CN102351368B - Loading flocculation pretreatment method of antibiotic fermentation wastewater - Google Patents
Loading flocculation pretreatment method of antibiotic fermentation wastewater Download PDFInfo
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Abstract
The invention discloses a loading flocculation pretreatment method of antibiotic fermentation wastewater and is suitable for processing mixed wastewater discharged during each antibiotic fermentation technological section. By the adoption of the loading flocculation technology, flocculation pretreatment is carried out on mixed wastewater of a crystallization solution, waste mother liquor, dona tub washing wastewater and washing wastewater for a fermentation cylinder during the antibiotic production process. A flocculating agent contains polyaluminum chloride and polyacrylamide; and the addition sequence of the flocculating agent is to add polyaluminum chloride at first and then add polyacrylamide. A loading agent contains one or two mixtures selected from active carbon, fly ash, activated sludge and settling sludge. By the adoption of the method provided by the invention, the flocculation treatment can be effectively carried out on high-density organic wastewater generated during the antibiotic fermentation production. The method provided by the invention is simple, requires low cost and has a stable effect. By the adoption of the method, the treated wastewater can reach the requirement of subsequent biochemical treatment.
Description
Technical field
The invention belongs to sewage treatment area, particularly a kind of loading coagulating/flocculating method for processing of antibiotic fermentation waste water.
Background technology
At present, China production of antibiotics enterprise is family more than 300 nearly, can produce the microbiotic of 70 kinds that account for world wide production 20%～30%, and output increases every year, has now become in the world one of main antibiotic formulations producing country.Production of antibiotics comprises microbial fermentation, filtration, extractive crystallization, refinement, the technological process such as refining.Usually take grain or molasses as raw material, the waste water of production process mainly comes the high concentrated organic wastewater of self-separation, extraction, refining pure metallization processes to antibiotic fermentative production, as crystal solution, waste liquor, seeding tank washes, fermentor tank washes etc.Such waste water COD content high (10000-15000mg/L), SS concentration high (1500～2500mg/L), high, the complicated component of sulfate concentration.In addition, antibiotic fermentation waste water also has the characteristics such as colourity is high, pH fluctuation large (being about 6.5-8.9), intermittently discharged, is one of poisonous organic wastewater that processing cost is high, difficulty of governance is large.
It is one of most important process in Waste Water Treatment that the biological chemistry of above-mentioned waste water is processed.The biochemical treatment of waste water is to utilize the vital movement process of microorganism with the organic matter removal in waste water.Inhibition component content and organism in biochemical treatment ability and reaction tank environment, waste water, concentration of suspension are relevant.Waste water after biochemical treatment produces biological activity mud and the supernatant liquor of recoverable through solid-liquid separation, waste water is purified.Compare with other treatment processs, biochemical treatment process has the characteristics such as energy consumption is low, treatment effect good, processing costs is low, is one for the treatment of process of extensively taking of present pharmacy waste water process field.At present, process the high concentrated organic wastewater that antibiotic fermentation technique produces, common technique is at first to adopt the composite macromolecule organic flocculating agent of inorganic coagulant to carry out pre-treatment, then adopts the biochemical treatment mode to carry out subsequent disposal.Due to this type of waste water complicated component, the concentration of suspension such as vitriol, nutritive ingredient organism and useless mycelia residual in waste water are high, colourity is high, the pH fluctuation is large, often cause existing processing mode pretreating effect not good, the flocculation sediment quantity not sufficient, increase the difficulty of follow-up biochemical treatment, thereby produced the phenomenon that the COD clearance is low, processing is not up to standard.For strengthening the flocculation sediment effect, need to increase the add-on of flocculation agent, cause processing cost to increase.Particularly for the pharmacy sewage of intermittently discharged, this kind processing mode is with high costs.
Summary of the invention
The technical issues that need to address of the present invention are to provide a kind of loading coagulating/flocculating method for processing to the high concentrated organic wastewater that produces in the microbiotic fermentation production process, it is easy, cost is low, effect stability, makes waste water after processing can reach the requirement of follow-up biochemical treatment.
