CN114775314A - Treatment method for removing reactive dye from fiber fabric - Google Patents
Treatment method for removing reactive dye from fiber fabric Download PDFInfo
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- CN114775314A CN114775314A CN202210425365.3A CN202210425365A CN114775314A CN 114775314 A CN114775314 A CN 114775314A CN 202210425365 A CN202210425365 A CN 202210425365A CN 114775314 A CN114775314 A CN 114775314A
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- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical compound C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 claims abstract description 15
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- OYYZSRVQTPSXRG-UHFFFAOYSA-N 1-amino-4-[3-[[4-chloro-6-(3-sulfoanilino)-1,3,5-triazin-2-yl]amino]-2,4,6-trimethyl-5-sulfoanilino]-9,10-dioxoanthracene-2-sulfonic acid Chemical compound CC1=C(S(O)(=O)=O)C(C)=C(NC=2C=3C(=O)C4=CC=CC=C4C(=O)C=3C(N)=C(C=2)S(O)(=O)=O)C(C)=C1NC(N=1)=NC(Cl)=NC=1NC1=CC=CC(S(O)(=O)=O)=C1 OYYZSRVQTPSXRG-UHFFFAOYSA-N 0.000 description 7
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 2
- 235000019289 ammonium phosphates Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
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- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/15—Locally discharging the dyes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/15—Locally discharging the dyes
- D06P5/151—Locally discharging the dyes with acids or bases
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The invention relates to the field of dye degradation, in particular to a treatment method for removing reactive dye from fiber fabric. The treatment method for removing the reactive dye from the fiber fabric comprises the steps of soil degradation and hydrolysis by using inorganic alkali; the soil in the soil degradation is compost soil; the fiber fabric is dyed by reactive dye. The method comprises the steps of firstly carrying out soil degradation on fiber fabrics dyed by reactive dyes in a specific environment, taking the degraded cotton fabrics as analysis objects, then carrying out alkaline hydrolysis on the degraded fabrics by inorganic alkali, and hydrolyzing dye substances subjected to soil degradation into hydrolyzed vinyl sulfone.
Description
Technical Field
The invention relates to the field of dye degradation, in particular to a treatment method for removing reactive dye from fiber fabric.
Background
In the textile industry, reactive dyes are widely used in cotton, rayon and other fiber fabrics due to their high solubility and stability, good diffusivity and dye penetration and good color fastness. However, most synthetic dyes are toxic and due to their complex chemical structures such as benzidine and other aromatics, the dyes in reactive dye dyed textiles are difficult to handle and remove. Meanwhile, the reactive dye on the cotton fiber fabric is difficult to remove due to the chemical bond between the reactive dye and cellulose (such as cotton).
Therefore, it is desirable to provide a treatment method for removing reactive dyes from fiber fabrics, which is used to remove the residual reactive dyes (such as reactive black 5, reactive red 198, etc.) on the fabrics.
Disclosure of Invention
The present invention has been made to solve at least one of the above-mentioned problems occurring in the prior art. To this end, the invention proposes a treatment for the decomposition of reactive dyes from textile fabrics, which allows the selective degradation of the reactive dyes into hydrolyzed vinylsulfones.
The invention conception of the invention is as follows: firstly, soil degradation under specific conditions is carried out on the fiber fabric dyed by the reactive dye through compost soil, the degraded fabric is used as an analysis object, then alkaline hydrolysis is carried out on the degraded fabric through inorganic alkali, and the dye material subjected to soil degradation is hydrolyzed into hydrolyzed vinyl sulfone.
The first aspect of the invention provides a treatment method for decomposing and removing reactive dyes from fiber fabrics, wherein the treatment method comprises the steps of soil degradation and hydrolysis by using inorganic alkali; the soil in the soil degradation is compost soil; the fiber is a fabric dyed by reactive dye.
The fiber fabric is cotton fiber fabric.
Compared with the prior art, the treatment method for removing the reactive dye from the fiber fabric has the following beneficial effects: according to the invention, soil degradation is carried out on the fiber fabric dyed by the reactive dye in a specific environment, and then strong inorganic base (such as NaOH and KOH) hydrolysis is carried out on the degraded soil degradation product, so that the reactive dye can be better removed from the fiber fabric, and the reactive dye can be specifically hydrolyzed into specific vinyl sulfone. Meanwhile, the method provides an idea for discussing the mechanism of degrading the active dye by the soil.
