CN113999322B - Low-energy-consumption preparation method of tempo oxidized cellulose with high carboxyl content - Google Patents

Low-energy-consumption preparation method of tempo oxidized cellulose with high carboxyl content Download PDF

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CN113999322B
CN113999322B CN202111467735.1A CN202111467735A CN113999322B CN 113999322 B CN113999322 B CN 113999322B CN 202111467735 A CN202111467735 A CN 202111467735A CN 113999322 B CN113999322 B CN 113999322B
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姜义军
陈常修
郗盼毅
夏延致
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Qingdao University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
    • C08B15/02—Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
    • C08B15/02—Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
    • C08B15/04—Carboxycellulose, e.g. prepared by oxidation with nitrogen dioxide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract

The invention relates to a low-energy-consumption preparation method of tempo oxidized cellulose with high carboxyl content, which comprises the steps of crushing a biomass raw material, soaking the biomass raw material in a peroxyacetic acid solution, stirring and reacting at 60-90 ℃, standing and layering the material, keeping a lower-layer precipitate, cleaning the lower-layer precipitate with an alkali solution and water, oxidizing the lower-layer precipitate with a tempo oxidized material, and repeatedly cleaning the precipitate after oxidation until a tempo oxidized cellulose colloid is obtained. The oxidized cellulose material prepared by the invention has high carboxyl content and has wide application prospect in various fields such as water treatment, nano composite materials and the like.

Description

Low-energy-consumption preparation method of tempo oxidized cellulose with high carboxyl content
Technical Field
The invention belongs to the technical field of nanocellulose manufacturing, relates to a method for directly converting biomass materials into oxidized cellulose nanofibrils, and particularly relates to a low-energy-consumption preparation method of tempo oxidized cellulose with high carboxyl content.
Background
The nano-cellulose has the characteristics of regeneration, degradability and the like of natural cellulose, and is widely applied to preparation of various functional composite materials due to the advantages of large specific surface area, high hydrophilicity, high transparency, high strength, low thermal expansion coefficient and the like. From the aspect of preparing raw materials, the biomass material has the advantages of wide source, abundant reserves, reproducibility, environmental friendliness and the like, and is beneficial to the current research on the nano-cellulose.
Cellulose is a polysaccharide with a crystal structure, is a natural polymer with the most abundant content on the earth, and oxidized nanocellulose has high length-diameter ratio, good dispersibility, more functional groups such as carboxyl content and the like, and is an important natural cellulose derivative. The TEMPO oxidation method is the most commonly used method of producing oxidized cellulose, and is a method of selectively oxidizing a hydroxyl group at the C6 position on a glucose unit to a carboxyl group, and separating cellulose filaments by electrostatic repulsion resulting from ionization of the carboxyl group on the surface of the cellulose filaments. In many other processes, such as etherification, oxidation, esterification, carboxymethylation etc., the principle is similar to the above processes, but these processes all require a pretreatment of the raw material, such as cooking multi-stage bleaching, in which the natural microfibril structure is destroyed to a varying extent, which drastically reduces the degree of polymerisation of the cellulose.
The preparation of the nano-cellulose comprises the following steps: (1) Preparing Hairy Cellulose Nanocrystalline (HCNC), cutting off amorphous area by chemical reagent, preserving crystalline area of cellulose, and having many polymer high molecular chains (about 100 nm) in the amorphous area; however, this method uses a hydrolysis material, so that cellulose is largely degraded, the yield of the product is low, and the requirement for equipment is high. And (2) preparing the nano microcrystalline cellulose (NCC). The amorphous region of cellulose is removed by strong acid or enzyme material, and the compact crystallization region is remained to obtain needle-like crystal whisker structure with high crystallinity (60% -90%), length of 100-400nm and diameter of 5-70nm. (3) preparation of microfibrillated cellulose (MFC). The MFC fiber is composed of amorphous areas and crystalline areas alternately, is in a fibrillar shape, has the diameter of 5-60nm and the length of 1000-10000nm, and has certain flexibility. However, conventional MFC production methods have certain disadvantages, and most production methods require pretreatment of the product followed by mechanical (e.g. high pressure homogenization, milling, etc.) fiber cutting and fiber separation. The pretreatment process (cooking, bleaching, etc.) consumes a large amount of electricity, heat, chemical reagents, water and other resources, and the mechanical treatment has high requirements on equipment and huge energy consumption. And (4) preparing bacterial cellulose (BNC). The glucose is produced by biological polymerization under the action of bacteria in biological enzyme, the crystallinity is higher than that of plant fiber bundles, the diameter is 20-100nm, the length is indefinite, the tensile strength is high, the method can regulate and control the structure, the crystal form and the particle size distribution of a product, and the energy consumption is low and no pollution is caused. But the production period is long, the yield is low, the cost is high, the processing technology is difficult to regulate and control, and the industrialization is difficult.
