CN106746198B - Integrated treatment method for high-salt high-concentration degradation-resistant organic wastewater for producing cellulose ether - Google Patents
Integrated treatment method for high-salt high-concentration degradation-resistant organic wastewater for producing cellulose ether Download PDFInfo
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Abstract
The invention discloses an integrated treatment method of high-salt high-concentration degradation-resistant organic wastewater for producing cellulose ether, which comprises the following steps: (1) sequentially carrying out coagulating sedimentation and Fenton reaction on the wastewater to be treated for pretreatment; (2) performing biochemical treatment on the Fenton reaction effluent sequentially through cellulose hydrolysis, anaerobic treatment, primary contact oxidation and secondary contact oxidation; adding cellulase in the hydrolysis process of cellulase to degrade the wastewater, and adding a salt-tolerant microbial inoculum for producing cellulase in the anaerobic treatment, the primary contact oxidation and the secondary contact oxidation processes to strengthen the treatment of the wastewater; (3) and performing advanced treatment on the secondary contact oxidation effluent through a Fenton reaction, and finally discharging. Compared with the existing treatment method, the integrated process has the characteristics of strong pertinence, economy and environmental protection, and solves the problem that the wastewater with high salt content and high concentration is difficult to degrade for enterprises producing cellulose ether.
Description
Technical Field
The invention relates to the technical field of treatment of high-salt high-concentration degradation-resistant organic wastewater for producing cellulose ether, in particular to a pretreatment, biochemical treatment and advanced treatment method for producing the high-salt high-concentration degradation-resistant organic wastewater for producing the cellulose ether.
Background
The cellulose ether is a synthetic high molecular polymer prepared by taking natural cellulose as a raw material and carrying out chemical modification. Cellulose ether is a derivative of natural cellulose, and unlike synthetic polymers, cellulose ether is produced as the most basic material, and is a natural high molecular compound. Due to the structural particularity of natural cellulose, the cellulose does not have the capacity of being reacted with an etherifying agent, but strong hydrogen bonds between molecular chains and in the chains are destroyed by treatment of a swelling agent, the activity release of hydroxyl is changed into alkali cellulose with reaction capacity, and-OH groups are converted into-OR groups after the reaction of the etherifying agent to obtain cellulose ether. The cellulose ether is applied to the aspects of building materials, latex paints, foods, medicines, daily chemicals and the like. Can be used as thickener, water-retaining agent, stabilizer, dispersant, and film-forming agent.
China is the largest world-wide country for cellulose ether production and consumption, and the annual production rate increases by more than 20%. According to preliminary statistics, the existing cellulose ether production enterprises in China reach about 50, the design capacity of the cellulose ether industry exceeds 40 ten thousand tons, and more than 1 ten thousand tons of enterprises have about 20, and are mainly distributed in Shandong, Hebei, Chongqing, Jiangsu, Zhejiang, Shanghai and the like. In 2011, the yield of the carboxymethyl cellulose ether (CMC) is about 30 ten thousand tons, and with the increasing demand of industries such as medicine, food, daily chemical and the like on high-quality cellulose ether, the domestic demand on other cellulose ether products except the CMC is more and more, the yield of the methyl cellulose ether (MC)/hydroxypropyl methyl cellulose ether (HPMC) is about 12 ten thousand tons, and the yield of the hydroxyethyl cellulose ether (HEC) is about 2 ten thousand tons.
Cellulose is a polyhydroxylated polymer which neither dissolves nor melts. The cellulose can be dissolved in water, dilute alkali solution and organic solvent after etherification, and has thermoplasticity. At present, the cellulose ether compound produced by production enterprises is nonionic cellulose mixed ether prepared by crushing refined cotton, treating with alkali, and carrying out a series of reactions by using epoxypropane and chloromethane as etherifying agents. In the production process, an etherifying agent such as chloromethane reacts with NaOH generated by alkalization reaction to generate NaCl, HCl in a byproduct reacts with the NaOH to generate NaCl, so that the salinity of wastewater generated in the production process is very high, the salinity of the wastewater with high concentration is about 19 percent generally, and even the salinity of comprehensive wastewater is 3-4 percent. At present, one of the problems of the waste water is high in salt content, and the treatment cost is very high by adopting physical methods such as triple-effect evaporation and the like, so that the waste water is unacceptable for enterprises. Some enterprises are limited by the total discharge amount of the wastewater, can not carry out biochemical treatment by a dilution method, and the conventional biochemical method for treating microorganisms can not reach the high salinity tolerance. And when the COD 7000-plus 8000mg/L of the wastewater is detected, the content of the cellulose ether can reach about 3g/L, and the substances are obtained by cellulose etherification and are difficult to be degraded by conventional biology due to the structural characteristics. The cellulose ether compound has both hydrophilic groups (hydroxyl groups and ether groups) and hydrophobic groups (methyl and glucose carbocycles), has the characteristics of a surfactant, generates a large amount of foam by aeration in a biochemical pond, and greatly reduces the effect of biochemical treatment. The cellulose ether can be dissolved in cold water, and the aqueous solution of the cellulose ether is very stable in the pH range of 3-12, so that the wastewater is high in salt content and stable in structure and is difficult to biodegrade, so that the problem of wastewater treatment is solved at present.