Preferably, the reactive dye is at least one of KN type reactive dye vinyl sulfone type, M type reactive dye and K type reactive dye; further preferred REACTIVE dyes are at least one of REACTIVE BLACK 5(REACTIVE BLACK 5, CAS: 17095-24-8), REACTIVE red 198(REACTIVE RED 198, CAS: 145017-98-7), REACTIVE BLUE 49(REACTIVE BLUE 49, CAS: 12236-92-9).
Preferably, the treatment method comprises the following steps:
(1) mixing the fiber fabric dyed by the reactive dye with soil, and degrading the soil for 30-60 days to obtain a first degradation product; the pH value of the soil is 7-8, and the C: N ratio is adjusted to (8-12) through ammonium phosphate: 1. the humidity is 55-65%; the degradation temperature is 15-25 ℃ in the soil degradation process;
(2) and (3) hydrolyzing the first degradation product by using 1-3 wt% of inorganic alkali aqueous solution, wherein the hydrolysis temperature is 50-90 ℃, so as to prepare a second degradation product, and the second degradation product contains hydrolyzed vinyl sulfone.
Preferably, in the step (1), the particle size of the soil is less than 5 mm; further preferably, the particle size of the soil is less than 3 mm; even more preferably, the soil has a particle size of less than 2 mm.
Preferably, in the step (1), the soil is compost soil.
Preferably, in the step (1), the raw materials of the compost soil comprise compost, base soil and auxiliary materials; further preferably, the raw materials of the compost soil comprise 25-75 parts of compost, 25-75 parts of base soil and 10-30 parts of auxiliary materials.
Preferably, the compost fertilizer is human or animal excrement, and the auxiliary materials comprise at least one of sawdust, straws, grass, leaves and vines; further preferably, the compost fertilizer is cow dung.
The preparation process of the compost soil comprises the following steps: controlling the water content of the compost fertilizer to be 15-25 wt%, mixing the compost fertilizer, the base soil and auxiliary materials, and carrying out stack retting fermentation, wherein ventilation is carried out for 0.5-1.5h every day in the stack retting fermentation process, pile turning is carried out every 7-12 days, and the stack retting fermentation time is 15-25 days.
Preferably, in the step (1), before the soil is mixed with the fiber fabric, the soil is stored for 5-10 days at the temperature of 0-10 ℃; further preferably, the soil is stored for 6 to 8 days at the temperature of 3 to 5 ℃; still more preferably, the soil is first stored at a temperature of 4 ℃ for 7 days.
Preferably, in the step (1), the degradation depth of the soil degradation is 1mm-500mm in terms of the soil thickness completely covered on the fiber fabric; further preferably, the degradation depth is 5mm to 50 mm.
Preferably, in step (1), each individual piece of said fiber fabric has a single-sided area of less than 100cm2(ii) a Further preferably, each individual piece of said fibrous web has a single face area of less than 25cm2(ii) a Even more preferably, each individual piece of said fiber fabric has a single-side area of 4cm or less2。
Preferably, in step (1), the soil has a pH of 7.4 to 7.8.
Preferably, in the step (1), the ratio of C to N is (9-11): 1; further preferably, the C: N ratio is (9-11): 1; still more preferably, the C: N ratio is 10: 1.
preferably, in the step (1), the humidity is 58-62%; further preferably, the humidity is 60%.
Preferably, in the step (1), the degradation temperature is 18-22 ℃; further preferably, the degradation temperature is 20-21 ℃.
Preferably, in the step (2), before the hydrolysis of the first degradation product, the first degradation product is further washed by a polar solvent; further preferably, the polar solvent comprises at least one of water, methanol, acetonitrile; still further preferably, the number of washing is 3 to 9; more preferably, the washing is performed 3 times by using water, methanol, and acetonitrile, respectively.
Preferably, in step (2), the inorganic base comprises at least one of NaOH and KOH.
Preferably, in the step (2), the concentration of the inorganic alkali aqueous solution is 1-2 wt%; further preferably, the concentration of the aqueous inorganic base is 1.5 wt%.
Preferably, when the REACTIVE dye is REACTIVE BLACK 5(REACTIVE BLACK 5, CAS: 17095-24-8), the hydrolysis temperature in step (2) is 50-75 ℃; further preferably, the hydrolysis temperature is 55-75 ℃.
Preferably, when the reactive dye is reactive red 198(REACTIVE RED 198, CAS: 145017-98-7), the hydrolysis temperature is 70-90 ℃ in step (2); further preferably, the hydrolysis temperature is 75-85 ℃.
Preferably, in the step (2), the hydrolysis time is 0.5-3 h; further preferably, the hydrolysis time is 0.5-1.5 h; still more preferably, the hydrolysis time is 1 h.