For solving the problems of the technologies described above, the technical solution adopted in the present invention is:
A kind of loading flocculation pretreatment method of antibiotic fermentation waste water, be production of antibiotics terminal waste water, comprise crystal solution, waste liquor, the seeding tank washes, various wash-down waters and washing water in fermentor tank washes and processing and production process, the processing step that loads flocculation pretreatment method comprises: first add supporting agent to carry out water quality regulation in the mode that stirs in waste water, and then add flocculation agent in the mode that stirs; Perhaps first add flocculation agent in the mode that stirs in waste water, and then add supporting agent in the mode that stirs; To pass in flocculation tank through the waste water that above-mentioned steps is processed, stir, mix, then carry out solid-liquid separation; Solid-liquid separation is precipitated mud and supernatant liquor, and this supernatant liquor passes into biochemical treatment apparatus and carries out biochemical treatment, after finishing dealing with, and the waste water that is isolated to active sludge and can discharges,
Described flocculation agent comprises polymerize aluminum chloride and polyacrylamide, and the addition sequence of flocculation agent is: first add polymerize aluminum chloride, then add polyacrylamide; Described wherein one or both mixture, gac, the flyash that adds active sludge that precipitating sludge that supporting agent comprises that antibiotic fermentation waste water obtains when loading flocculation pre-treatment solid-liquid separation, supernatant liquor that solid-liquid separation obtains produce when biochemical treatment; Through flocculation agent with add the waste water that supporting agent processed and pass in flocculation tank, take the rotating speed of 40～60r/min stir, mixing time is as 1～5min.
It is of the present invention when to add supporting agent be one or both of active sludge or precipitating sludge, detailed directions is: one or both of active sludge or precipitating sludge are mixed with the suspension liquid of 6000～10000mg/L, and with the pH regulator to 7.0 of suspension liquid～9.0, the volume ratio that adds 0.1～20 part of suspension liquid according to 100 parts of waste water, low whipping speed is under the condition of 250～350r/min, suspension liquid to be joined in waste water, and mixing time is 5～15s.
Of the present invention when adding supporting agent and being flyash or pulverous gac, detailed directions is: with flyash or pulverous gac, according to adding 5～200mg to add the consumption of supporting agent in every 1L waste water, low whipping speed is to join in waste water under the condition of 250～350r/min, and mixing time is 5～15s.
The detailed directions of polymerize aluminum chloride of the present invention is: it is 5～15% mixed solution that polymerize aluminum chloride is mixed with mass concentration, according to adding the consumption of 200～1000mg polymerize aluminum chloride in every 1L waste water, low whipping speed is under the condition of 200～400r/min, mixed solution to be joined in waste water, and mixing time is 5～10s.
The detailed directions of polyacrylamide of the present invention is: it is 0.1～0.3% mixed solution that polyacrylamide is mixed with mass concentration, according to adding the consumption of 2.5～10mg polyacrylamide in every 1L waste water, low whipping speed is under the condition of 200～400r/min, mixed solution to be joined in waste water, and mixing time is 10～20s.
Flocculation tank of the present invention is preferably the folded plate flocculation reaction tank.
Owing to having adopted technique scheme, the technical progress that the present invention obtains is:
The present invention adopts the flocculation loading technique to carry out pre-treatment to the waste water that the microbiotic fermenting process produces, and has greatly promoted flocculating effect, is convenient to carry out follow-up biochemical treatment.Employing adds supporting agent and carries out modified to waste water, can increase the SS in waste water, improve the collision efficiency of colloid, and add supporting agent and also can serve as sorbent material, adsorb the dissolved organic matter in waste water, thereby effectively improve the removal efficient of dissolved organic matter, reduce the usage quantity of chemical floc, and can make pretreated stable water outlet, reach the needs of follow-up biochemical treatment.Add in waste water in the process that supporting agent and flocculation agent mix, adopt stirring velocity faster, make to add in supporting agent and flocculation agent short period of time Uniform Dispersion in waste water, become glue core, realize synergy, utilization adds the absorption of supporting agent and the flocculating effect that settling property improves flocculation agent.
