Large algal compositions and methods for decolorizing and removing textile production wastewater pollutants from textile production wastewater

Abstract

Large algal compositions and methods for decolorizing and removing contaminants from textile production wastewater. The method is based on the biodegradation of dyes and organic substances in the wastewater by at least one type of green macroalgae.

Description

[0001] Cross-reference to related applications

[0002] This application claims priority to U.S. Provisional Patent Application Serial No. 63 / 266,767, filed January 14, 2022, the disclosure of which is incorporated herein by reference in its entirety. Technical Field

[0003] This invention relates to compositions and methods for treating colored wastewater from textile production, and more particularly to compositions and methods for the biodegradation of colored dyes from textile production wastewater by green macroalgae. Background Technology

[0004] Denim manufacturing is one of the most important sub-sectors of the textile industry. It generates wastewater at different stages of the manufacturing process. Dyeing and finishing, or washing operations, are the main sources of wastewater pollution. The resulting wastewater contains large amounts of dyes, suspended solids, and dissolved solids. 1,2 .

[0005] Indole-derived indigo (blue) dye is the primary dye used in dyeing jeans. Indigo (blue) dye accounts for 70% to 80% of all dyes used in denim production. It is a synthetic dye, and thousands of tons are produced annually due to the ever-increasing demand for jeans. 3 The resulting water opacity 4 Wastewater containing dyes can have a negative impact on aquatic life.

[0006] Table 1 below summarizes the typical characteristics of wastewater from denim mills:

[0007] Table 1:

[0008]

[0009]

[0010] Currently, due to its known technology and ease of maintenance, most denim manufacturing plant wastewater is treated using traditional activated sludge (biological) systems. Figure 1 A conventional activated sludge system for wastewater originating from denim mill operations is illustrated schematically. For example... Figure 1As shown, the treatment plant first allows the wastewater to undergo acid neutralization and homogenization processes (1 and 2) to reduce the alkalinity to acceptable levels for biological treatment (pH 7-9). The activated sludge process consists of aeration tanks (3 and 4). At this stage of treatment, a tank may be optionally included, using a (polymer) coagulant aid to remove dissolved solids. The wastewater then enters parallel clarifiers (5 and 6) and is stored in tank (7) before discharge. Sludge from the clarifiers is collected in a settling tank (8), and the purified water from the sludge is recycled through a pipeline.

[0011] Traditional activated sludge (biological) systems effectively remove chemical oxygen demand (COD) from wastewater. Therefore, COD levels decrease significantly after activated sludge (biological) treatment. However, due to the persistence of dyes, the problem is that color removal is not always successful.

[0012] Physicochemical treatment technologies, such as advanced oxidation processes, membrane filtration, and adsorption, can be used to decolorize wastewater. Generally, these methods can remove color from water, but they consume energy, chemicals, or materials. Table 2 below summarizes the mechanisms and drawbacks of these conventional treatment methods.

[0013] Table 2:

[0014]

[0015] Some studies have reported that algae are desirable for the biodecolorization of certain dyes. The two main mechanisms by which algae remove dye color include biosorption and biodegradation, which are two distinct mechanisms. Biosorption converts the dye from the aqueous phase to the solid phase, while biodegradation involves the decomposition of the dye. Table 3 below summarizes the decolorization of different common dyes by different algal species (mainly divided into microalgae and macroalgae):

[0016] Table 3:

[0017]

[0018]

[0019]

[0020]

[0021] Based on the aforementioned studies, although some research focuses on removing indigo dye using microalgae (such as *Chlorella*, cyanobacteria, *Anabaena*, *Synechococcus*, and *Chlorella*), their main drawback is the difficulty in controlling their growth, as they typically grow rapidly under favorable conditions, requiring careful monitoring of biomass increases. Otherwise, this is not an ideal method for treating industrial wastewater containing indigo dye.

[0022] Therefore, there is a need for an improved composition and method for treating wastewater containing indigo dye, which eliminates or reduces the aforementioned disadvantages and problems. Summary of the Invention

[0023] Therefore, a first aspect of the present invention provides a composition comprising at least one macroalgae and its related families for decolorizing and removing contaminants from textile production wastewater.