Preferably, in the step (2), the second degradation product is further neutralized by acid; further preferably, the acid comprises at least one of hydrochloric acid, sulfuric acid, acetic acid; even more preferably, the concentration of the acid is 0.5 to 1.5 mol/L.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the soil degradation is carried out on the fabric dyed by the reactive dye through a specific environment, and then the strong inorganic base hydrolysis is carried out on the degraded fabric, so that not only can the reactive dye be better removed from the fiber fabric, but also the reactive dye can be specifically hydrolyzed into specific vinyl sulfone. Meanwhile, the method provides an idea for discussing the mechanism of degrading the active dye by the soil.
Drawings
FIG. 1 is a mass spectrum of a second degradant from example 1;
FIG. 2 is a mass spectrum of the second degradant of example 2;
FIG. 3 is a mass spectrum of the second degradation product of comparative example 5.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples are given for illustration. It should be noted that the following examples are not intended to limit the scope of the claimed invention.
The starting materials, reagents or apparatuses used in the following examples are, unless otherwise specified, either commercially available from conventional sources or can be obtained by known methods.
The LC-MS used was: agilent 1200LC and 6520Q-TOF MS (quadrupole time of flight liquid mass spectrometer) mass spectrometer (Agilent) with Electrospray (ESI) ion source; HPLC (high performance liquid chromatography) uses a reverse phase chromatographic column C18 column, at 40 deg.C, Mobile Phase A (MPA) is water, Mobile Phase B (MPB) is MeOH/ACN (methanol/acetonitrile), flow rate is 0.6mL/min, and each injection is 10. mu.L.
The raw materials of the compost soil comprise 55 parts of compost fertilizer, 30 parts of base soil and 15 parts of auxiliary materials, wherein the compost fertilizer of the compost soil is cow dung, and the auxiliary materials are 1:1 mixture of sawdust and straws.
The preparation process of the compost soil comprises the following steps: air-dry the cow dung, control cow dung water content and be 20 wt%, mix cow dung, substrate earth, saw-dust, stack retting fermentation, ventilate 1h every day in the stack retting fermentation process, once turn over the heap every 10 days, stack retting fermentation time is 25 days.
Example 1
Soil degradation method of active black 5 dyed cotton fiber fabric
(1) Sieving the compost soil to ensure that the particle size of the compost soil is less than 2mm, and freezing the sieved compost soil at 4 ℃ for 7 days; detecting that the pH value of the soil is 7.68, and adjusting the ratio of C to N of the soil to be 10:1 by adding ammonium phosphate;
(2) cutting the reactive black 5 dyed fiber fabric into 2cm multiplied by 2cm reactive black 5 dyed fiber fabric, wherein the total number of the fiber fabric is 25;
(3) each piece of 2cm by 2cm piece of reactive Black 5 dyed fiber fabric was placed in a beaker (diameter 150mm) containing frozen compost soil. The degradation depth of soil degradation is 10mm by taking the thickness of the soil completely covered on the fiber fabric as a standard, the degradation temperature is controlled between 20 and 21 ℃, the humidity is controlled at 60 percent, and the soil degradation is carried out for 45 days to prepare a first degradation product;
(4) washing the first degradation product with water, methanol and acetonitrile respectively three times;
(5) each first degradation product was added to a glass vial containing 1mL of 1.5 wt% NaOH solution, and the vial was heated to 60 ℃ for hydrolysis, and the reaction was continued with stirring for 1 hour. After 1 hour, stirring to cool, then adding 300 mu L of 1M hydrochloric acid respectively for neutralization treatment to prepare a second degradation product;
(6) the second degradent was filtered with a Polytetrafluoroethylene (PTFE) syringe and filter and analyzed using liquid phase mass spectrometry (LC-MS).
Judging the degradation degree: since the SDC dyed standard deep color chart does not completely represent the color of the fiber fabric in each degradation stage, the fiber fabric is graded with the undyed fiber fabric color depth of 0 grade and the reactive black 5 dyed fiber fabric without any treatment with the color depth of 10 grade (corresponding to the SDC dyed standard deep color chart color R, 2/1 grade), the first degradation product is judged to be 7 grade (corresponding to the SDC dyed standard deep color chart color R, 1/3 grade), and the fiber fabric in the second degradation product is judged to be 2 grade.
