material, ACCB, is around 2.1. Sodium percarbonate having a chemical formula of Na2CO3.1.5H2O2 is added to ACCB at 0.75-3% w/w equivalent hydrogen peroxide concentration (EHPC). The samples are heated at 60° C. in baffle shake flasks with agitation at 250 rpm using MaxQ™8000 Stackable Orbital Shakers (Thermo Scientific) to ensure consistency of the agitation speed and temperatures of all samples.
- A reduction in color of the samples with sodium percarbonate addition are shown in
FIGS. 3 and 4 . - Sodium hydroxide (NaOH) is added to the samples with sodium percarbonate addition less than 2% EHPC in order to bring the pH ˜7. The amount of sodium percarbonate and NaOH added to the samples are shown in Table 1 along with the concentration of residue H2O2 in the samples after 4 hours of heating at 60° C.
-
TABLE 1 The amount of sodium percabonate, NaOH and hydrogen peroxide in the samples % % Na % % H2O2 % H2O2 EHPC percarbonate NaOH pH residue consumption 0.75% 2.3% 3.6% 6.9 0.50% 33% 1.00% 3.1% 1.9% 6.9 0.55% 45% 1.25% 3.8% 1.7% 7.0 0.65% 48% 1.50% 4.6% 1.5% 7.1 0.69% 54% 1.75% 5.4% 1.2% 7.4 0.78% 55% 2.00% 6.2% 1.0% 7.6 0.63% 69% 2.50% 7.7% 0% 7.7 0.25% 90% 3.00% 9.2% 0% 8.1 0.18% 94%
The color of the concentrated clarified broth (CCB) is significantly reduced with the addition of sodium percarbonate from dark brown to very light yellow as seen in theFIG. 5 . - The quantity of light absorbance or optical density (OD) of samples is measured at various wavelengths using a
GENESYS™ 20 Visible Spectrophotometers (Thermo Scientific) in order to compare the concentration of light-absorbing constituent in the medium samples. Based on Beer's and Lambert's Laws, the higher the OD, the darker the sample.FIG. 6 clearly shows that the CCB sample designated as 0% EHPC (the 1st left sample inFIG. 5 ) has the highest OD than the other samples with sodium percarbonate addition. By diluting the CCB sample (0% EHPC) 5 times with deionized water, the OD appears to be in the same range as those reduced color concentrated clarified broth (CR-CCB). This suggests that the color of the CR-CCB is relatively about the same darkest as 20% CCB. Please note that the starting material ACCB for this example is taken from the same batch/source and thus, the variation of the material is zero. - The starting material of this process is an acid-form concentrated clarified broth (ACCB) as described in Example 1. Sodium percarbonate is added to the starting material, ACCB, at 1%, 1.5%, 2% and 2.5% w/w equivalent hydrogen peroxide concentration (EHPC). Sodium hydroxide (NaOH) is also added to the samples with sodium percarbonate addition less than 2.5% w/w EHPC in order to bring the pH ˜7.
- The samples are then heated at 45° C. in non-baffle flasks with agitation at 350 rpm using MaxQ™ 8000 Stackable Orbital Shakers (Thermo Scientific) to ensure consistency of the agitation speed and temperatures of all samples. The degree of darkness of the samples is quantified with a
GENESYS™ 20 Visible Spectrophotometers (Thermo Scientific) to measure the optical density (OD) of the samples at various wavelengths. The lower the OD value, the lighter the sample color. The optical density of the samples is shown inFIG. 7 . The darkness color of the sample reduced with increasing the concentration of sodium percarbonate addition so as the OD value. The % reduction in optical density or color of the samples is also calculated against the sample without sodium percarbonate (0% w/w EHPC) and plotted inFIG. 8 which clearly supports this invention. - The aqueous (water) layer obtained from acid precipitation step of clarified broth (CB) to obtain concentrated rhamnolipid products described in Examples 2-6 of US20160272667is considered a wastewater from this process which is a starting material for this example. Sodium percarbonate is added into this acidic wastewater stream at 0.25%, 0.5% and 0.75% w/w EHPC. After 1 hour of gentle agitation at 60° C., the samples are removed from heat and let to cool to room temperatures during 1-2 hours. Afterwards, the samples are subjected to optical density (OD) measurement and biological oxygen demand (BOD) and total suspended solid (TSS) analysis.
- The optical density (OD) of the samples is measured with a
GENESYS™ 20 Visible Spectrophotometers (Thermo Scientific). BOD and TSS are performed based on Standard Methods for the Examination of Water and Wastewater (available form www.standardmethods.org) 5210B and 2540, respectively). The % optical density at various wavelength (nm), %BOD and %TSS reductions of the samples are shown in Table 2. It clearly shows that treating the aqueous waste stream with sodium percarbonate at 0.5% w/w EHPC gives rise to the highest reduction of BOD and TSS while the most reduction in color is observed with 0.75% w/w EHPC sample at the studied wavelengths (400-800 nm). The color of the aqueous layer is reduced with the addition of sodium percarbonate from brown to yellow. -
TABLE 2 % Reduction of optical density at various wavelength, BOD and TSS of samples with sodium percarbonate addition. For example, OD 400 indicates optical density of samples at 400 nm.% Reduction % EHPC OD 400 OD 500OD 600OD 700OD 800BOD TSS 0.25% 0% 0% 38% 52% 63% 40% 45% 0.50% 32% 72% 88% 92% 99% 68% 53% 0.75% 78% 90% 95% 95% 96% 28% 42% -
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Claims (8)
1. An organic solvent-free process for obtaining a neutralized composition comprising one or more rhamnolipids (RLs) comprising:
(a) providing an aqueous medium comprising at least one rhamnolipid;
(b) treating said medium provided with acid to obtain an acidic medium comprising a solid, liquid and oily phase;
(c) removing at least the liquid phase from said acidic medium of (b) to obtain an acidic solid phase and optionally acidic oily phase;
(d) treating said acidic solid phase and optionally acidic oily phase obtained in (c) with a composition comprising a percarbonate salt in an amount effective to neutralize and decolorize said acidic solid phase and optionally said acidic oil phase of step (c) to obtain said neutralized composition.
2. The method according to claim 1 , wherein said neutralization and decolorization step occurs at a temperature of between about 35-85C for at least about 30 minutes.
3. The method according to claim 1 , wherein said composition in step (d) further comprises a second base.
4. The method according to claim 1 , wherein said percarbonate salt in step (d) is present in the amount of about 0.5 to about 3% equivalent hydrogen peroxide concentration (EHPC).
5. A composition comprising a neutralized and decolorized solution obtainable according to the method of claim 1 .
6. A method for increasing the quality of the liquid phase obtained in step (b) of the process of claim 1 , comprising treating said liquid phase with an amount of percarbonate salt effective to increase said quality.
7. A method of reducing the BOD and/or TSS of at least about 25% in the liquid phase obtained in the process of claim 1 , comprising treating said liquid phase with a composition comprising a percarbonate salt in an amount effective to reduce BOD and/or TSS of at least about 25% in said liquid phase.
8. The method according to claim 7 , wherein said percarbonate salt is present in an amount of about 0.2% to about 0.8% w/w EHPC.
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