[0024] In some embodiments, the at least one type of macroalgae includes green macroalgae.

[0025] In an exemplary embodiment, the at least one type of macroalgae is selected from green macroalgae.

[0026] In some implementations, the green macroalgae include species of the genera *Cladophora* and *Streptococcus*, and related species.

[0027] Preferably, in the composition used to decolorize and remove textile production wastewater, Marimo and Chaetomorpha antennina (Chaeto) are selected as large green algae.

[0028] Preferably, the large green algae in this composition exist in the form of aggregates, such as spherical or sheet-like structures.

[0029] In some implementations, large green algae are supported by physical structures such as frames or shells that allow objects to move freely.

[0030] Preferably, the green algae exists in the composition in a spherical structure and can be placed in a closed structure when applied to textile production wastewater.

[0031] Preferably, the algae exists in the composition in a sheet-like structure and, when applied to textile production wastewater, can be mounted on a frame supported by two layers of netting.

[0032] Besides *Cladophora*, other Cladophora genera that can be used in this composition include, but are not limited to, *Cladophora glomerata*, *Cladophora albida*, *Cladophora abrasiliana*, *Cladophora columbiana*, *Cladophora acrispata*, *Cladophora graminea*, *Cladophora prolifera*, and *Cladophora rivularis*.

[0033] In addition to Chaetomorpha, other Chaetomorpha species that can be used in this composition include, but are not limited to, Chaetomorpha akineta, Chaetomorpha brachygona, Chaetomorpha californica, Chaetomorpha cannabina, Chaetomorpha geniculate, Chaetomorpha kerguelensis, and Chaetomorpha pacifica.

[0034] In some embodiments, other green algae that may form part of the composition include, but are not limited to, species belonging to the family Cladophyceae, such as Brybesia, Rhizoclonium, and Lychaete.

[0035] A second aspect of the invention provides a method for decolorizing and removing contaminants from textile production wastewater using a composition of the first aspect or any embodiment described herein, the composition comprising at least one macroalgae.

[0036] In some embodiments, the optimal range for the amount of dye in the wastewater that is effectively removed by the composition is from 10 mg / L to 500 mg / L.

[0037] In some embodiments, the dyes removed from the wastewater by the composition include indigo dye or derivatives thereof.

[0038] Other dyes that can be removed by the compositions / methods of the present invention include, but are not limited to, vat dyes, reactive dyes, and disperse dyes.

[0039] In some implementations, the wastewater originates from the textile manufacturing industry, which includes denim production or processing plants.

[0040] In some implementations, the method is carried out at a temperature of about 5°C to about 35°C.

[0041] Preferably, the temperature is about 15°C to 30°C.

[0042] In some implementations, the method is performed under visible light irradiation.

[0043] In some implementations, the method is carried out at a pH of 7 to 9.

[0044] In some embodiments, the pollutants removed (or reduced) from textile production wastewater by the compositions or methods of the present invention include, but are not limited to, chemical oxygen demand (COD), total dissolved solids (TOD), total organic carbon (TOC), and total suspended solids (TSS).

[0045] This summary is provided to present a simplified description of the selected concepts, which will be further described in the detailed embodiments below. This summary is not intended to identify key or essential features of the claimed subject matter, nor is it intended to be used as an aid in determining the scope of the claimed subject matter. Other aspects of the invention are disclosed as shown in the embodiments below. Attached Figure Description

[0046] In the accompanying drawings, the same reference numerals refer to the same or similarly functional elements. The drawings include figures of certain embodiments to further illustrate and clarify the above and other aspects, advantages, and features of the invention. It should be understood that these drawings depict embodiments of the invention and are not intended to limit its scope. The invention will be described and explained with additional specificity and detail using the accompanying drawings, in which:

[0047] Figure 1 A schematic description of a traditional biological treatment plant using activated sludge for the denim industry.