FIG. 1 is a mass spectrum of a second degradation product of example 1, with the ordinate representing ionic strength and the abscissa representing Charge-to-mass ratio (Counts vs. Mass-to-Charge, m/z); the Mass spectrum data of the substance can be seen to be m/z 370.4922, and the structure of the substance can be determined to be m/z 370.4922 by analyzing and determining the quality by using Mass Hunter software of Agilent
(hydrolyzed vinyl sulfone of reactive black 5), the theoretical mass spectrum characteristic peak of the divalent molecular ion peak is: m/z 370.5093 (100.0%), 371.0110 (28.1%), 371.5072 (18.1%), 372.0089 (5.1%), 371.0090 (3.2%), 371.5127 (2.7%), 371.5114 (2.7%), 371.0078 (1.8%), 372.5051 (1.2%), 371.5127 (1.1%).
Example 2
Dye soil degradation method of cotton fiber fabric dyed by reactive red 198
Example 2 differs from example 1 in that: the degradation object of example 2 was "reactive red 198 dyed fiber fabric" and the hydrolysis temperature in step (5) was 80 ℃.
The fiber fabrics in the fiber fabrics of the first degradation product were rated at a color depth of 0 grade and the fiber fabrics dyed with reactive red 198 without any treatment were rated at a color depth of 10 grade (corresponding to the SDC dyed standard depth color chart color C, 2/1 grade), the fiber fabrics in the fiber fabrics of the second degradation product were rated at 6 grade (corresponding to the SDC dyed standard depth color chart color C, 1/6 grade), and the fiber fabrics in the fiber fabrics of the second degradation product were rated at 1 grade.
FIG. 2 is a mass spectrum of a second degradant from example 2, with ionic strength on the ordinate and Charge-to-mass ratio (Counts vs. Mass-to-Charge, m/z) on the abscissa; the Mass spectrum data of the substance can be seen to be m/z 397.5004, and the structure of the substance can be determined by analyzing and qualifying by using Mass Hunter software of Agilent
(hydrolyzed vinyl sulfone of activated Red 198), the theoretical mass spectral characteristic peaks of the divalent molecular ion peaks are: m/z 397.5020 (100.0%), 398.0037 (29.2%), 398.4999 (18.1%), 399.0016 (5.3%), 398.5053 (4.1%), 398.0017 (3.2%), 398.5041 (2.9%), 398.0005 (2.6%), 399.4978 (1.2%).
Example 3
Soil degradation method of cotton fiber fabric dyed by reactive blue 49
Example 3 differs from example 1 in that: the degradation object of example 3 was "reactive blue 49 dyed fiber fabric".
The fiber fabrics were graded with the undyed fiber fabric color depth of 0 grade and the undyed reactive blue 49 color depth of 10 grade (corresponding to SDC dyed standard depth color chart color J, 2/1 grade), the first degradation product was judged to be grade 6 (corresponding to SDC dyed standard depth color chart color J, 1/6 grade), and the fiber fabrics in the second degradation product was judged to be grade 1.
The Mass spectral data for the second degradant of example 3 was m/z 397.5341 and was analytically characterized using Agilent's Mass Hunter software to determine that the material was hydrolyzed vinyl sulfone of reactive blue 49.
Comparative example 1
The reactive black 5 dye powder was used as it was, placed in an 80mL beaker, 50mL of 0.15% NaOH solution was added, wherein the concentration of the reactive black 5 dye solution was 0.001M, and stirred at 60 ℃ for 3 hours to obtain a hydrolysate. The hydrolysate was confirmed by Thin Layer Chromatography (TLC) monitoring (solvent system isopropanol/butanol/ethanol), High Resolution Mass Spectrometry (HRMS). In the obtained hydrolysis result, the hydrolysis product can find the hydrolyzed vinyl sulfone of the active black 5, and the signal peak is m/z 370.5053.
Comparative example 2
Comparative example 2 differs from comparative example 1 in that: the hydrolysis target is active red 198 powder.
In the obtained hydrolysis result, the hydrolysis product can find the hydrolyzed vinyl sulfone of the active red 198, and the signal peak is m/z 397.5040.
Comparative example 3
Comparative example 3 differs from comparative example 1 in that: the hydrolysis target is active blue 49 powder.
In the obtained hydrolysis result, the hydrolysis product can find the hydrolyzed vinyl sulfone of the active blue 49, and the signal peak is m/z 397.5340.
Comparative example 4
Comparative example 4 differs from comparative example 1 in that: and (4) degrading the soil in the step (3) for 0 day.
The fiber fabrics were graded with the undyed fiber fabric color depth of 0 grade and the undyed reactive black 5 color depth of 10 grade (corresponding to SDC dyed standard depth color card color R, 2/1 grade), the first degradation product was judged to be 10 grade (corresponding to SDC dyed standard depth color card color R, 2/1 grade), and the fiber fabrics in the second degradation product was judged to be 4 grade (corresponding to SDC dyed standard depth color card color R, 1/12 grade).
