CN110937727A - PROBAN flame-retardant wastewater treatment method - Google Patents
PROBAN flame-retardant wastewater treatment method Download PDFInfo
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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- C02F1/00—Treatment of water, waste water, or sewage
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Abstract
The invention discloses a PROBAN flame-retardant wastewater treatment method, and belongs to the field of water pollution treatment and textile printing and dyeing wastewater treatment technologies. Comprises (1) PROBAN fire-retardant waste water grouping: aiming at an oxidation washing process for producing flame-retardant cloth by a PROBAN method, the oxidation washing process comprises washing tanks which are connected in series with 10 levels, and the washing tanks which are connected in series with 10 levels are sequentially divided into a group A and a group B; merging the wastewater discharged from each stage of rinsing tanks in the group A to obtain high-concentration PROBAN flame-retardant wastewater; merging the wastewater discharged from each stage of rinsing tanks in the group B to obtain low-concentration PROBAN flame-retardant wastewater; (2) PROBAN flame-retardant wastewater treatment: treating high-concentration PROBAN flame-retardant wastewater; treating low-concentration PROBAN flame-retardant wastewater; according to the invention, the flame-retardant wastewater is divided into high-concentration flame-retardant wastewater and low-concentration flame-retardant wastewater through technical transformation, the high-concentration flame-retardant wastewater is dephosphorized by adopting an evaporation process, and the low-concentration flame-retardant wastewater is dephosphorized by adopting an advanced oxidation process. Effectively solves the problem of organic phosphorus pollution and realizes the reuse of reclaimed water.
Description
Technical Field
The invention belongs to the technical field of textile printing and dyeing wastewater treatment, and particularly relates to a PROBAN flame-retardant wastewater treatment method.
Background
Printing and dyeing are one of the national support industries, and have the characteristics of large printing and dyeing wastewater discharge amount, complex water quality components, high COD (chemical oxygen demand), high chroma, high treatment difficulty and the like. Particularly, with the improvement of the printing and dyeing after-finishing technology, functional fabrics such as flame-retardant fabrics, radiation-proof fabrics, antistatic fabrics and the like are widely applied in life and production. In the production process of the functional fabric, a plurality of printing and dyeing and after-finishing auxiliaries which are difficult to biodegrade are added, so that the treatment difficulty of printing and dyeing wastewater is further increased.
At present, a Pluronic (PROBAN) method flame retardant process is usually adopted in a flame retardant cloth production process, and is a padding and post-baking process adopting a tetramethylol phosphorus chloride-urea prepolymer as a flame retardant, and the process flow is that a fabric is padded with tetramethylol phosphorus chloride-urea pre-condensed flame retardant finishing liquid (room temperature) → pre-baking (100-120 ℃) → ammonia fumigation → oxidative washing → drying (130-140 ℃) → pre-shrinking → finished products, so that the flame retardant cloth is an important method for the flame retardant finishing of the existing durable cotton fabrics, and has the advantages of good flame retardant effect, small fabric strength reduction, little hand feeling influence and the like.
The PROBAN flame-retardant wastewater generated in the whole production process of the flame-retardant cloth mainly comes from an oxidation washing process. The prior oxidation washing usually adopts a washing machine, the oxidation washing of the fabric is realized by connecting ten-stage washing tanks in series, the flame retardant is more stable after being cured by ammonia fumigation, and P must be treated3+By oxidation to P5+Adding hydrogen peroxide into an oxidation rinsing bath close to the ammonia fumigation process section for soaking, and then rinsing and neutralizing the residual flame retardant, hydrogen peroxide and other materials on the fabric in sequence by a subsequent oxidation rinsing bath. The water used for oxidation washing enters the washing machine from the cloth outlet end of the washing machine, flows through ten-stage washing tanks in series in sequence,and discharging from a rinsing bath for padding hydrogen peroxide. In each stage of oxidation rinsing bath, the content of hydrogen peroxide and organic phosphorus in water washed by the rinsing bath padded with hydrogen peroxide is highest, and the content of hydrogen peroxide and organic phosphorus in water washed by the subsequent oxidation rinsing bath is gradually reduced, so that the produced PROBAN flame-retardant wastewater has the characteristics of high chemical demand (COD) content, high residual hydrogen peroxide content, high organic phosphorus content and the like, is typical difficult to treat, and can cause serious pollution to the environment if directly discharged.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a PROBAN flame-retardant wastewater treatment method.