Disclosure of Invention
The invention provides an integrated treatment method of high-salt high-concentration degradation-resistant organic wastewater for producing cellulose ether, which solves the problem that the high-salt high-concentration degradation-resistant organic wastewater for producing cellulose ether is difficult to treat.
An integrated treatment method of high-salt high-concentration refractory organic wastewater for producing cellulose ether comprises the following steps:
(1) sequentially carrying out coagulating sedimentation and Fenton reaction on the wastewater to be treated for pretreatment;
(2) performing biochemical treatment on the Fenton reaction effluent sequentially through cellulose hydrolysis, anaerobic treatment, primary contact oxidation and secondary contact oxidation; adding cellulase in the hydrolysis process of cellulase to degrade the wastewater, and adding a salt-tolerant microbial inoculum for producing cellulase in the anaerobic treatment, the primary contact oxidation and the secondary contact oxidation processes to strengthen the treatment of the wastewater;
(3) and performing advanced treatment on the secondary contact oxidation effluent through a Fenton reaction, and finally discharging.
The method comprises the steps of pretreatment, biochemical treatment and advanced treatment of the wastewater generated in the production of cellulose ether.
The invention can stably reach the nano-tube discharge standard after treating the wastewater by the coagulation reaction, the Fenton oxidation, the cellulase hydrolysis, the biochemical treatment of various cellulase-producing salt-resistant degrading bacteria and the Fenton reaction advanced treatment integrated process. In the process, cellulose ether is hydrolyzed by cellulase and then enters an anaerobic tank and an aerobic tank, and cellulose ether wastewater is intensively treated by producing cellulase salt-tolerant microbial inoculum, so that not only is the foam in the aerobic tank greatly reduced, but also the biochemical treatment effect is improved. Therefore, the integrated process solves the problems of difficult sewage treatment and high treatment cost for production enterprises producing cellulose ether products.
The coagulating sedimentation is as follows: adjusting the pH of high-salt organic wastewater for producing cellulose ether to subacidity, adding polyaluminum chloride (PAC) to a final concentration of 50-200mg/L, stirring for reaction, adding Polyacrylamide (PAM) to a final concentration of 0.5-2mg/L, continuing stirring for reaction, and then standing for settling to obtain a supernatant.
Preferably, the COD of the high-salt organic wastewater is 7000-10000 mg/L, and the salt content is 10-45 g/L; the concentration range of the cellulose ether in the wastewater is 1.9 g/L-2.5 g/L.
Further preferably, the pH value is adjusted to 5.5-6.5, and further preferably 6.0 during coagulating sedimentation; stirring for 3-8 minutes at 200-400 rpm after adding PAC, and preferably stirring for 5 minutes at 300 rpm; stirring for 3-8 minutes at 50-150 rpm after PAM is added, and preferably stirring for 5 minutes at 100 rpm.
The Fenton reaction in the step (1) is as follows: adding 0.6-1.5% of FeSO into the supernatant after the coagulating sedimentation treatment according to the mass-volume ratio4After stirring and dissolving, adjusting the pH value to 3 by using dilute sulfuric acid, and adding 0.6-2.5% of H according to the volume ratio2O2，H2O2Adding the mixture for multiple times, adding the mixture once every 20-30 min, aerating for 2-4 h, adjusting the pH to 8-9 by using lime milk after the aeration is finished, and allowing supernatant after static precipitation to enter a biochemical system.
The unit of the mass-volume ratio is g/mL, and 0.6-1.5 percent of FeSO is added according to the mass-volume ratio as described above4Namely, 0.6-1.5 g of FeSO is added into every 100mL of wastewater4If not specifically stated, the units of the mass-to-volume ratios are g/mL; the H is added into the mixture according to the volume ratio of 0.6 to 2.5 percent2O2Here H2O2The adding amount refers to the total amount of multiple times of adding.