Disclosure of Invention
The invention aims to solve the technical problem of providing a low-energy-consumption preparation method of Tempo oxidized nano-cellulose, which is based on a Tempo oxidation system, introduces peroxyacetic acid for bleaching, removes lignin in a biomass raw material, primarily degrades cellulose, then selectively oxidizes the cellulose by using the Tempo oxidation system to further oxidize and degrade the fiber, finally obtains the Tempo oxidized nano-cellulose with high carboxyl content at a nano level, and realizes the conversion from wood to a nano material. The whole process completely does not need high-energy-consumption mechanical equipment such as a high-pressure homogenizer for treatment, the whole system is simple and energy-saving, and the high production efficiency and the low production cost of industrialization are ensured.
The invention discloses a novel low-energy-consumption method for preparing tempo oxidized cellulose with high carboxyl content, which reduces the requirements of high-energy-consumption disc mills, ball mills and high-pressure homogenizers in the prior art. The method comprises the following operation steps: chopping wood, soaking in 5% peracetic acid solution, stirring at 60-90 deg.c for 24 hr, standing to separate the material, washing the lower precipitate with 1mol/l NaOH solution and deionized water, and oxidizing with oxidizing material in 0.4-0.9 times the weight of the bleached material. After oxidation, the precipitate was repeatedly washed with deionized water until a tempo oxidized cellulose gel was obtained. The method has the advantages of simple process, few chemical varieties, easy obtainment, low price, no need of high-pressure homogenization, smaller particle size of the finally obtained cellulose, higher oxidation degree and wide application prospect in the fields of nano composite materials, power generation materials and the like.
A low-energy-consumption preparation method of a tempo oxidized cellulose with high carboxyl content comprises the steps of crushing a biomass raw material, soaking the crushed biomass raw material in a peroxyacetic acid solution, stirring the crushed biomass raw material at 60-90 ℃ for reaction, standing the material for layering, keeping a lower-layer precipitate, washing the lower-layer precipitate with an alkali solution and water, oxidizing the lower-layer precipitate with a tempo oxidized material, and repeatedly washing the oxidized precipitate until a tempo oxidized cellulose colloid is obtained.
Preferably, the method comprises the following steps:
(1) Chopping a biomass raw material, soaking the biomass raw material in a peroxyacetic acid solution, stirring and reacting for 12-24 hours, standing the material for layering, keeping a lower-layer precipitate, washing the lower-layer precipitate with 1mol/l NaOH solution and deionized water until the precipitate is neutral, removing lignin in the biomass raw material, and finally obtaining a mixed material of cellulose and hemicellulose;
(2) Placing the mixture of cellulose and hemicellulose in a reaction kettle, adding Tempo and sodium bromide, then adding water, stirring at 500r/min, slowly adding a sodium hypochlorite solution, and stirring; adjusting the pH value to be within the range of 10-10.5, continuing to react for 1h, adjusting the pH value to be neutral, stopping the reaction, and then standing for layering;
(3) And repeatedly washing the reacted precipitate with deionized water until a Tempo oxidized cellulose colloid is obtained.
It is preferable that: the concentration of the peroxyacetic acid is 4-6%.
It is preferable that: the Tempo oxidizing material is Tempo (2, 6-tetramethylpiperidine-nitrogen-oxide).