In order to achieve the aim, the invention provides a PROBAN flame-retardant wastewater treatment method, which comprises the following steps:
(1) PROBAN flame-retardant wastewater grouping
Aiming at an oxidation washing process for producing flame-retardant cloth by a PROBAN method, the oxidation washing process comprises washing tanks which are connected in series with 10 levels, and the washing tanks which are connected in series with 10 levels are sequentially divided into a group A and a group B; wherein, group A contains 3, 4 or 5-grade rinsing tanks for first oxidation rinsing of the flame-retardant cloth, and the corresponding group B contains 7, 6 or 5-grade rinsing tanks for second oxidation rinsing of the flame-retardant cloth;
merging the wastewater discharged from each stage of rinsing tanks in the group A to obtain high-concentration PROBAN flame-retardant wastewater;
merging the wastewater discharged from each stage of rinsing tanks in the group B to obtain low-concentration PROBAN flame-retardant wastewater;
(2) PROBAN flame-retardant wastewater treatment
Treating high-concentration PROBAN flame-retardant wastewater: treating the high-concentration PROBAN flame-retardant wastewater obtained in the step (1) by evaporation, wherein the evaporated condensate water is reused for oxidation water washing in the group B water washing tank in the step (1); disposing the evaporated crystal according to solid waste; adding ferrate into the evaporated concentrated solution, performing catalytic oxidation by ozone, reacting for 1-2 hours to obtain a wastewater sludge mixture, and then discharging the wastewater sludge mixture to a sludge concentration tank for further treatment;
treating low-concentration PROBAN flame-retardant wastewater: and (2) treating the low-concentration PROBAN flame-retardant wastewater obtained in the step (1) by adopting a strong oxidation and precipitation process.
Preferably, each stage of rinsing bath in the group A and each stage of rinsing bath in the group B are respectively provided with a water inlet and a water outlet.
Preferably, the water requirements of the rinsing baths in the group A and the rinsing baths in the group B are equal.
Preferably, the ferrate is one or two of sodium ferrate and potassium ferrate, and the addition amount is 5-15 g/L.
Preferably, the adding amount of the ozone is 300-400 g/h.
Preferably, the low-concentration PROBAN flame-retardant wastewater is treated by adopting a strong oxidation and precipitation process, and the method comprises the following steps:
s1, introducing the low-concentration PROBAN flame-retardant wastewater into a reaction container, adding sulfuric acid or hydrochloric acid to adjust the pH value to 2-4, then adding 8-15 g/L ferrous sulfate, and stirring to react for 1-3 hours to obtain primary reaction wastewater;
s2, carrying out catalytic ozonation on the primary reaction wastewater obtained in the step S1 in the presence of a catalyst, and reacting for 1-2 hours to obtain intermediate reaction wastewater; wherein the adding amount of the ozone is 0.1-0.4 g/L, and the filling amount of the catalyst is 1/20-1/5 of the volume of the reaction container in S1;
s3, adding an oxidizing chemical agent into the middle-grade reaction wastewater obtained in the step S2, reacting for 1-2 hours, adjusting the pH value to 8-9, and coagulating to obtain coagulation wastewater;
s4, precipitating the coagulated wastewater obtained in the step S3 for 1-3 hours to obtain phosphorus-containing sludge and wastewater, and then separating the phosphorus-containing sludge from the wastewater, wherein the wastewater is reused as the water for group A oxidation washing; and (4) discharging the phosphorus-containing sludge to a sludge concentration tank for further treatment, and carrying out outward treatment after dehydration.
Preferably, the oxidizing chemical agent is one or more of sodium ferrate, potassium ferrate, sodium hypochlorite, calcium hypochlorite, chlorine gas and chlorine dioxide.