Successively add polymerize aluminum chloride and polyacrylamide as flocculation agent successively, can bring into play fully both synergies.First add organism and suspended impurity reaction in polymerize aluminum chloride and waste water, regulate the electrical of waste water, strengthened the coherency of Pollutants in Wastewater; Add again the macromolecule organic flocculating agent polyacrylamide, utilize the backbone of polyacrylamide, further make the pollutent conglomerate in waste water, thereby realized the purpose of solid-liquid separation.
Adopt the active sludge of antibiotic fermentation waste water biochemical treatment generation and the precipitating sludge conduct of antibiotic fermentation waste water flocculation sediment generation to add supporting agent, can take full advantage of the active sludge that the precipitating sludge that produces in technical process of the present invention and follow-up biochemical treatment produce, thereby the partially recycled of waste material and recycling have been realized, treating processes is integrated effectively as a whole, saved processing cost.
Activated carbon and flyash have good settlement action, after the flocculation agent coupling, can make promptly flocculating settling of the pollutent that condenses in waste water.Gac be except can increase the collision of particle, the soluble substance in can also absorption waste water to a certain degree, and settling velocity that can accelerate sludge.Flyash has larger specific surface area, and can produce adsorption to impurity in waste water, and can increase colloid contact-impact chance in waste water, the settling velocity of accelerate sludge etc., thus improve the follow-up treatment condition of mud.
To add supporting agent and flocculation agent join short mix in waste water (after 250r/min～350r/min), adopt low rate mixing mode (40～60r/min), process 1～5min, flocculation reaction is carried out fully.
The present invention can significantly improve COD, the SS clearance of antibiotic fermentation waste water.For the terminal waste water of certain production of antibiotics factory, adopt existing processing mode, COD, SS clearance are respectively 6～18% and 65～80%; The waste water COD and the SS clearance that adopt treatment process of the present invention to load flocculation treatment reach respectively 24～29% and 80～94%.Thereby the present invention can effectively improve the COD of waste water, the load that the SS clearance reduces follow-up biochemical treatment, improves overall process efficiency.
Embodiment
Below in conjunction with specific embodiments, the present invention is described in further details:
Embodiment 1
Certain pharmaceutical factory antibiotic fermentation technique terminal equalizing tank waste water, 36 ℃ of wastewater temperatures, pH are that 7.69, COD is that 11514mg/L, SS are 2355mg/L, and its treating processes is as follows:
A certain amount of polymerize aluminum chloride is dispersed in water, be mixed with mass concentration and be 5% mixed solution, this mixed solution joined waste water under the state that stirs, making the content of polymerize aluminum chloride in waste water is 300mg/L, stirring velocity is 300r/min, and churning time is 10s.
A certain amount of polyacrylamide is dispersed in water, be mixed with mass concentration and be 0.1% mixed solution, above-mentioned mixed solution is joined the above-mentioned waste water of processing with polymerize aluminum chloride under the state that stirs in, making the content of polyacrylamide in waste water is 2.5mg/L, stirring velocity is 300r/min, and churning time is 20s.
Get a certain amount of antibiotic fermentation waste water flocculation pre-treatment by the precipitating sludge of solid-liquid separation gained, the active sludge that produces during again by biochemical treatment by the supernatant liquor of solid-liquid separation gained with a certain amount of antibiotic fermentation waste water flocculation treatment, ratio with 1: 1 is dispersed in water, be mixed with the suspension liquid that total content is 8000mg/L, the pH that regulates suspension liquid is 8.In waste liquid: the ratio of suspension liquid volume ratio=100: 3 joins the above-mentioned waste liquid of processing with polyacrylamide with this suspension under the state that stirs in, stirring velocity is 300r/min, and churning time is 10s.