[0048] Figure 2 Images of typical green algae spheres and stiff hair algae are shown;

[0049] Figure 3 Images of *Chlorella vulgaris* used in the composition of Example 1 are shown;

[0050] Figure 4 The test results of Example 1 are shown;

[0051] Figure 5 The differences in indigo dye removal rates of compositions with different algal biomass according to Example 2 are shown;

[0052] Figure 6The effect of increasing algal biomass in the composition as in Example 2 on the removal efficiency of colored dyes (e.g., indigo dye and its derivatives) was quantitatively shown; Top and middle graphs: Removal rate over time in two independent experiments; Bottom graph: Average removal rate over time obtained from the two experiments; Arrows indicate the end of the test time; SD = 0.02;

[0053] Figure 7 The difference in indigo dye blue removal rate between the two algae (Chlorella vulgaris and Sterculia salina) under the treatment conditions according to Example 3 is shown;

[0054] Figure 8 The differences in color removal efficiency between compositions containing *Chlorella vulgaris* and *Streptococcus faecium* after one day of treatment according to Example 3 are quantitatively shown (top figure) and their appearance (bottom figure); general Pt-Co and UV-Vis relationship curves are also provided.

[0055] Figure 9 The difference in total organic carbon (TOC) between *Chlorella vulgaris* and *Streptococcus faecium* according to Example 3 was described quantitatively.

[0056] Figure 10 The effect of increasing the indigo dye concentration according to Example 4 on the indigo dye removal rate of *Chlorella vulgaris* is shown.

[0057] Figure 11 The figure shows the color removal rate (top) and appearance (bottom) of *Chlorella vulgaris* after one day of exposure to a high concentration of indigo dye, according to Example 4.

[0058] Those skilled in the art will understand that the elements in the diagram are for illustrative purposes and need not be drawn to scale. Detailed Implementation

[0059] definition

[0060] The following abbreviations used in this document refer to their respective meanings in order to avoid any confusion for those skilled in the art:

[0061] 3D – Three-dimensional

[0062] COD – Chemical Oxygen Demand

[0063] LED – Light Emitting Diode

[0064] NaCl – Sodium chloride

[0065] PLC – Programmable Logic Controller

[0066] TDS – Total Dissolved Solids

[0067] TOC – Total Organic Carbon

[0068] TSS – Total Suspended Solids

[0069] UV – Ultraviolet rays

[0070] The embodiments described in this disclosure, such as "one embodiment," "implementation," and "exemplary embodiment," may include specific features, structures, or characteristics, but each embodiment does not necessarily include those specific features, structures, or characteristics. Furthermore, such phrases do not necessarily refer to the same embodiment. Additionally, when a specific feature, structure, or characteristic is described in connection with an embodiment, it is believed, to the knowledge of those skilled in the art, that the combination of other embodiments affects that feature, structure, or characteristic, whether explicitly described or not.

[0071] In the context of describing the invention (especially in the context of the following claims), the terms “a” and “an,” “the,” and “at least one,” and similar designations should be interpreted to cover both the singular and the plural, unless otherwise stated herein or the context clearly contradicts this. Unless otherwise stated, the terms “comprising,” “having,” “including,” and “containing” should be interpreted as open-ended terms (i.e., meaning “including but not limited to”).

[0072] Values ​​in the range format should be interpreted flexibly, including not only the numerical values ​​of the explicitly described range limits, but also all individual numerical values ​​or subranges contained within the range, as if each numerical value and subrange were explicitly described. For example, a concentration range of “about 0.1% to about 5%” should be interpreted as including not only the explicitly described concentrations of about 0.1 wt.-% to about 5 wt.-%, but also individual concentrations (e.g., 1%, 2%, 3%, and 4%) and subranges (e.g., 0.1% to 0.5%, 1.1% to 2.2%, and 3.3% to 4.4%) within the indicated range.

[0073] In the methods for preparing or using certain objects, articles, compositions, systems, or apparatuses described herein, these steps may be performed in any order without departing from the principles of the invention, unless the time or order of operations is explicitly enumerated. A claim describing the general order of execution of one step followed by several other steps should be interpreted as the first step being performed before any other steps; however, the other steps may be performed in any suitable order unless a further order is enumerated in the other steps. For example, a claim element reciting "step A, step B, step C, step D, and step E" should be interpreted as step A being performed first, step E last, and steps B, C, and D being performed in any order between steps A and E, which still falls within the literal scope of the claimed method. A given step or subset of steps may also be repeated. Detailed Implementation

[0075] Example

[0076] Those skilled in the art will appreciate that modifications, including additions and / or substitutions, can be made without departing from the scope and spirit of the invention. Specific details may be omitted to avoid obscuring the invention; however, this disclosure is intended to enable those skilled in the art to practice the teachings herein without excessive experimentation.