Compared with the prior art, the invention has the beneficial effects that:
(1) aiming at the water quality characteristics of the PROBAN flame-retardant wastewater and the change gradient of the concentration of a pollution factor in the wastewater generation process, the PROBAN flame-retardant wastewater is divided into high-concentration flame-retardant wastewater and low-concentration flame-retardant wastewater, and is subjected to targeted individual treatment, so that the treatment problem of the PROBAN flame-retardant wastewater is thoroughly solved at low cost, the reclaimed water is recycled, the production cost is reduced, and meanwhile, the removal rate of organic phosphorus is further improved, and the total phosphorus content is less than 1 mg/L; compared with an evaporation process, the investment cost is saved by 45 percent, and the cost of water treatment per ton is saved by 40 percent.
(2) The ferrate added in the invention has strong oxidizing property, can oxidize and decompose organic matters in the wastewater, oxidize organic phosphorus in the wastewater into inorganic phosphorus, the existence of iron ions can catalyze ozone oxidation, the capability and efficiency of oxidizing the organic matters and the organic phosphorus in the wastewater by the ozone are improved, the ferrate and the ozone are oxidized cooperatively, the oxidative decomposition rate of the organic phosphorus is improved to 98 percent from 55 percent, and simultaneously, Fe produced by the reduced ferrate3+And the inorganic phosphorus generated by oxidation is combined to form ferric phosphate salt precipitate, so that the aim of removing phosphorus from the wastewater is fulfilled.
(3) The invention thoroughly eliminates the potential safety hazard and toxic and side effects of the PROBAN flame-retardant wastewater on the stable operation of the wastewater treatment process of the comprehensive sewage treatment plant of the printing and dyeing enterprise, the total phosphorus content of the treated wastewater is less than 1mg/L, and the treated wastewater can be utilized, decomposed and absorbed by microorganisms in a biochemical treatment system even if discharged into the comprehensive sewage treatment plant, thereby being beneficial to the stable operation of the biochemical treatment system and leading the discharged water to stably reach the standard.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments.
Example 1
A PROBAN flame-retardant wastewater treatment method comprises the following steps:
(1) PROBAN flame-retardant wastewater grouping
Aiming at an oxidation washing process for producing flame-retardant cloth by a PROBAN method, the oxidation washing process comprises washing tanks which are connected in series with 10 levels, and the washing tanks which are connected in series with 10 levels are sequentially divided into a group A and a group B;
wherein, the group A comprises flame-retardant cloth and is firstly oxidized and washedThe corresponding group B comprises a 6-level rinsing tank for oxidizing and rinsing the flame-retardant cloth again; meanwhile, the water consumption of the group A oxidation washing is 4m3The water consumption for oxidizing and washing the group B is 6m3/h；
Merging the wastewater discharged from each stage of rinsing tanks in the group A to obtain high-concentration PROBAN flame-retardant wastewater;
merging the wastewater discharged from each stage of rinsing tanks in the group B to obtain low-concentration PROBAN flame-retardant wastewater;
(2) PROBAN flame-retardant wastewater treatment
Treating high-concentration PROBAN flame-retardant wastewater: the amount of water obtained in (1) was 4m3High-concentration PROBAN flame-retardant wastewater with a phosphorus content (TP) of 1500mg/L is treated by adopting a reduced-pressure triple-effect evaporation process, wherein the water amount of evaporated condensed water is measured to be 3.6m3/h、TP 0.1mg/L，CODCr20mg/L, 1 time of chroma and less than 1mg/L of suspended matters (SS), meets the water quality index requirement of the B group oxidation washing water, and is reused for the oxidation washing water in the B group washing tank in the step (1);
disposing the evaporated crystal according to solid waste;