Further preferably, FeSO4The addition amount of (C) is 0.7-0.8% (W/V), H2O2The amount of (A) is 1.5-1.6% (V/V).
The biochemical treatment process is carried out in a cellulase hydrolysis tank, an anaerobic tank, a primary contact oxidation tank and a secondary contact oxidation tank in sequence, combined fillers are added into the anaerobic tank, the primary contact oxidation tank and the secondary contact oxidation tank, inoculated activated sludge is a salt-tolerant microbial inoculum for producing cellulase, cellulase is added into the cellulase hydrolysis tank, and DO in the primary contact oxidation tank and the DO in the secondary contact oxidation tank are controlled to be 3-4 mg/L, and are further preferably controlled to be 3.5 mg/L; HRT of the whole biochemical treatment process is 6-8 days (preferably 7 days).
The combined filler is preferably selected from fiber bundles, plastic snowflake discs, sleeves and central ropes.
The cellulase added in the cellulase hydrolysis tank is purchased from Soochow bioengineering Limited company, preferably, the adding amount of the cellulase is 0.01-0.8 per mill (W/V), namely 0.01-0.8 g of cellulase is added in each 1000mL of wastewater, the temperature in the cellulase hydrolysis tank is controlled to be 25-35 ℃, and the stirring speed is controlled to be 50-150 r/min (preferably 100 r/min) in the hydrolysis process; the addition amount of the cellulase is more preferably 0.01-0.1 ‰ (W/V), and the hydrolysis temperature is more preferably 30 ℃.
After enzyme hydrolysis, the obtained product sequentially enters an anaerobic tank and a contact oxidation tank to be subjected to biochemical treatment, the salt-tolerant microbial inoculum for producing the cellulase is a mixed microbial inoculum of Bacillus (Bacillus sp.) CICC 10829, Bacillus (Bacillus sp.) CICC10830, Bacillus licheniformis (Bacillus licheniformis) CICC10831 and Bacillus subtilis subspecies (Bacillus subtilis) CICC 10832, the mixed microbial inoculum is prepared by a conventional microbial inoculum preparation method respectively, and is mixed according to the proportion when used, preferably, the proportion of four strains in the mixed microbial inoculum is 1:1:1: 1.
the salt-tolerant microbial inoculum used by the invention is 4 strains of salt-tolerant bacteria screened from a plurality of strains for producing cellulase purchased from the China center for industrial microbial strain preservation. The salt tolerance can reach 4-8%, and the mixed bacteria is prepared and fed into anaerobic tank and contact oxidation tank.
The culture method of the salt-tolerant microbial inoculum comprises the following steps:
(1) preparing salt-tolerant microbial inoculum inclined-plane seeds: in a slant seed culture medium (10 g/L of peptone, 5g/L of yeast extract powder, 10g/L of NaCl, 2% of agar and pH 7.0-7.2), bacillus subtilis, bacillus licheniformis and bacillus subtilis subspecies are respectively streaked and inoculated into test tubes for activation culture for later use.
(2) Preparing shake flask seeds: inoculating the activated single colony in a culture medium (10 g/L of peptone, 5g/L of yeast extract powder, 10g/L of NaCl and 7.0-7.2 of pH), carrying out shake culture at 35 ℃ until the late logarithmic growth stage, and preparing to inoculate in a seed tank.
(3) Preparing a seeding tank culture medium (the components of the culture medium are 10g/L of peptone, 5g/L of yeast extract powder, 10g/L of NaCl, 1g/L of glucose and 7.0-7.5 of pH), adding 30L of the seed culture medium into a 50L seeding tank, carrying out high-pressure damp-heat sterilization at 121 ℃, cooling to 33 ℃, inoculating the prepared shake flask strain into the seeding tank according to the inoculation amount of 10% (V/V), culturing at 35 ℃ to a logarithmic phase, stirring at 180 r/min, and introducing sterile air at the rate of 1:0.8 (V/V).