To pass into through the waste liquid of above-mentioned processing in the folded plate flocculation reaction tank and carry out flocculation sediment, stirring velocity is 50r/min, and the reaction times is 2min.In the material of the non-solubilities such as the suspended substance in waste water, colloid, throw out and waste water, the dissolved organic matter of part generates sedimentation and dehydration property floss preferably, and the waste water that forms floss carries out solid-liquid separation by settling tank.The precipitated solid of solid-liquid separation gained is used as adding supporting agent.Solid-liquid separation gained supernatant liquor enters follow-up biochemical treatment process, this supernatant liquor is passed into biochemical reaction tank carry out biochemical treatment, the waste water that discharges after producing active sludge and purify through solid-liquid separation again, the part active sludge of generation uses as adding supporting agent.In loading the pretreated waste water of flocculation, SS is 117mg/L, and COD is 8418mg/L, and the clearance of SS and COD is respectively 90.03% and 26.89%.
Embodiment 2～10
Certain pharmaceutical factory antibiotic fermentation technique terminal equalizing tank waste liquid, 34 ℃ of waste liquid temperatures, pH are that 7.06, COD is that 14264mg/L, SS are 1724mg/L, and its treating processes is as follows:
Get a certain amount of supporting agent that adds, be dispersed in water, being mixed with concentration is C
1Suspension liquid, regulate the pH of suspension liquid.Add above-mentioned suspension liquid under the condition that stirs in waste liquid, stirring velocity is V
1, churning time is T
1The volume ratio of waste liquid and suspension liquid is 100: a.
A certain amount of polymerize aluminum chloride is dispersed in water, and being mixed with the quality percentage composition is C
2Mixed solution, this polymerize aluminum chloride mixed solution joined the above-mentioned waste water of crossing with active sludge treatment under the condition that stirs, stirring velocity is V
2, churning time is T
2The consumption of polymerize aluminum chloride mixed solution is that to make the content of polymerize aluminum chloride in waste water be b.
A certain amount of polyacrylamide is dispersed in water, and being mixed with mass concentration is C
3Mixed solution joins this polyacrylamide mixed solution above-mentionedly in the waste water that the polymerize aluminum chloride mixed solution was processed under the condition that stirs, stirring velocity is V
3, churning time is T
3The consumption of polyacrylamide mixed solution is that to make the content of polyacrylamide in waste water be c.
To pass into through the waste liquid of above-mentioned processing in the folded plate flocculation reaction tank and carry out flocculation sediment under the condition that stirs, stirring velocity is V
4, the time is T
4In the material of the non-solubilities such as the suspended substance in waste water, colloid, throw out and waste water, the dissolved organic matter of part generates sedimentation and dehydration property floss preferably, and the waste water that forms floss carries out solid-liquid separation by settling tank.Solid-liquid separation gained supernatant liquor enters follow-up biochemical treatment process, this supernatant liquor is passed into biochemical reaction tank carry out biochemical treatment, the waste water that discharges after producing active sludge and purify through solid-liquid separation again, the part active sludge of generation can be used as and adds the supporting agent use.SS, the COD of mensuration in loading the pretreated waste water of flocculation calculates SS and COD clearance; Technique under above-mentioned different experimental conditions is adopted parameter (as: C
1～C
3, T
1～T
4, V
1～V
4, a, b, c etc.) and experimental result see table 1, table 2 for details, wherein,
The active sludge that to add supporting agent be the antibiotic fermentation waste water flocculation treatment produces by biochemical treatment by the supernatant liquor of solid-liquid separation gained of embodiment 2～4;
The supporting agent that adds of embodiment 5～7 is that antibiotic fermentation waste water flocculation pre-treatment is by the precipitating sludge of solid-liquid separation gained;
The active sludge that to add supporting agent be the antibiotic fermentation waste water flocculation treatment produces by biochemical treatment by the supernatant liquor of solid-liquid separation gained of embodiment 8 and antibiotic fermentation waste water flocculation pre-treatment are by the precipitating sludge of solid-liquid separation gained,, mix with the ratio of 1: 1;
The difference that adds supporting agent and embodiment 8 of embodiment 9 is that blending ratio is 1: 2;
The difference that adds supporting agent and embodiment 8 of embodiment 10 is that blending ratio is 3: 1.