[0077] To improve the color removal efficiency of indigo dye and optimize the operating conditions of the decolorization process, a laboratory-scale apparatus based on macroalgae was established for the treatment of indigo (blue) dye in wastewater. In this invention, parameters such as temperature, pH, salinity, CO2 concentration level, dissolved oxygen level, and light intensity are carefully controlled.

[0078] To achieve the required experimental conditions, the apparatus consists of various types of devices:

[0079] cylindrical water tank

[0080] pH, conductivity, temperature, dissolved oxygen, and dissolved CO2 sensors

[0081] Full-spectrum PAR sensor

[0082] Circulating pump

[0083] Temperature control coil

[0084] LED light panel

[0085] CO2 proportional regulator

[0086] rack and sealing cover

[0087] PLC (Programmable Logic Controller) is used for data acquisition via a network-accessible interface.

[0088] Temperature control system

[0089] This invention provides a method for decolorizing indigo dye from wastewater from textile manufacturing plants (e.g., denim factories) after conventional biological treatment using at least one type of green macroalgae (including species of the genera *Marimo* and *Chaeto*, and related families and genera). The effects of dye concentration, algal biomass load, pH, and salinity on the decolorization rate of the green macroalgae species were analyzed using a UV-Vis spectrophotometer. The dye decolorization method of this invention utilizes *Marimo* and *Chaeto*. Table 3 summarizes the living conditions under which *Marimo* and *Chaeto*, as effective agents, remove synthetic indigo dye from the environment.

[0090] Table 3:

[0091]

[0092] exist Figure 2 The image shows typical Chlorella and Sterculia at their mature stage.

[0093] Example 1

[0094] The large green algae, *Marimo balls*, was purchased from a local algae distributor in Goldfish Street, Hong Kong. Dye decolorization experiments were conducted in a 20L water tank containing a stock solution (70 mg / L), pH 7, and 200 g of *Marimo balls* to study the decolorization effect. The dye used in this study was a synthetic indigo dye from Acrōs Organics. This dye is one of the main indigo (blue) dyes in the textile industry. The experimental environment was controlled at 25°C, using 24-hour LED lighting with a full visible spectrum from 380 nm to 750 nm. The test conditions and results are summarized in Table 4. Figure 3 and Figure 4 middle.

[0095] Table 4:

[0096]

[0097] Figure 3 In the stock solution, the indigo (blue) color faded over time. Meanwhile, no indigo (blue) color was found on the surface of the *Chlorella vulgaris* spheres compared to the initial capture.

[0098] Example 2

[0099] A consistent stock solution (70 mg / L) of synthetic indigo dye was prepared by dissolving an appropriate amount of dye in distilled water under the same environmental conditions as in Example 1 (Table 4), except that the pH was 9 instead of 7, and approximately 8 to 9 g of each type of algae / chlorococcus was used. In this example, the biomass of the chlorococcus was increased and its pH was adjusted to 9 to investigate color removal efficiency.

[0100] Figure 5 The study showed the effect of increasing algal biomass (green algae balls) on the blue removal rate of indigo dye. Four groups of samples were included: samples without algae, samples with 200 / 600 / 1200 g of algal biomass, and samples with algal biomass of 1200 g / g. It was found that the color removal rate increased with increasing algal biomass load. This means that more algal mass can shorten the dye decolorization time.

[0101] Dye concentration was determined by measuring the absorbance of indigo dye and its derivatives at the wavelength of maximum absorption using a UV-Vis spectrophotometer. Decolorization activity was expressed as a percentage of decolorization and determined by observing the decrease in absorbance of indigo dye and its derivatives at the maximum absorption value. Color removal efficiency was expressed as a percentage of the decolorized dye concentration relative to the initial value.

[0102]

[0103] Where Abs0 represents the initial concentration of the dye, Abs t This represents the dye concentration at time t.