(4) Preparing a fermentation tank culture medium: (culture medium: 10g/L of peptone, 2.5g/L of yeast extract powder, 2.5g/L of beef extract, 10g/L of NaCl, 0.5g/L of glucose and pH 7.0-7.5), the filling amount of the fermentation tank culture medium is 500L, 300L of fermentation medium is filled in the fermentation tank, and the filling amount is 1.1Kg/cm2Sterilizing at 121 deg.C, cooling to below 35 deg.C, introducing sterile air, and keeping sterile state; inoculating the seed liquid cultured in the step (3) to a logarithmic phase into a fermentation tank according to an inoculation amount of 10% (V/V), controlling the temperature of the inoculated fermentation tank to be about 35 ℃, and controlling the ventilation volume of sterile air in the culture process of the fermentation tank to be 1: (0.8-1.0) (V/V), the stirring speed is 200-220 r/m, and the culture time of the whole process flow is 18-20 hours; the number of the thalli after fermentation is over 10 hundred million/mL. The four kinds of bacteria are bacillus, the culture method is the same, and the four kinds of bacteria are mixed when used after being cultured.
(5) And (4) directly packaging the fermentation liquor after fermentation in the step (4) into liquid dosage forms by using plastic packaging bottles sterilized by ethylene oxide. The salt tolerance of the four microbial inoculums is 4% -8%, the cellulase production capacity is equivalent, so that the four microbial inoculums are mixed and added according to the volume ratio of 1:1:1:1 when in use, and the total amount is added into an anaerobic tank and a contact oxidation tank according to the amount of 0.01-0.1 per mill (V/V) per day.
Transparent rings generated by the 4 cellulase-producing degrading bacteria on the congo red plate are shown in figures 1-3, wherein figure 1 is Bacillus sp CICC 10829 and Bacillus sp CICC 10830; fig. 2 is Bacillus subsp. FIG. 3 shows Bacillus licheniformis CICC 10831.
The effluent of the secondary contact oxidation tank is subjected to advanced treatment through Fenton reaction, and the effluent can stably reach the nano-tube discharge standard for a long time.
The Fenton reaction advanced treatment conditions are as follows: adding 0.5-1.0% of FeSO4(W/V) into the wastewater, stirring and dissolving, and adding 10% of H2SO4(V/V) adjusting the pH value to 3.0, and adding 0.5-1.2% of H2O2(V/V)，H2O2Adding the materials for multiple times, adding the materials once every 30min, aerating for 2-4 h, adjusting the pH value to 8-9 by using lime milk, and standing and precipitating to obtain effluent which enters a nano tube.
Further preferably, FeSO4The addition amount of (C) is 0.5-0.6% (W/V), H2O2The amount of (A) is 0.7-0.86% (V/V).
The method comprises pretreatment, biochemical treatment and advanced treatment. After PAC and PAM coagulating sedimentation and Fenton reaction pretreatment, wastewater enters a biochemical treatment system, and the biochemical treatment system comprises cellulase hydrolysis, anaerobism, primary contact oxidation, secondary contact oxidation and effluent. The treatment efficiency of the wastewater is improved by the cellulose hydrolysis and the strengthening treatment of adding a salt-tolerant microbial inoculum for producing cellulose in the biochemical tank, and the problem that cellulose ether is difficult to oxidize and decompose is solved; after entering the contact oxidation tank, a large amount of foam is generated by aeration, so that the biochemical treatment effect is greatly reduced, and the biochemical effect is reduced because the conventional biochemical treatment is difficult to tolerate the high salinity; and the Fenton reaction is matched for advanced treatment, so that the wastewater can stably reach the nano-tube discharge standard for a long time.
Compared with the prior pretreatment, biochemical treatment and advanced treatment integrated process, the enterprise wastewater treatment effect is greatly improved, and the main reason is that the invention has the following characteristics:
(1) the cellulose ether compound has both hydrophilic groups (hydroxyl groups and ether groups) and hydrophobic groups (methyl and glucose carbocycles), has the characteristics of a surfactant, is high in water solubility, and contains a cellulose structure which is difficult to be oxidized and decomposed, so that the cellulose ether cannot be completely oxidized after pretreatment, and after the cellulose ether enters a biochemical aerobic tank, a large amount of foam is generated during aeration, and the conventional microorganisms are difficult to degrade the cellulose ether, so that the biochemical treatment effect is greatly reduced. According to the invention, the cellulase is added to carry out enzymatic hydrolysis on the wastewater after pretreatment, so that the content of the cellulose ether is greatly reduced. Reduces the biochemical effect reduction caused by the foam generated by aeration in the contact oxidation tank. Meanwhile, 4 kinds of salt-tolerant bacteria for producing cellulase are added into the anaerobic tank and the contact oxidation tank, and the cellulose ether is further enhanced to be degraded, so that the sewage treatment effect is greatly improved compared with that of the conventional integrated treatment process.