the water content of the evaporated concentrate is 0.4m3The concentration ratio of the waste water to the sludge is 14000mg/L, 10g/L of sodium ferrate is added into the mixture, the mixture is subjected to catalytic oxidation reaction for 1h by 400g/h of ozone to obtain a waste water sludge mixture, and the waste water sludge mixture is discharged to a sludge concentration tank for further treatment;
treating low-concentration PROBAN flame-retardant wastewater: the amount of water obtained in (1) was 6m3The method is characterized in that the low-concentration PROBAN flame-retardant wastewater of/h and TP 40mg/L is treated by adopting a strong oxidation and precipitation process, and comprises the following steps:
s1, introducing the low-concentration PROBAN flame-retardant wastewater into a reaction vessel, adding sulfuric acid or hydrochloric acid to adjust the pH value to 3, then adding 8g/L ferrous sulfate, and stirring to react for 1.5h to obtain primary reaction wastewater;
s2, carrying out ozone catalytic oxidation on the primary reaction wastewater obtained in the step S1 by taking copper oxide loaded on an alumina plate as a catalyst, and reacting for 1h to obtain intermediate reaction wastewater; wherein the adding amount of the ozone is 100mg/L, and the filling amount of the catalyst is 1/20 of the volume of the reaction vessel in S1;
s3, adding 6g/L of sodium hypochlorite with the effective chlorine content of 11% into the middle-grade reaction wastewater obtained in the step S2, reacting for 1h, adjusting the pH value to 8, and coagulating to obtain coagulation wastewater;
s4, precipitating the coagulation wastewater obtained in the step S3 for 1h to obtain phosphorus-containing sludge and wastewater, separating the phosphorus-containing sludge from the wastewater, filtering the wastewater by using a ceramic ultrafiltration membrane, and measuring the effluent to be 5.4m3/h、TP 0.4mg/L、CODCr50-100mg/L, 1 time of chroma and less than 1mg/L of SS, meets the water quality index requirement of the group A oxidation washing water, and takes 4m3The waste water/h is reused as the water for washing the group A oxidation water, and the rest is 1.4m3The wastewater enters a comprehensive sewage treatment system for further treatment; discharging the phosphorus-containing sludge to a sludge concentration tank for further treatment, and carrying out outward treatment after dehydration; the ceramic ultrafiltration backwashing water enters a comprehensive sewage treatment system for further treatment.
Example 2
A PROBAN flame-retardant wastewater treatment method comprises the following steps:
(1) PROBAN flame-retardant wastewater grouping
Aiming at an oxidation washing process for producing flame-retardant cloth by a PROBAN method, the oxidation washing process comprises washing tanks which are connected in series with 10 levels, and the washing tanks which are connected in series with 10 levels are sequentially divided into a group A and a group B;
wherein, the group A comprises a 3-level rinsing bath for firstly carrying out oxidation rinsing on the flame-retardant cloth, and the corresponding group B comprises a 7-level rinsing bath for carrying out oxidation rinsing on the flame-retardant cloth again; meanwhile, the water consumption of the group A oxidation washing is 3m3The water consumption for oxidizing and washing the group B is 7m3/h；
Merging the wastewater discharged from each stage of rinsing tanks in the group A to obtain high-concentration PROBAN flame-retardant wastewater;
merging the wastewater discharged from each stage of rinsing tanks in the group B to obtain low-concentration PROBAN flame-retardant wastewater;
(2) PROBAN flame-retardant wastewater treatment
Treating high-concentration PROBAN flame-retardant wastewater: the amount of water obtained in (1) was 3m3Treating high-concentration PROBAN flame-retardant wastewater with concentration/h and TP of 3000mg/L by adopting a reduced-pressure triple-effect evaporation process, wherein the evaporated condensed water is measured and subjected toThe water amount is 2.7m3/h、TP 0.2mg/L，CODCr50mg/L, 1 time of chroma and less than 1mg/L of SS, meets the water quality index requirement of the B group oxidation washing water, and is reused for the oxidation washing water in the B group washing tank in the step (1);
disposing the evaporated crystal according to solid waste;