Embodiment 11～16
Certain pharmaceutical factory antibiotic fermentation technique terminal equalizing tank waste water, 34 ℃ of wastewater temperatures, pH are that 6.71, COD is that 12382mg/L, SS are 2036mg/L, and its treating processes is as follows:
Take a certain amount of supporting agent that adds, join waste water under the condition that stirs, make that to add the concentration of supporting agent in waste water be a ', stirring velocity is V
1', churning time is T
1'.
A certain amount of polymerize aluminum chloride is dispersed in water, and being mixed with mass concentration is C
2' mixed solution, this mixed solution is joined above-mentioned in the waste water that flyash was processed under the state that stirs, making the content of polymerize aluminum chloride in waste water is b ', stirring velocity is V
2', churning time is T
2'.
Table 1
Table 2
A certain amount of polyacrylamide is dispersed in water, and being mixed with mass concentration is C
3' mixed solution, this mixed solution is joined above-mentioned in polymerize aluminum chloride waste water under the state that stirs, making the content of polyacrylamide in waste water is c ', stirring velocity is V
3', churning time is T
3'.
Carry out flocculation sediment in passing into the folded plate flocculation reaction tank under the condition that will stir through the waste liquid of above-mentioned processing, stirring velocity is V
4', the reaction times is T
4'.In the material of the non-solubilities such as the suspended substance in waste water, colloid, throw out and waste water, the dissolved organic matter of part generates sedimentation and dehydration property floss preferably, and the waste water that forms floss carries out solid-liquid separation by settling tank.Solid-liquid separation gained supernatant liquor enters follow-up biochemical treatment process, this supernatant liquor is passed into biochemical reaction tank carry out biochemical treatment, the waste water that discharges after producing active sludge and purify through solid-liquid separation again, the part active sludge of generation can be used as and adds the supporting agent use.SS, the COD of mensuration in loading the pretreated waste water of flocculation calculates SS and COD clearance, and the technique under different experimental conditions adopts parameter and experimental result sees table 3, table 4 for details, wherein,
The supporting agent that adds of embodiment 11～13 is flyash;
The supporting agent that adds of embodiment 14～16 is pulverous gac.
Table 3
Table 4
Claims (5)
1. the loading flocculation pretreatment method of an antibiotic fermentation waste water, described waste water is production of antibiotics terminal equalizing tank waste water, comprise crystal solution, waste liquor, the seeding tank washes, various wash-down waters and washing water in fermentor tank washes and processing and production process, the processing step that loads flocculation pretreatment method comprises: first add supporting agent to carry out water quality regulation in the mode that stirs in waste water, and then add flocculation agent in the mode that stirs; Perhaps first add flocculation agent in the mode that stirs in waste water, and then add supporting agent in the mode that stirs; To pass in flocculation tank through the waste water that above-mentioned steps is processed, stir, mix, then carry out solid-liquid separation; Solid-liquid separation is precipitated mud and supernatant liquor, and this supernatant liquor passes into biochemical treatment apparatus and carries out biochemical treatment, and after finishing dealing with, the waste water that is isolated to active sludge and can discharges is characterized in that:
Described flocculation agent comprises polymerize aluminum chloride and polyacrylamide, and the addition sequence of flocculation agent is: first add polymerize aluminum chloride, then add polyacrylamide; Described add active sludge that suspension liquid that supporting agent comprises the precipitating sludge that antibiotic fermentation waste water obtains when loading flocculation pre-treatment solid-liquid separation, supernatant liquor that solid-liquid separation obtains produce when biochemical treatment suspension liquid one or both mixture, pulverous gac, flyash wherein; Through flocculation agent with add the waste water that supporting agent processed and pass in flocculation tank, take the rotating speed of 40～60r/min stir, mixing time is as 1～5min;
The described supporting agent that adds is for being mixed with the suspension liquid of 6000～10000mg/L with one or both of described active sludge or precipitating sludge, and with the pH regulator to 7.0 of suspension liquid～9.0, the volume ratio that adds 0.1～20 part of suspension liquid according to 100 parts of waste water, low whipping speed is under the condition of 250～350r/min, suspension liquid to be joined in waste water, and mixing time is 5～15s.