(2) The invention adopts 4 kinds of salt-tolerant bacteria for producing cellulase to be added into a biochemical system, and compared with the prior method of only adding salt-tolerant bacteria, the method has the advantages that the pertinence of the treatment of the wastewater is enhanced, and the treatment effect of the wastewater is improved.
(3) The added 4 cellulase-producing halotolerant bacteria are halotolerant bacteria screened from a plurality of cellulase-producing strains purchased from the China center for industrial microbial strain preservation, and the salinity tolerance reaches 4-8% at most.
(4) Compared with the existing treatment method, the integrated process has the characteristics of strong pertinence, economy and environmental protection, and solves the problem that the wastewater with high salt content and high concentration is difficult to degrade for enterprises producing cellulose ether.
Drawings
FIG. 1 shows a transparent circle produced by Bacillus sp CICC 10829 and Bacillus sp CICC10830 on a congo red plate, wherein the upper part is Bacillus sp CICC 10829, and the lower part is Bacillus sp CICC 10830.
Fig. 2 is a transparent circle produced by Bacillus subtilis cic 10832 on congo red plates.
FIG. 3 is a transparent circle produced by Bacillus licheniformis CICC10831 on a congo red plate.
Detailed Description
Example 1
The COD of the comprehensive waste water for producing the methyl cellulose ether and the hydroxypropyl methyl cellulose ether is 7000-8000mg/L, and NH420-25mg/L of-N and 35-40 g/L of salt, and taking in each time in a laboratoryAfter pretreatment of 10L of wastewater, 4 devices of 3L were connected in series, and the biochemical small-scale treatment was as follows.
(1) The organic wastewater from the production of methyl cellulose ether and hydroxypropyl methyl cellulose ether was adjusted to pH 6.0, PAC was added to a final concentration of 100mg/L, and stirred at 300 rpm for 5 minutes, and then PAM was added to a final concentration of 1mg/L and stirred at 100 rpm for 5 minutes. Standing to precipitate and collecting supernatant.
(2) Taking the supernatant of the wastewater treated in the step (1) for Fenton reaction pretreatment, and adding 0.8% of FeSO4(W/V) dissolved with stirring, and then 10% H2SO4(V/V) to adjust the pH to 3.0, and 1.6% H was added2O2(V/V)，H2O2Adding the mixture for multiple times, adding the mixture once every 30min, aerating for 3h, adjusting the pH value to 8-9 by using lime milk, and standing and precipitating.
(3) And (3) performing biochemical treatment on the supernatant after the wastewater treated in the step (2) is precipitated, wherein the biochemical treatment process comprises anaerobic treatment, first-stage contact oxidation, second-stage contact oxidation and water outlet, combined fillers are added into the anaerobic tank and the contact oxidation tank, and the biochemical treatment effect is inspected in one period of a conventional activated sludge film-forming after-treatment wastewater test. Then 4 kinds of salt-tolerant bacteria agents cultured in a laboratory are inoculated, the wastewater is subjected to biofilm culturing stabilization post-treatment for one period, and the biochemical treatment effect is inspected. The whole process flow HRT is 7 days, and the DO of the contact oxidation pond is 3.5 mg/L.
(4) The microbial inoculum added in the step (3) can degrade cellulose and resist salt, the salinity tolerance is up to 4-8%, and the microbial inoculum comprises Bacillus subtilis (Bacillus sp) CICC 10829, Bacillus subtilis (Bacillus sp) CICC10830, Bacillus licheniformis (Bacillus licheniformis) CICC10831 and Bacillus subtilis subspecies (Bacillus subtilis) CICC 10832. The salt-tolerant microbial inoculum consisting of the four salt-tolerant cellulase degrading bacteria is preferably added into the anaerobic tank and the contact oxidation tank according to the amount of 0.02 per mill to 0.03 per mill (V/V) per day.
(5) And (4) after the effects of the salt-tolerant microbial inoculum added in the step (3) on wastewater treatment are inspected, adding a cellulase hydrolysis tank at the front end of the process, and changing the process into cellulase hydrolysis, anaerobic treatment, first-stage contact oxidation, second-stage contact oxidation and water outlet.
(6) The cellulase added in the cellulase hydrolysis tank in the step (5) is purchased from Sokohaman bioengineering limited company, the adding amount is 0.03 per mill (W/V), the temperature is kept at 30 ℃, and the cellulase enters an anaerobic tank for biochemical treatment after being subjected to enzymatic hydrolysis by stirring for 100 r/min.