the water content of the evaporated concentrate is 0.3m3Adding 10g/L of sodium ferrate into the mixture with the TP of 25000mg/L, performing catalytic oxidation reaction for 2 hours by using 300g/h of ozone to obtain a wastewater sludge mixture, and then discharging the wastewater sludge mixture to a sludge concentration tank for further treatment;
treating low-concentration PROBAN flame-retardant wastewater: the amount of water obtained in (1) was 7m3The method is characterized in that the low-concentration PROBAN flame-retardant wastewater of per hour and TP 80mg/L is treated by adopting a strong oxidation and precipitation process, and comprises the following steps:
s1, introducing the low-concentration PROBAN flame-retardant wastewater into a reaction vessel, adding sulfuric acid or hydrochloric acid to adjust the pH value to 2, then adding 15g/L ferrous sulfate, and stirring to react for 3 hours to obtain primary reaction wastewater;
s2, carrying out ozone catalytic oxidation on the primary reaction wastewater obtained in the step S1 by using manganese oxide loaded on an alumina plate as a catalyst, and reacting for 2 hours to obtain intermediate-grade reaction wastewater; wherein the adding amount of the ozone is 0.4g/L, and the filling amount of the catalyst is 1/5 of the volume of the reaction container in S1;
s3, adding 4g/L of sodium ferrate into the middle-grade reaction wastewater obtained in the step S2, reacting for 2 hours, adjusting the pH value to 8.5, and coagulating to obtain coagulation wastewater;
s4, precipitating the coagulation wastewater obtained in the step S3 for 3 hours to obtain phosphorus-containing sludge and wastewater, separating the phosphorus-containing sludge from the wastewater, filtering the wastewater by using a ceramic ultrafiltration membrane, and measuring the effluent to be 6.3m3/h、TP0.8mg/L、CODCr100mg/L, 1 time of chroma and SS less than 1mg/L, meets the water quality index requirement of the group A oxidation washing water, and takes 3m3The waste water is reused as the water for washing the group A oxidation water, and the rest is 3.3m3The wastewater enters a comprehensive sewage treatment system for further treatment, and the phosphorus-containing sludge enters a sludge treatment system for treatment; the ceramic ultrafiltration backwashing water enters a comprehensive wastewater treatment system for further treatment;
example 3
A PROBAN flame-retardant wastewater treatment method comprises the following steps:
(1) PROBAN flame-retardant wastewater grouping
Aiming at an oxidation washing process for producing flame-retardant cloth by a PROBAN method, the oxidation washing process comprises washing tanks which are connected in series with 10 levels, and the washing tanks which are connected in series with 10 levels are sequentially divided into a group A and a group B;
wherein, the group A comprises a 5-level rinsing bath for firstly carrying out oxidation rinsing on the flame-retardant cloth, and the corresponding group B comprises a 5-level rinsing bath for carrying out oxidation rinsing on the flame-retardant cloth again; meanwhile, the water consumption of the group A oxidation washing is 5m3The water consumption for oxidizing and washing the group B is 5m3/h；
Merging the wastewater discharged from each stage of rinsing tanks in the group A to obtain high-concentration PROBAN flame-retardant wastewater;
merging the wastewater discharged from each stage of rinsing tanks in the group B to obtain low-concentration PROBAN flame-retardant wastewater;
(2) PROBAN flame-retardant wastewater treatment
Treating high-concentration PROBAN flame-retardant wastewater: the amount of water obtained in (1) was 5m3Treating high-concentration PROBAN flame-retardant wastewater with concentration of 2000mg/L and TP by reduced-pressure triple-effect evaporation process, wherein the water amount of evaporated condensate water is 4.7m by measuring3/h、TP 0.15mg/L，CODCr30mg/L, 1 time of chroma and less than 1mg/L of SS, meets the water quality index requirement of the B group oxidation washing water, and is reused for the oxidation washing water in the B group washing tank in the step (1);
disposing the evaporated crystal according to solid waste;
the water content of the evaporated concentrate is 0.3m3Adding 10g/L of sodium ferrate into the mixture with TP of 20000mg/L, performing catalytic oxidation reaction for 1.5h by using 350g/h of ozone to obtain a wastewater sludge mixture, and then discharging the wastewater sludge mixture to a sludge concentration tank for further treatment;