Comparative example 5
Comparative example 5 differs from comparative example 1 in step (5), step (5): the first degradation product was treated with 100. mu.L of 3M NaOH solution at 0 ℃ for 4h, then washed with 500. mu.L of acetic acid for 1min, after removal of the acetic acid, 1.5mL of 0.1M sodium acetate buffer was added for 1min, after removal of the buffer, 1mL of enzyme solution (prepared by dissolving cellulase, CAS: 9012-54-8, in pH 4.8 sodium acetate buffer) was added, and incubated at 50 ℃ for 24 h.
The mass spectrum results for comparative example 5 were: degraded productThe mass to charge ratio signals were m/z 694.6064 (double charge-2, dye-cellobiose), m/z 638.1355, m/z 570.1470 (single charge-1, degradation product), respectively. FIG. 3 is a mass spectrum (m/z 694.6064) of the second degradation product of comparative example 5, with ionic strength on the ordinate and Charge-to-mass ratio (Counts vs. Mass-to-Charge, m/z) on the abscissa; the Mass spectrum data of the substance can be seen to be m/z 694.6064, and the structure of the substance can be determined by analyzing and qualifying by using Mass Hunter software of Agilent
(dye-cellobiose structure), and the theoretical mass spectrum characteristic peaks of the divalent molecular ion peaks are as follows: m/z 694.6150 (100.0%), 695.1166 (54.1%), 695.6129 (18.1%), 695.6183 (14.3%), 696.1145 (9.8%), 695.6171 (6.8%), 696.1188 (3.7%), 695.1146 (3.2%), 696.6162 (2.6%), 696.1200 (2.5%), 695.1135 (1.8%), 695.6163 (1.7%), 695.1170 (1.3%), 696.6150 (1.2%), 696.6107 (1.2%), 695.6151 (1.0%), 696.6204 (1.0%). It can be shown that there is a chemical bond between the reactive dye and the fiber.
According to the invention, the soil degradation is carried out on the fiber fabric dyed by the reactive dye through a specific environment, and then NaOH hydrolysis is carried out on the degraded soil degradation product, so that not only can the reactive dye be successfully removed, but also the reactive dye can be specifically hydrolyzed into specific vinyl sulfone, and other substances (products of general hydrolysis of reactive black 5 which does not participate in fabric dyeing) with the charge-mass ratios of m/z 797.7, 725.6 and 707.5 as described in the literature can not be found in the mass spectrum result of the embodiment 1. Meanwhile, the method provides an idea for discussing the mechanism of degrading the active dye by the soil.
Claims (10)
1. A treatment process for removing reactive dyes from a fibre fabric, characterised in that the treatment process comprises soil degradation and hydrolysis using an inorganic base; the soil in the soil degradation is compost soil; the fiber fabric is dyed by reactive dye.
2. The processing method according to claim 1, characterized in that it comprises the steps of:
(1) mixing the fiber fabric dyed by the reactive dye with soil, and degrading the soil for 30-60 days to prepare a first degradation product; the soil pH is 7-8, and the ratio of C to N is (8-12): 1. the humidity is 55-65%; the degradation temperature is 15-25 ℃ in the soil degradation process;
(2) hydrolyzing the first degradation product by using 1-3 wt% of inorganic alkali water solution, wherein the hydrolysis temperature is 50-90 ℃.
3. The treatment method according to claim 2, wherein the reactive dye is at least one of KN type reactive dyes of vinyl sulfone type, M type reactive dyes and K type reactive dyes.
4. The treatment method according to claim 2, wherein in the step (1), the soil is compost soil, raw materials of the compost soil comprise compost fertilizer, substrate soil and auxiliary materials, and the compost fertilizer is human or animal excrement.
5. The method of claim 2, wherein the soil is stored at a temperature of 0-10 ℃ for 5-10 days before being mixed with the fiber fabric in step (1).
6. The treatment method according to claim 2, wherein the concentration of the aqueous inorganic base in the step (2) is 1 to 2 wt%.
7. The process according to claim 2, wherein in step (2), when the reactive dye is reactive black 5, the hydrolysis temperature is 50 to 75 ℃.
8. The process of claim 2, wherein in step (2) the hydrolysis temperature is 70-90 ℃ when the reactive dye is reactive red 198.
9. The process according to claim 2, wherein in step (2), the hydrolysis time is between 0.5 and 3 h.
10. The treatment method according to claim 2, wherein in the step (2), the second degradation product is further subjected to neutralization treatment with an acid.
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