(7) And (4) performing advanced treatment on the effluent treated in the step (3) or the step (5) through Fenton reaction, wherein the effluent can stably reach the nano-tube discharge standard.
(8) The deep treatment conditions of the Fenton reaction in the step (7) are as follows: FeSO of 0.6 percent is added4(W/V) dissolved with stirring, and then 10% H2SO4(V/V) adjusting the pH to 3.0, adding 0.8% H2O2(V/V), aeration for 3H, H2O2Adding the mixture for multiple times, adding the mixture once every 30min, adjusting the pH to 8-9 by lime milk, and standing and precipitating to obtain water.
(9) Test results of the cellulose ether production wastewater before and after the treatment of the steps (1) to (8) and the addition of the salt-tolerant microbial inoculum and the cellulase are shown in table 1.
Table 1 treatment of cellulose ether production wastewater before and after adding salt-tolerant microbial inoculum and cellulase
As can be seen from Table 1, the conventional microorganisms have poor treatment effect on high-salinity wastewater, the highest biochemical removal rate is only 63.3%, and the highest biochemical removal rate is improved to 78.5% and the removal rate is improved by 15.2% after the salt-tolerant microbial agent is added. After the cellulase is added, the removal effect of the whole biochemical system is improved to 85.4 percent, and the removal rate is improved by 6.9 percent compared with the effect of adding the salt-tolerant microbial inoculum. After the cellulase and the salt-tolerant microbial inoculum are added, the biochemical removal rate of the wastewater is improved by 22.1 percent compared with the original biochemical removal rate under the synergistic effect of the cellulase and the salt-tolerant microbial inoculum
Example 2
The method mainly produces methyl cellulose ether and hydroxypropyl methyl cellulose ether in a certain enterprise, the comprehensive wastewater amount is 500t/d, the COD is 7000-8000mg/L, and NH is4N20-25 mg/L, salt content 35-40 g/L, and the total amount of wastewater discharged by enterprises is controlled and can not be diluted to reduce salt content for generatingThe cost of chemical treatment is too high for 500t/d water volume through triple effect evaporation, and the wastewater treatment by adopting the integrated technology can reach the nano-tube discharge standard.
(1) The organic wastewater from the production of methyl cellulose ether and hydroxypropyl methyl cellulose ether was adjusted to pH 6.0, PAC was added to a final concentration of 100mg/L, and stirred at 300 rpm for 5 minutes, and then PAM was added to a final concentration of 1mg/L and stirred at 100 rpm for 5 minutes. Standing to precipitate and collecting supernatant.
(2) Taking the supernatant of the wastewater treated in the step (1) for Fenton reaction pretreatment, and adding 0.8% of FeSO4(W/V) dissolved with stirring, and then 10% H2SO4(V/V) adjusting the pH to 3.0, adding 1.6% H2O2(V/V)，H2O2Adding the mixture for multiple times, adding the mixture once every 30min, aerating for 3h, adjusting the pH value to 8-9 by using lime milk, and standing and precipitating.
(3) And (3) performing biochemical treatment on the supernatant after the wastewater treated in the step (2) is precipitated, wherein the biochemical treatment process comprises the steps of cellulase hydrolysis, anaerobism, primary contact oxidation, secondary contact oxidation and water outlet, combined fillers are added into an anaerobic tank and a contact oxidation tank, and the inoculated activated sludge is a salt-tolerant microbial inoculum cultured in a laboratory. The whole process flow HRT is 7 days, and the DO of the contact oxidation pond is 3.5 mg/L.
(4) And (3) adding cellulase in an amount of 0.03 per mill (W/V) through enzymatic hydrolysis, wherein the cellulase is purchased from Soochehan bioengineering Co. Keeping the temperature at 30 ℃, stirring for 100 r/min, and performing aerobic biochemical treatment in a primary contact oxidation tank after enzymatic hydrolysis.
(5) The microbial inoculum added in the step (3) can degrade cellulose and resist salt, the salinity tolerance reaches 4-8% at most, and the microbial inoculum comprises Bacillus subtilis (Bacillus sp) CICC 10829, Bacillus subtilis (Bacillus sp) CICC10830, Bacillus licheniformis (Bacillus licheniformis) CICC10831 and Bacillus subtilis subspecies (Bacillus subtilis) CICC 10832. The salt-tolerant microbial inoculum consisting of the four salt-tolerant cellulase degrading bacteria is added into an anaerobic pool and a contact oxidation pool according to the amount of 0.02 per mill (V/V) per day.