treating low-concentration PROBAN flame-retardant wastewater: the amount of water obtained in (1) was 5m3The method is characterized in that the low-concentration PROBAN flame-retardant wastewater of per hour and TP 60mg/L is treated by adopting a strong oxidation and precipitation process, and comprises the following steps:
s1, introducing the low-concentration PROBAN flame-retardant wastewater into a reaction vessel, adding sulfuric acid or hydrochloric acid to adjust the pH value to 4, then adding 10g/L ferrous sulfate, and stirring to react for 2 hours to obtain primary reaction wastewater;
s2, carrying out catalytic ozonation on the primary reaction wastewater obtained in the step S1 by using titanium oxide loaded on an alumina plate as a catalyst, and reacting for 1h to obtain intermediate reaction wastewater; wherein the adding amount of the ozone is 0.2g/L, and the filling amount of the catalyst is 1/10 of the volume of the reaction container in S1;
s3, adding 8g/L of calcium hypochlorite with the effective chlorine content of 8% into the middle-grade reaction wastewater obtained in the step S2, reacting for 1 hour, then adjusting the pH value to 9, and coagulating to obtain coagulation wastewater;
s4, precipitating the coagulated wastewater obtained in the step S3 for 2 hours to obtain phosphorus-containing sludge and wastewater, wherein the wastewater is filtered by a ceramic ultrafiltration membrane, and the measured water outlet is 4.8m3/h、TP 0.6mg/L、CODCr70mg/L, chroma of 1 time and SS of less than 1mg/L, meets the water quality index requirement of the group A oxidation washing water, and is 4.8m3The upper layer water is completely reused as the group A oxidation water washing water; the phosphorus-containing sludge enters a sludge treatment system for disposal; the ceramic ultrafiltration backwashing water enters a comprehensive sewage treatment system for further treatment;
comparative example 1
A PROBAN flame-retardant wastewater treatment method comprises the following steps:
s1, the process for producing the flame-retardant cloth by the PROBAN method comprises an oxidation washing process, wherein the oxidation washing process comprises washing tanks of 10 levels in series connection, and the total water consumption is 10m3H, combining the waste water discharged from each stage of rinsing tanks into water with the volume of 10m3Introducing PROBAN flame-retardant wastewater with TP of 500-700mg/L into a reaction container, adding sulfuric acid or hydrochloric acid to adjust the pH value to 2-4, then adding ferrous sulfate of 8-15 g/L, and stirring to react for 1-3 h to obtain primary reaction wastewater;
s2, carrying out ozone catalytic oxidation on the primary reaction wastewater obtained in the step S1 by using manganese oxide loaded on an alumina plate as a catalyst, and reacting for 1-2 hours to obtain intermediate reaction wastewater; wherein the adding amount of the ozone is 0.1-0.4 g/L, and the filling amount of the catalyst is 1/20-1/5 of the volume of the reaction container in S1;
s3, adding an oxidizing chemical agent into the middle-stage reaction wastewater obtained in the S2, reacting for 1-2 hours, adjusting the pH value to 8-9, and coagulating to obtain coagulation wastewater;
s4, precipitating the coagulation wastewater obtained in the step S3 for 1-3 hours to obtain phosphorus-containing sludge and wastewater, separating the phosphorus-containing sludge from the wastewater, filtering the wastewater by using a ceramic ultrafiltration membrane, and measuring the effluent to be 9.0m3H, TP 3-7 mg/L; the phosphorus-containing sludge enters a sludge treatment system for disposal; the ceramic ultrafiltration backwashing water enters a comprehensive sewage treatment system for further treatment.
The embodiment 1-3 shows that the method for treating the organophosphorus-containing flame-retardant cloth production wastewater has high organophosphorus removal rate, can meet the index requirement of entering a comprehensive sewage treatment system, and ensures that the discharged wastewater meets the emission standard requirement.
In order to further illustrate the effect of examples 1-3 on treating PROBAN flame retardant wastewater, wherein the effects of examples 1-3 are similar, only example 1 and comparative example 1 are selected for comparison and analysis of the effects, as shown in Table 1.