It is preferable that: the mass ratio is as follows: biomass feedstock Tempo (2, 6-tetramethylpiperidine-nitrogen-oxide), sodium bromide: sodium hypochlorite = 10.
It is preferable that: the biomass raw material comprises: at least one of fir, bamboo chips, cotton and hemp.
It is preferable that: the pH value of the system in the reaction process is controlled to be between 7 and 12.
It is preferable that: the reaction time before the pH value is adjusted is controlled to be 6h-48h and the reaction time after the pH value is adjusted is controlled to be 0.5h-2h;
it is preferable that: the concentration range of the active chlorine in the system is controlled to be 5-10%.
It is preferable that: in the step of washing the oxidized cellulose, the pH =3 of the centrifuged supernatant is adjusted to separate out the oxidized cellulose with smaller size in the supernatant, and finally the yield of the oxidized cellulose can be improved.
The invention has the beneficial effects that:
1. the preparation method is simple in preparation process, does not need high-strength high-energy-consumption mechanical treatment, and is suitable for large-scale industrial production;
2. the raw materials used in the present invention include all the biomass raw materials that can be used, such as bamboo, cedar, hemp, etc., and also include biomass such as unutilized weeds, shrubs, etc.;
3. the chemical medicine materials used in the invention are few in variety and easy to obtain and low in price;
4. the oxidized cellulose material prepared by the invention has high carboxyl content and has wide application prospect in various fields such as water treatment, nano composite materials and the like.
Drawings
FIG. 1 is a graph showing the particle size of Tempo oxidized cellulose prepared in the present invention as a function of various process conditions.
Detailed Description
The present invention is further described in detail below with reference to operation examples so that those skilled in the art can better understand the technical solutions of the present invention.
Example 1
Adding 100g of Chinese fir chips and 400ml of peroxyacetic acid with the mass concentration of 5% into a 1000ml beaker, stirring for 24 hours at 85 ℃, standing for 1 hour, pouring out the supernatant, reserving the lower-layer precipitate, and repeatedly washing the precipitate with 0.1mol/L NaOH and deionized water in sequence until the material is neutral.
2g of dry fiber material, 0.021g of Tempo (2, 6-tetramethylpiperidine-nitrogen-oxide), 0.1g of sodium bromide and 50ml of sodium hypochlorite (active chlorine 10%) are put into a 250ml three-mouth flask and stirred for 24 hours at a speed of 500r/min, the pH value is adjusted by 0.1M NaOH to be about 10.3, the mixture is stirred and reacted for 1 hour, then the solution is kept stand for 2 hours to be layered, finally, supernatant liquid is poured out, and precipitates are repeatedly washed by deionized water until uniform colloid appears, so that the oxidized nano-cellulose is obtained.
The obtained oxidized nanofibrils have a particle size of 350-400nm and a carboxyl content of 1.35mmol/g.
Example 2
Adding 100g of Chinese fir chips and 400ml of peroxyacetic acid with the mass concentration of 5% into a 1000ml beaker, stirring for 24 hours at 85 ℃, standing for 1 hour, pouring out supernatant, reserving precipitate at the lower layer, and repeatedly washing the precipitate with 0.1mol/L NaOH and deionized water in sequence until the material is neutral.
2g of dry fiber material, 0.042g of Tempo (2, 6-tetramethylpiperidine-nitrogen-oxide), 0.2g of sodium bromide and 100ml of sodium hypochlorite (active chlorine 10%) are put into a 250ml three-mouth flask and stirred for 24 hours at a speed of 500r/min, the pH value is adjusted by 0.1M NaOH to be about 10.3, the mixture is stirred and reacted for 1 hour, then the solution is kept stand for 2 hours to separate the solution, finally, the supernatant is poured out, and the precipitate is repeatedly washed by deionized water until uniform colloid appears, so that the oxidized nano-cellulose is obtained.
The obtained oxidized nanofibrils have a particle size of 200-250nm and a carboxyl group content of 2.3mmol/g.