(6) And (4) performing advanced treatment on the effluent treated in the step (3) through Fenton reaction, wherein the effluent can stably reach the nano-tube discharge standard.
(7) The deep treatment conditions of the Fenton reaction in the step (6) are as follows: FeSO of 0.6 percent is added4(W/V) dissolved with stirring, and then 10% H2SO4(V/V) adjusting the pH to 3.0, adding 0.8% H2O2(V/V), aeration for 3H, H2O2Adding the mixture for multiple times, adding the mixture once every 30min, adjusting the pH to 8-9 by lime milk, and standing and precipitating to obtain water.
(8) The test results after the treatments in the steps (1) to (7) are shown in Table 2.
TABLE 2 treatment of wastewater from cellulose ether production
The results in Table 2 show that the total degradation rate of COD in the wastewater by the method of the invention reaches about 96%, wherein the biochemical removal rate reaches 85.1-87.3% at most.
Example 3:
a certain enterprise mainly produces methyl cellulose ether and hydroxypropyl methyl cellulose ether, the high-concentration wastewater amount is about 60-70t/d, COD is 12000-15000 mg/L, salt content is 10-15 g/L, and the treatment difficulty is increased because the COD of the wastewater is high and the content of cellulose ether which is a difficultly-degradable substance in the wastewater is also high, about 3.3 g/L.
(1) Considering the small amount of high concentration waste water, the method of low temperature vacuum distillation desolventizing is adopted, the waste water is desolventized at 50 ℃ in vacuum for recycling the solvent, after desolventizing, the COD has about 30 percent of removal rate, and the COD can be reduced to 8000 plus 10000 mg/L. And then the wastewater is treated by adopting an integrated treatment process.
(2) The pH of the high-salt organic wastewater for producing cellulose ether is adjusted to 6.0, PAC is added to the final concentration of 100mg/L, the mixture is stirred for 5 minutes at 300 revolutions/min, PAM is added to the final concentration of 1mg/L, and the mixture is stirred for 5 minutes at 100 revolutions/min. Standing to precipitate and collecting supernatant.
(3) Taking supernatant from the wastewater treated in the step (2) to enterPretreating by Fenton reaction, and adding 1.0% of FeSO4(W/V) with 10% H2SO4(V/V) adjusting the pH to 3.0, adding 2.0% H2O2(V/V)，H2O2Adding the mixture for multiple times, adding the mixture once every 30min, aerating for 3h, adjusting the pH value to 8-9 by using lime milk, and standing and precipitating.
(4) And (4) performing biochemical treatment on the supernatant after the wastewater treated in the step (3) is precipitated, wherein the biochemical treatment process comprises the steps of cellulase hydrolysis, anaerobism, primary contact oxidation, secondary contact oxidation and water outlet, combined fillers are added into an anaerobic tank and a contact oxidation tank, and the inoculated activated sludge is a salt-tolerant microbial inoculum cultured in a laboratory. The whole process flow HRT is 7 days, and the DO of the contact oxidation pond is 3.5 mg/L.
(5) And (4) adding cellulase in the step (4) through enzymatic hydrolysis, wherein the adding amount is 0.8 per mill (W/V), and the cellulase is purchased from Soochow bioengineering Co. Keeping the temperature at 30 ℃, stirring for 100 r/min, and performing aerobic biochemical treatment in a primary contact oxidation tank after enzymatic hydrolysis.
(6) The microbial inoculum added in the step (4) can degrade cellulose and resist salt, the salinity tolerance reaches 4-8% at most, and the microbial inoculum comprises Bacillus subtilis (Bacillus sp) CICC 10829, Bacillus subtilis (Bacillus sp) CICC10830, Bacillus licheniformis (Bacillus licheniformis) CICC10831 and Bacillus subtilis subspecies (Bacillus subtilis) CICC 10832. The salt-tolerant microbial inoculum consisting of the four salt-tolerant cellulase degrading bacteria is added into an anaerobic pool and a contact oxidation pool according to the amount of 0.08 per mill (V/V) per day.
(7) And (4) performing advanced treatment on the effluent treated in the step (4) through Fenton reaction, wherein the effluent can stably reach the nano-tube discharge standard.