TABLE 1 analysis of effect of example 1 and comparative example 1 on PROBAN flame retardant wastewater treatment
As can be seen from table 1, in example 1, by dividing the flame retardant waste water of PROBAN into high concentration flame retardant waste water and low concentration flame retardant waste water, and performing targeted individual treatment, the treatment problem of the flame retardant waste water of PROBAN is thoroughly solved at low cost, reclaimed water reuse is realized, the production cost is reduced, and simultaneously, the removal rate of organic phosphorus is further improved, so that the total phosphorus content is substantially less than 1 mg/L.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (7)
1. The method for treating PROBAN flame-retardant wastewater is characterized by comprising the following steps:
(1) grouping PROBAN flame-retardant wastewater:
aiming at an oxidation washing process for producing flame-retardant cloth by a PROBAN method, the oxidation washing process comprises washing tanks which are connected in series with 10 levels, and the washing tanks which are connected in series with 10 levels are sequentially divided into a group A and a group B; wherein, group A contains 3, 4 or 5-grade rinsing tanks for first oxidation rinsing of the flame-retardant cloth, and the corresponding group B contains 7, 6 or 5-grade rinsing tanks for second oxidation rinsing of the flame-retardant cloth;
merging the wastewater discharged from each stage of rinsing tanks in the group A to obtain high-concentration PROBAN flame-retardant wastewater;
merging the wastewater discharged from each stage of rinsing tanks in the group B to obtain low-concentration PROBAN flame-retardant wastewater;
(2) PROBAN flame-retardant wastewater treatment:
treating high-concentration PROBAN flame-retardant wastewater: treating the high-concentration PROBAN flame-retardant wastewater obtained in the step (1) by evaporation, wherein the evaporated condensate water is reused for oxidation water washing in the group B water washing tank in the step (1); disposing the evaporated crystal according to solid waste; adding ferrate into the evaporated concentrated solution, performing catalytic oxidation by ozone, reacting for 1-2 hours to obtain a wastewater sludge mixture, and then discharging the wastewater sludge mixture to a sludge concentration tank for further treatment;
treating low-concentration PROBAN flame-retardant wastewater: and (2) treating the low-concentration PROBAN flame-retardant wastewater obtained in the step (1) by adopting a strong oxidation and precipitation process.
2. The method of treating PROBAN fire-retardant wastewater as recited in claim 1, wherein each stage of rinsing bath in group A and each stage of rinsing bath in group B are respectively provided with a water inlet and a water outlet.
3. The PROBAN fire-retardant wastewater treatment method as recited in claim 1, wherein the water demand of each stage of rinsing bath in the group A and each stage of rinsing bath in the group B is 1m3/h。
4. The PROBAN flame-retardant wastewater treatment method of claim 1, wherein the ferrate is one or two of sodium ferrate and potassium ferrate, and the addition amount is 5-15 g/L.
5. The method for treating PROBAN flame-retardant wastewater as recited in claim 1, wherein the amount of ozone added is 0.1-0.4 g/L.
6. The method for treating PROBAN flame-retardant wastewater as recited in claim 1, wherein the low-concentration PROBAN flame-retardant wastewater is treated by a strong oxidation + precipitation process, comprising the following steps:
s1, introducing the low-concentration PROBAN flame-retardant wastewater into a reaction container, adding sulfuric acid or hydrochloric acid to adjust the pH value to 2-4, then adding 8-15 g/L ferrous sulfate, and stirring to react for 1-3 hours to obtain primary reaction wastewater;
s2, carrying out catalytic ozonation on the primary reaction wastewater obtained in the step S1 in the presence of a catalyst, and reacting for 1-2 hours to obtain intermediate reaction wastewater; wherein the adding amount of the ozone is 0.1-0.4 g/L, and the filling amount of the catalyst is 1/20-1/5 of the volume of the reaction container in S1;
s3, adding an oxidizing chemical agent into the middle-grade reaction wastewater obtained in the step S2, reacting for 1-2 hours, adjusting the pH value to 8-9, and coagulating to obtain coagulation wastewater;
s4, precipitating the coagulated wastewater obtained in the step S3 for 1-3 hours to obtain phosphorus-containing sludge and wastewater, and then separating the phosphorus-containing sludge from the wastewater, wherein the wastewater is reused as the water for group A oxidation washing; and (4) discharging the phosphorus-containing sludge to a sludge concentration tank for further treatment, and carrying out outward treatment after dehydration.
7. The method of treating PROBAN fire-retardant wastewater of claim 6, wherein said oxidizing chemical is one or more of sodium ferrate, potassium ferrate, sodium hypochlorite, calcium hypochlorite, chlorine dioxide.
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