Example 3
Adding 100g of Chinese fir wood chips and 400ml of peroxyacetic acid with the mass concentration of 5% into a 1000ml beaker, stirring at 85 ℃ for 24h, standing for 1h, pouring out the supernatant, reserving the lower-layer precipitate, and repeatedly washing the precipitate with 0.1mol/L NaOH and deionized water in sequence until the material is neutral.
2g of dry fiber material, 0.063g of Tempo (2, 6-tetramethylpiperidine-nitrogen-oxide), 0.3g of sodium bromide and 150ml of sodium hypochlorite (active chlorine 10%) are put into a 250ml three-mouth flask and stirred for 24 hours at a speed of 500r/min, the pH value is adjusted by 0.1M NaOH to be about 10.3, the mixture is stirred and reacted for 1 hour, then the solution is kept stand for 2 hours to be layered, finally, supernatant is poured out, and precipitates are repeatedly washed by deionized water until uniform colloid appears, so that the oxidized nano-cellulose is obtained.
The obtained oxidized nanofibrils have a particle size of 200-260nm and a carboxyl content of 1.4mmol/g.
Example 4
Adding 100g of Chinese fir wood chips and 400ml of peroxyacetic acid with the mass concentration of 5% into a 1000ml beaker, stirring at 85 ℃ for 24h, standing for 1h, pouring out the supernatant, reserving the lower-layer precipitate, and repeatedly washing the precipitate with 0.1mol/L NaOH and deionized water in sequence until the material is neutral.
2g of dry fiber material, 0.042g of Tempo (2, 6-tetramethylpiperidine-nitrogen-oxide), 0.2g of sodium bromide and 100ml of sodium hypochlorite (active chlorine 10%) are put into a 250ml three-mouth flask and stirred at 500r/min for 24h, the pH value is adjusted by 0.1M NaOH to be about 12, stirring and reacting are carried out for 1h, then the solution is kept still for 2h to stratify the solution, finally, the supernatant is poured out, and the precipitate is repeatedly washed by deionized water until uniform colloid appears, so that the oxidized nano-cellulose is obtained.
The obtained oxidized nanofibrils have a particle size of 240-280nm and a carboxyl group content of 2.2mmol/g.
Example 5
Adding 100g of Chinese fir wood chips and 400ml of peroxyacetic acid with the mass concentration of 5% into a 1000ml beaker, stirring at 85 ℃ for 24h, standing for 1h, pouring out the supernatant, reserving the lower-layer precipitate, and repeatedly washing the precipitate with 0.1mol/L NaOH and deionized water in sequence until the material is neutral.
2g of dry fiber material, 0.042g of Tempo (2, 6-tetramethylpiperidine-nitrogen-oxide), 0.2g of sodium bromide and 100ml of sodium hypochlorite (active chlorine 10%) are put into a 250ml three-mouth flask and stirred for 24 hours at a speed of 500r/min, the pH value is adjusted by 0.1M NaOH to be about 7, stirring and reaction are carried out for 1 hour, then the solution is kept still for 2 hours to separate the solution, finally, the supernatant is poured out, and the precipitate is repeatedly washed by deionized water until uniform colloid appears, so that the oxidized nano-cellulose is obtained.
The obtained oxidized nanofibrils have a particle size of 250-300nm and a carboxyl group content of 1.4mmol/g.
Example 6
Adding 100g of Chinese fir wood chips and 400ml of peroxyacetic acid with the mass concentration of 5% into a 1000ml beaker, stirring at 85 ℃ for 24h, standing for 1h, pouring out the supernatant, reserving the lower-layer precipitate, and repeatedly washing the precipitate with 0.1mol/L NaOH and deionized water in sequence until the material is neutral.
2g of dry fiber material, 0.042g of Tempo (2, 6-tetramethylpiperidine-nitrogen-oxide), 0.2g of sodium bromide and 100ml of sodium hypochlorite (active chlorine 10%) are put into a 250ml three-mouth flask and stirred for 12 hours at a speed of 500r/min, the pH value is adjusted by 0.1M NaOH to be about 10.3, the mixture is stirred and reacted for 1 hour, then the solution is kept stand for 2 hours to separate the solution, finally, the supernatant is poured out, and the precipitate is repeatedly washed by deionized water until uniform colloid appears, so that the oxidized nano-cellulose is obtained.