[0104] Figure 6 The effect of increasing algal biomass (twice the original biomass) on the change in absorbance at 660 nm was shown. As mentioned above, the dye removal efficiency improved with increasing *Chlorella vulgaris* biomass. The optimal color removal rate reached 98% within the first 24 hours (Table 5).

[0105] Table 5:

[0106] sample Color dye removal % Green algae balls (200g) 93％ Green algae balls (600g) 98％ Green algae balls (1200g) 98％ Comparison 69％

[0107] Example 3

[0108] A consistent stock solution (70 mg / L) of synthetic indigo dye was prepared by dissolving an appropriate amount of dye in distilled water under the same environmental conditions as in Example 1. However, in this example, the salinity was adjusted to 1% and the pH to 9 by adding sea salt NaCl to the stock solution. Detailed salt content of the stock solution is shown in Table 6. Additionally, another large green algae—Chaeto—was introduced to investigate the color removal rate of the indigo dye. For both Chlorella vulgaris and Chaeto, 20 L stock solutions were prepared using 1200 g of biomass each.

[0109] Table 6:

[0110]

[0111] Figure 7 In the study, it was found that both *Chlorella vulgaris* and *Streptococcus faecium* effectively removed the color of indigo (blue) dye, especially within the first 3 hours. Ultimately, as... Figure 8 As shown in Table 7, after one day, the color removal rates of *Chlorella vulgaris* and *Streptococcus faecium* were 99% and 94%, respectively. Furthermore, the total organic carbon (TOC) values ​​of all three samples were measured using a TOC analyzer (model: TOC-VCPH, manufactured by Shimadzu, Japan). Figure 9 This shows that organic matter in the water sample was degraded during treatment.

[0112] Table 7:

[0113] sample Color dye removal % Green algae balls (x6) 99％ Sterculia lanceolata 94％ Comparison 41％

[0114] Example 4

[0115] In this example, the concentration of indigo dye was increased to 280 mg / L (3000 Pt-Co), and the environmental conditions were the same as in Example 1 (25°C, 24-hour LED lighting with a full visible spectrum of 380 nm to 750 nm). The biomass, salinity, and pH were the same as in Example 3 (1200 g of Chlorella balls, 1% NaCl salinity, and pH 9). Figure 10 The observations showed that even at high concentrations, indigo dye maintained a good decolorization effect in a slightly alkaline environment. Ultimately, as... Figure 11 As shown in Table 8, a 99% color removal rate can be achieved within one day. Subsequently, it was confirmed that no indigo dye remained on the surface of the *Chlorella vulgaris* spheres. In this case, biodegradation is considered the key mechanism, as no treatment of the colored algal biomass is required after treatment.

[0116] Table 8:

[0117] sample % removal of color dye after 1 day Green algae balls (x6) 99％ Comparison 11％

[0118] In view of the results of the above embodiments, several findings are worth highlighting, as follows:

[0119] Given the selection of Marimo and Chaeto to study dye removal rates, species of the green macroalgae genus Chaeto and their related families and genera can be used to effectively remove the color of indigo (blue) dye.

[0120] With increased algal biomass load, at least 90% dye color removal rate can be achieved within 3 hours, and even 99% can be achieved after one day of treatment.

[0121] For Chlorella species, it can perform well even in environments with high dye concentrations, such as up to 280 mg / L indigo stock solution.

[0122] For both *Chlorella* and *Streptococcus* species, no additional TOC was generated during the treatment. This means that the organic matter in the water sample was degraded.

[0123] This indicates that biodegradation is the key mechanism of the method of the present invention, because there is no need to remove the stained algal biomass after treatment.

[0124] Therefore, this invention provides a purely biological, efficient, and scalable decolorization method for textile production wastewater, with virtually no increase in biomass from the decolorizing agent (green macroalgae) after treatment. Thus, the method of this invention can significantly reduce the level of organic matter generated in the corresponding wastewater from textile production or treatment plants without cumbersome and complex post-treatment methods.

[0125] Although the invention has been described according to certain embodiments, other embodiments that will be apparent to those skilled in the art are also within the scope of the invention. Therefore, the scope of the invention is intended to be defined only by the following claims.