2. the loading flocculation pretreatment method of an antibiotic fermentation waste water, described waste water is production of antibiotics terminal equalizing tank waste water, comprise crystal solution, waste liquor, the seeding tank washes, various wash-down waters and washing water in fermentor tank washes and processing and production process, the processing step that loads flocculation pretreatment method comprises: first add supporting agent to carry out water quality regulation in the mode that stirs in waste water, and then add flocculation agent in the mode that stirs; Perhaps first add flocculation agent in the mode that stirs in waste water, and then add supporting agent in the mode that stirs; To pass in flocculation tank through the waste water that above-mentioned steps is processed, stir, mix, then carry out solid-liquid separation; Solid-liquid separation is precipitated mud and supernatant liquor, and this supernatant liquor passes into biochemical treatment apparatus and carries out biochemical treatment, and after finishing dealing with, the waste water that is isolated to active sludge and can discharges is characterized in that:
Described flocculation agent comprises polymerize aluminum chloride and polyacrylamide, and the addition sequence of flocculation agent is: first add polymerize aluminum chloride, then add polyacrylamide; Described add active sludge that suspension liquid that supporting agent comprises the precipitating sludge that antibiotic fermentation waste water obtains when loading flocculation pre-treatment solid-liquid separation, supernatant liquor that solid-liquid separation obtains produce when biochemical treatment suspension liquid one or both mixture, pulverous gac, flyash wherein; Through flocculation agent with add the waste water that supporting agent processed and pass in flocculation tank, take the rotating speed of 40～60r/min stir, mixing time is as 1～5min;
The described supporting agent that adds is flyash or pulverous gac, with flyash or pulverous gac, according to adding 5～200mg to add the consumption of supporting agent in every 1L waste water, low whipping speed is to join in waste water under the condition of 250～350r/min, and mixing time is 5～15s.
3. according to claim 1 or the loading flocculation pretreatment method of the 2 described a kind of antibiotic fermentation waste waters of any one, it is characterized in that: the mode that adds of described polymerize aluminum chloride is that polymerize aluminum chloride is mixed with mass concentration is 5～15% mixed solution, according to adding the consumption of 200～1000mg polymerize aluminum chloride in every 1L waste water, low whipping speed is under the condition of 200～400r/min, mixed solution to be joined in waste water, and mixing time is 5～10s.
4. according to claim 1 or the loading flocculation pretreatment method of the 2 described a kind of antibiotic fermentation waste waters of any one, it is characterized in that: the mode that adds of described polyacrylamide is that polyacrylamide is mixed with mass concentration is 0.1～0.3% mixed solution, according to adding the consumption of 2.5～10mg polyacrylamide in every 1L waste water, low whipping speed is under the condition of 200～400r/min, mixed solution to be joined in waste water, and mixing time is 10～20s.
5. according to claim 1 or the loading flocculation pretreatment method of the 2 described a kind of antibiotic fermentation waste waters of any one, it is characterized in that: described flocculation tank is the folded plate flocculation reaction tank.
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| CN112250155B (en) * | 2019-12-31 | 2023-03-17 | 中煤（北京）环保工程有限公司 | Heavy medium quick-settling water treatment method |
| CN111792713A (en) * | 2020-07-15 | 2020-10-20 | 天津大学 | Domestic sewage loading coagulation treatment method based on carbon-phosphorus separation |
| CN112375693A (en) * | 2020-11-19 | 2021-02-19 | 陕西麦可罗生物科技有限公司 | Method for preparing microbial agent by utilizing natural bioflocculant to pretreat kasugamycin fermentation hyphae |
| CN112919463B (en) * | 2021-04-09 | 2021-10-26 | 南京理工大学 | Activated carbon prepared from tiamulin waste salt and preparation method thereof |
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