(8) The deep treatment conditions of the Fenton reaction in the step (7) are as follows: FeSO of 0.8 percent is added4After (W/V) dissolution, 10% H was added2SO4(V/V) to adjust the pH to 3.0, adding 1.8% H2O2(V/V)，H2O2Adding the materials for multiple times, adding the materials once every 30min, aerating for 3h, adjusting the pH value to 8-9 by using lime milk, and standing and precipitating to obtain water.
(9) The wastewater treated in the steps (1) to (8) is shown in Table 3.
TABLE 3 treatment of wastewater from cellulose ether production
The results in Table 3 show that the total degradation rate of COD in the wastewater by the method of the invention reaches about 95%, wherein the biochemical removal rate reaches 82.1-85.2%.
Claims (5)
1. An integrated treatment method for high-salt high-concentration refractory organic wastewater for producing cellulose ether is characterized by comprising the following steps:
(1) sequentially carrying out coagulating sedimentation and Fenton reaction on the wastewater to be treated for pretreatment; the coagulating sedimentation is as follows: adjusting the pH of high-salt organic wastewater for producing cellulose ether to subacidity, adding polyaluminium chloride to a final concentration of 50-200mg/L, stirring for reaction, adding polyacrylamide to a final concentration of 0.5-2mg/L, continuing stirring for reaction, and standing for settling to obtain a supernatant;
(2) performing biochemical treatment on the Fenton reaction effluent sequentially through cellulose hydrolysis, anaerobic treatment, primary contact oxidation and secondary contact oxidation; adding cellulase in the hydrolysis process of cellulase to degrade the wastewater, and adding a salt-tolerant microbial inoculum for producing cellulase in the anaerobic treatment, the primary contact oxidation and the secondary contact oxidation processes to strengthen the treatment of the wastewater;
the conditions of the cellulase hydrolysis are as follows: adding cellulase according to the mass-volume ratio of 0.01-0.8 per mill, wherein the unit of the mass-volume ratio is g/mL, the temperature in a cellulase hydrolysis tank is controlled to be 25-35 ℃, and the stirring speed is controlled to be 50-150 r/min in the hydrolysis process;
the salt-tolerant microbial inoculum is a mixed microbial inoculum prepared from Bacillus (Bacillus sp.) CICC 10829, Bacillus (Bacillus sp.) CICC10830, Bacillus licheniformis (Bacillus licheniformis) CICC10831 and Bacillus subtilis subs (Bacillus subsp.) CICC 10832; in the anaerobic treatment process, the salt-tolerant microbial inoculum is added into an anaerobic pool according to the volume ratio of 0.01-0.1 per thousand every day; adding the salt-tolerant microbial inoculum into an aerobic pool according to the volume ratio of 0.01-0.1 per mill every day in the processes of primary contact oxidation and secondary contact oxidation;
(3) and performing advanced treatment on the secondary contact oxidation effluent through a Fenton reaction, and finally discharging.
2. The integrated treatment method of claim 1, wherein the high-salinity organic wastewater has a COD of 7000 to 10000mg/L, a salt content of 10 to 45g/L and a cellulose ether concentration of 1.9 to 2.5 g/L.
3. The integrated process of claim 1, wherein the Fenton reaction in step (1) is: adding 0.6-1.5% of FeSO into the supernatant after the coagulating sedimentation treatment according to the mass-volume ratio4The unit of the mass volume ratio is g/mL, after stirring and dissolving, the pH value is adjusted to 3 by dilute sulphuric acid, and then 0.6 to 2.5 percent of H is added according to the volume ratio2O2，H2O2Adding the mixture for multiple times, adding the mixture once every 20-30 min, aerating for 2-4 h, adjusting the pH to 8-9 by using lime milk after the aeration is finished, and allowing supernatant after static precipitation to enter a biochemical system.
4. The integrated treatment method according to claim 1, wherein the total hydraulic retention time of the biochemical treatment is 6-8 days.
5. The integrated process of claim 1, wherein the Fenton reaction conditions in step (3): FeSO with the mass volume ratio of 0.5-1.0 percent is added4In the wastewater, the unit of mass volume ratio is g/mL, after stirring and dissolving, dilute sulphuric acid is used for adjusting the pH value to 3.0, and 0.5-1.2% of H is added according to the volume ratio2O2，H2O2Adding the materials for multiple times, adding the materials once every 20-30 min, aerating for 2-4 h, adjusting the pH to 8-9 by using lime milk, standing for precipitation, and discharging outlet water into a nano tube.
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