The obtained oxidized nanofibrils have a particle size of 200-250nm and a carboxyl content of 2.2mmol/g.
Example 7
Adding 100g of Chinese fir wood chips and 400ml of peroxyacetic acid with the mass concentration of 5% into a 1000ml beaker, stirring at 85 ℃ for 24h, standing for 1h, pouring out the supernatant, reserving the lower-layer precipitate, and repeatedly washing the precipitate with 0.1mol/L NaOH and deionized water in sequence until the material is neutral.
2g of dry fiber material, 0.042g of Tempo (2, 6-tetramethylpiperidine-nitrogen-oxide), 0.2g of sodium bromide and 100ml of sodium hypochlorite (active chlorine 10%) are put into a 250ml three-mouth flask and stirred for 48 hours at a speed of 500r/min, the pH value is adjusted by 0.1M NaOH to be about 10.3, the mixture is stirred and reacted for 1 hour, then the solution is kept stand for 2 hours to separate the solution, finally, the supernatant is poured out, and the precipitate is repeatedly washed by deionized water until uniform colloid appears, so that the oxidized nano-cellulose is obtained.
The obtained oxidized nanofibrils have a particle size of 280-330nm and a carboxyl content of 1.76mmol/g.
Example 8
Adding 100g of Chinese fir wood chips and 400ml of peroxyacetic acid with the mass concentration of 5% into a 1000ml beaker, stirring at 85 ℃ for 24h, standing for 1h, pouring out the supernatant, reserving the lower-layer precipitate, and repeatedly washing the precipitate with 0.1mol/L NaOH and deionized water in sequence until the material is neutral.
2g of dry fiber material, 0.042g of Tempo (2, 6-tetramethylpiperidine-nitrogen-oxide), 0.2g of sodium bromide and 100ml of sodium hypochlorite (active chlorine 10%) are put into a 250ml three-mouth flask and stirred for 24 hours at a speed of 500r/min, then 0.1M NaOH is used for adjusting the pH value to be about 10.3 and stirred for reaction for 0.5 hour, then the solution is kept stand for 2 hours for layering, finally the supernatant is poured out, and the precipitate is repeatedly washed by deionized water until uniform colloid appears, so that the oxidized nano-cellulose is obtained.
The obtained oxidized nanofibrils have a particle size of 350-400nm and a carboxyl content of 1.3mmol/g.
Example 9
Adding 100g of Chinese fir wood chips and 400ml of peroxyacetic acid with the mass concentration of 5% into a 1000ml beaker, stirring at 85 ℃ for 24h, standing for 1h, pouring out the supernatant, reserving the lower-layer precipitate, and repeatedly washing the precipitate with 0.1mol/L NaOH and deionized water in sequence until the material is neutral.
2g of dry fiber material, 0.042g of Tempo (2, 6-tetramethylpiperidine-nitrogen-oxide), 0.2g of sodium bromide and 100ml of sodium hypochlorite (active chlorine 10%) are put into a 250ml three-mouth flask and stirred for 24 hours at a speed of 500r/min, then 0.1M NaOH is used for adjusting the pH value to be about 10.3 and stirred for reaction for 1.5 hours, then the solution is kept stand for 2 hours for layering, finally the supernatant is poured out, and the precipitate is repeatedly washed by deionized water until uniform colloid appears, so that the oxidized nano-cellulose is obtained.
The obtained oxidized nanofibrils have a particle size of 230-280nm and a carboxyl content of 2.1mmol/g.
Example 10
Adding 100g of bamboo fragments and 400ml of peroxyacetic acid with the mass concentration of 5% into a 1000ml beaker, stirring at 85 ℃ for 24h, standing for 1h, pouring out the supernatant, retaining the lower-layer precipitate, and repeatedly washing the precipitate with 0.1mol/L NaOH and deionized water in sequence until the material is neutral.
