CN102775019B - Coupling type sewage de-phosphorization purification regeneration treatment technique - Google Patents

Coupling type sewage de-phosphorization purification regeneration treatment technique Download PDF

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CN102775019B
CN102775019B CN201210259354.9A CN201210259354A CN102775019B CN 102775019 B CN102775019 B CN 102775019B CN 201210259354 A CN201210259354 A CN 201210259354A CN 102775019 B CN102775019 B CN 102775019B
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soil
water
parts
agent
mud
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CN201210259354.9A
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CN102775019A (en
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牛晓君
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华南理工大学
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Abstract

The invention discloses a coupling type sewage de-phosphorization purification regeneration treatment technique. Urban sewage is used as a treated object, the regeneration treatment method comprises the following steps of: a), preliminary precipitation, b), conversion of phosphor in the sewage to hydrogen phosphide in order to remove phosphor; c), conversion of hydrogen phosphide; and d), recovering of purified water; and in this way, the urban sewage is recovered and reused, all the mud after the sewage treatment is recovered, organic pollutants and nitrogen are removed. With the adoption of the technique, the defects of large mud treatment difficulty and large occupied area in the mud exhaust de-phosphorization of the existing normal biochemical treatment process and membrane bioreactor process are overcome; and meanwhile, new coagulant, adsorbent and flocculent are used in order to recover and regenerate water better, the sterilization is performed by nitrogen-ultrasonic-ultraviolet combination, hydrogen phosphide is converted into phosphatic fertilizer, in this way, the blank of effective conversion and utilization of hydrogen phosphide at home and abroad is filled.