[0126] Industrial applicability

[0127] The method for producing macroalgae compositions according to the present invention has been shown to significantly reduce pollutants, save energy, reduce CO2 gas production, and is cost-effective and environmentally friendly. The method of the present invention should be suitable for industrial application.

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Claims

1. An algal composition for decolorizing and removing contaminants from textile production wastewater containing indigo dye or any derivative thereof, the algal composition comprising at least one type of green macroalgae capable of degrading indigo dye or any derivative thereof in the textile production wastewater without significantly increasing biomass after degrading the indigo dye or any derivative thereof, wherein the green macroalgae includes *Cladophora* (*Cladophora* genus). Cladophora ) species and the genus *Streptococcus* ( Chaetomorpha One or more species.

2. The composition according to claim 1, wherein the Cladophora species includes Chlorella vulgaris (… Cladophora aegagropila ) 、 Cladophora clasticis ( Cladophora glomerata ) 、 Pale bristle algae ( Cladophora albida ) 、 Brazilian Cladosporium ( Cladophora brasiliana ) 、 Columbian filamentosa ( Cladophora columbiana ) 、 Creeping bristle algae ( Cladophora crispata ) 、 Grass leaf bristle algae ( Cladophora graminea ) 、 Cladophora yuzhi ( Cladophora prolifera ) and habitat filamentous algae ( Cladophora rivularis ) ， Or any of its related species.

3. The composition according to claim 1, wherein the *Streptococcus* species includes *Streptococcus* (… Chaetomorpha antennina ), immobile bristle algae ( Chaetomorpha akineta ) 、 Short-segmented bristle algae ( Chaetomorpha brachygona ) 、 California stearotherm ( Chaetomorpha californica ) 、 Hemp-like bristle algae ( Chaetomorpha cannabina ) 、 Knee-shaped bristle algae ( Chaetomorpha geniculate ) and Sterculia clarithii ( Chaetomorpha kerguelensis ) 、 Pacific stenophylloides ( Chaetomorpha pacifica ) ， Or any of its related species.

4. The composition according to claim 1, wherein the textile production wastewater originates from a denim production or treatment plant.

5. A method for decolorizing and removing contaminants from textile production wastewater containing indigo dye or any derivative thereof, the method comprising treating the textile production wastewater with a composition comprising at least one type of green macroalgae capable of degrading indigo dye or any derivative thereof in the textile wastewater without significantly increasing biomass after degradation of the indigo dye or any derivative thereof, wherein the green macroalgae comprises any species of the genera *Cladophora* and *Streptococcus*.

6. The method according to claim 5, wherein the Cladophora species includes Chlorella vulgaris. 、 Cladophora 、 Pale bristle algae 、 Brazilian Cladosporium 、 Colombian Cladosporium 、 Creeping bristle 、 Grass Leaf Cladosporium 、 Cladophora bryophylla and Cladophora scavenger ， Or any of its related species.

7. The method according to claim 5, wherein the species of the genus *Streptococcus* includes *Streptococcus* and *Streptococcus immobile*. 、 Short-segmented stiff hair algae, California stiff hair algae, hemp-like stiff hair algae, geniculate stiff hair algae, and Kreutz stiff hair algae 、 Pacific stearotherm ， Or any of its related species.

8. The method according to any one of claims 5 to 7, wherein the composition removes up to 500 mg / L of the indigo dye or any derivative thereof from the textile production wastewater within a time not exceeding 24 hours.

9. The method according to claim 5, wherein the textile production wastewater originates from a denim production or treatment plant.

10. The method of claim 5, wherein the composition comprises 1200 g of the at least one type of green macroalgae to remove 99% of the indigo dye or any derivative thereof from 200 mL of textile production wastewater within 24 hours.

11. The method according to any one of claims 5 to 7, 9 and 10, wherein the method is performed at a temperature of 5°C to 35°C.

12. The method according to claim 11, wherein the temperature is from 15°C to 30°C.

13. The method according to any one of claims 5 to 7, 9 and 10, wherein the method is performed under visible light irradiation.

14. The method according to any one of claims 5 to 7, 9 and 10, wherein the method is performed at a pH value of 7 to 9.

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