2g of dry fiber material, 0.042g of Tempo (2, 6-tetramethylpiperidine-nitrogen-oxide), 0.2g of sodium bromide and 100ml of sodium hypochlorite (active chlorine 10%) are put into a 250ml three-mouth flask and stirred for 24 hours at a speed of 500r/min, the pH value is adjusted by 0.1M NaOH to be about 10.3, the mixture is stirred and reacted for 1 hour, then the solution is kept stand for 2 hours to separate the solution, finally, the supernatant is poured out, and the precipitate is repeatedly washed by deionized water until uniform colloid appears, so that the oxidized nano-cellulose is obtained.
The resulting oxidized nanofibrils had a particle size of 280-330nm and a carboxyl content of 1.04mmol/g.
Example 11
2g of dry cedar chips, 0.042g of Tempo (2, 6-tetramethylpiperidine-nitrogen-oxide), 0.2g of sodium bromide and 100ml of sodium hypochlorite (active chlorine 10%) are put into a 250ml three-mouth flask and stirred at 500r/min for 24h, then 0.1M NaOH is used for regulating the pH value to be about 10.3 and stirring for reaction for 1h, then the solution is kept stand for 2h for layering, finally the supernatant is poured out, and the precipitate is repeatedly washed by deionized water until uniform colloid appears, so that the oxidized nano-cellulose is obtained.
The obtained oxidized nanofibrils have a particle size of 1800-2500nm and a carboxyl group content of 1.3mmol/g.
TABLE 1 comparison of carboxyl content of TEMPO oxidized cellulose from the commercial supplier to that of the example
Figure BDA0003392239090000071
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Figure BDA0003392239090000081
According to examples 1-11 and table one, after the biomass raw material needs to be treated by PAA, the ratio of the oxidized material to the biomass raw material is 0.6, 1, and after 24 hours of reaction time, the reaction is carried out for 1 hour again under the condition of adjusting the pH value to 10.3, so that the Tempo oxidized cellulose with high carboxyl content (2.3 mmol/g) can be obtained.

Claims (4)

1. A low-energy-consumption preparation method of tempo oxidized cellulose with high carboxyl content is characterized in that: the method comprises the following steps:
(1) Chopping a biomass raw material, soaking the chopped biomass raw material in a peroxyacetic acid solution with the concentration of 1-35%, stirring and reacting for 12-24 h at the temperature of 60-90 ℃, standing and layering the material, keeping a lower-layer precipitate, washing the lower-layer precipitate with 1mol/l NaOH solution and deionized water until the precipitate is neutral, removing lignin in the biomass raw material, and finally obtaining a mixed material of cellulose and hemicellulose;
(2) Placing a mixture of cellulose and hemicellulose in a reaction kettle, adding a tempo oxidation material and sodium bromide, then adding water, stirring at 500r/min, slowly adding a sodium hypochlorite solution, and stirring; adjusting the pH value to be within the range of 8-14, continuously reacting for 1h, adjusting the pH value to be neutral, terminating the reaction, and then standing for layering; the tempo oxidation material is tempo2, 6-tetramethylpiperidine-nitrogen-oxide;
(3) Repeatedly washing the reacted precipitate with deionized water until a tempo oxidized cellulose colloid is obtained;
biomass raw material tempo2, 6-tetramethylpiperidine-nitrogen-oxide sodium bromide: the mass ratio of sodium hypochlorite =10:0.1-0.5:0.5-2:0.5-2.
2. A low-energy production method of tempo-oxidized cellulose with high carboxyl group content according to claim 1, characterized in that: the biomass raw material comprises: at least one of wood chip, bamboo chip, cotton, hemp and straw.
3. A low-energy production method of tempo-oxidized cellulose with high carboxyl group content according to claim 1, characterized in that: the reaction time before the pH is adjusted to be in the range of 8-14 in the step (2) is controlled to be 6-48 h.
4. A low energy method for preparing tempo-oxidized cellulose with high carboxyl group content according to claim 1, wherein: the concentration range of active chlorine in the system is controlled to be 5-10%.
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