Description

A kind of manifold type sewage dephosphorization purifying regeneration treatment process
Technical field
The present invention relates to sewage disposal and reclaim field, relate in particular to a kind of manifold type sewage dephosphorization purifying regeneration treatment process.
Background technology
Phosphorus is as a kind of limited resources that can not Natural re generation on the earth, in global range ubiquity landing field phosphate mineral resources day by day deficient with water surrounding in phosphorus content too high and cause this contradiction of body eutrophication.Body eutrophication problem is one of current main environmental problem, has seriously restricted society and economic Sustainable development.Phosphorus is one of important factor of bringing out body eutrophication as nutritional factor.Wherein the phosphorus in water body is mainly derived from sanitary sewage, washing composition and trade effluent, and the phosphorus of how effectively removing in waste water is the hot issue of countries in the world environmental engineering investigator research always.Investigator has carried out a large amount of research to dephosphorization theory, technology and related process thereof both at home and abroad.But major part be take consumption ample resources, energy as cost is by pollutant removals such as the nitrogen in sewage, phosphorus, exists " consuming energy " to pollute the shortcoming of marrying again.So, the technology of phosphorus removal from wastewater that breaks traditions, it is the focus that scientific circles pay close attention to that the resource utilization that realizes phosphor in sewage becomes.
In recent years with struvite (MAP:MgNH 4pO 46H 2o) form is recovered as study hotspot.The dephosphorization technique reclaiming with struvite form can be used for processing high-concentration ammonia nitrogenous wastewater and high concentration phosphorus hydrochlorate waste water and contain ammonia nitrogen in high density and phosphate waste simultaneously, can also reduce the atmosphere greenhouse gases that produce some oxynitride types in waste water.But these researchs mainly lay particular emphasis on chemical recovering method and process, chemical method dephosphorization is not only that medicament is expensive, working cost is higher, make in addition a large amount of anionic residues stay in water, cause the salinity of water to increase, cause secondary pollution, the content of nitrogen and phosphorous of water outlet simultaneously does not all also reach emission standard, also needs to be used as further processing.
And biological phosphate-eliminating coupling phosphor resource process is the technological line of economical rationality, this technology also becomes possibility gradually.When the total amount migration and variation rule of research sewage work phosphorus, find that first its total phosphorus loss reaches 30%-45%, and confirmed that the loss of phosphorus enters atmosphere mainly with gaseous phosphine form.And then phosphuret-(t)ed hydrogen all detected in places such as wetland, refuse landfill, plants, even in the biosphere in the South Pole, all there is the existence of phosphuret-(t)ed hydrogen.Now there are some researches show, the phosphorus in sewage may under anaerobion effect, be reduced generation phosphuret-(t)ed hydrogen as the precursor of phosphuret-(t)ed hydrogen completely, with free state, matrix ADSORPTION STATE phosphuret-(t)ed hydrogen (matrix-bound) form, exists.According to us, early stage the investigation of phosphorus in anaerobic waste water treating processes is found, wherein total phosphorus loss maximum reaches 78%.These find sewage dephosphorization and phosphorus recovery working cycle that thinking is provided, and it not only shows that, in sewage dephosphorization process, phosphorus can be removed with gaseous form, also shows that phosphorus can carry out with gaseous form resource utilization recovery in working cycle.So the discovery of phosphuret-(t)ed hydrogen in sewage treatment process caused people's common concern at once, how does it produce in technology of phosphorus removal from wastewater? how does it participate in removal and the resource recycling of sewage phosphorus? after phosphuret-(t)ed hydrogen produces, enter how water body, atmosphere are collected, resource utilization? new way machine-processed for the anaerobe removal, the resource utilization that disclose sewage phosphorus, that develop sewage phosphorus removal, circulation has important scientific meaning and application prospect.
In the biogeochemical cycle of phosphorus, think that for a long time gaseous phosphine is non-existent at nature always.Until 1988, investigator finds that the phosphorus of sewage work's loss enters atmosphere with gaseous phosphine form first.Subsequently, in refuse landfill, plant, river and organism, detected successively the phosphuret-(t)ed hydrogen existing with free state form, along with phosphuret-(t)ed hydrogen is detected one after another in varying environment, phosphuret-(t)ed hydrogen is finally confirmed to be a kind of trace gas being extensively present in atmosphere.The discovery of Phosphine in Natural Environment is the important supplement to phosphorus Cyclical Theory, and having changed the phosphorus of thinking in the past in atmosphere is the incorrect view consisting of the inorganic phosphate being attached on air participates or depositing dust particle.Therefore,, in the biogeochemical cycle of phosphorus, must consider existence and status and the effect of phosphuret-(t)ed hydrogen.Because Phosphine in Natural Environment content is very micro-, be subject to the impact of the conditions such as collection, preservation, enrichment and detection technique of sample, early stage analytical procedure and technique means are difficult to realize the quantitative assay to Environmental Trace phosphuret-(t)ed hydrogen, and in relevant environment, the research of phosphuret-(t)ed hydrogen behavior is not also extensively carried out.
Phosphuret-(t)ed hydrogen is a kind of poisonous and active reducing gas that can be carcinogenic, human body suck just can cause on a small quantity feeling sick, the symptom such as vomiting, uncomfortable in chest, diarrhoea, when serious, can cause the pulmonary edema death of even going into a coma.So the discovery of this compound in environment causes people's common concern at once, setting up sensitive reliable analytical procedure is the prerequisite of carrying out phosphuret-(t)ed hydrogen research in environment.
Therefore study phosphorus in sewage dephosphorization anaerobic reactor system and technique thereof how to change into phosphuret-(t)ed hydrogen, phosphuret-(t)ed hydrogen how about to waste water water body discharge, how it produces in reactor and the final problem such as stable resources how, and then disclose the conversion process of Phosphorus From Wastewater and remove mechanism, set up resource utilization process engineering for regenerating, to widening the range of application of sewage dephosphorization biotechnology, the technology that changes tradition " consuming energy " is significant.
Having there are some researches show that lake, wetland, rice terrace are one of source of gaseous phosphine in atmosphere, is also the most important remittance of gaseous phosphine.Gassmann detects PH first in Hamburg, Germany port and German gulf bottom unfiltered water body 3, its concentration is up to 12.5 pgL-1, and PH after identical water body filtration, do not detected 3.The applicant all detects PH in Taihu Lake and the filtration of oolong pool and unfiltered water body 3exist, do not filter lake water than the PH filtering in lake water 3content is high 2～14 times, PH in lake water 3vertical change very little, also find that concentration in the concentration ratio lake water of ADSORPTION STATE phosphuret-(t)ed hydrogen in settling is up to 103-105 doubly simultaneously.These investigators all think PH in water body 3mainly the form with matrix-bound phosphine (MBP) exists.Within 2002, the bright grade of Yu Zhi detects the matrix-bound phosphine of ng/kg (dry weight) order of magnitude first in the settling of typical case's cultivation marine site, Jiaozhou Bay, and its concentration reaches as high as 685ng/kg.Female clear woods etc. been has also has been investigated and analysed content and the distribution of Sediments In Jiaozhou Bay mesostroma combined hydrogen phosphide, and detected result shows that phosphuret-(t)ed hydrogen maximum concentration reaches 43.75ng/kg (dry weight).The generation of sewage phosphuret-(t)ed hydrogen, sludge absorption not only directly affect dephosphorization efficiency by using, and directly and its resource utilization process closely related, therefore, necessary mud mesostroma combined hydrogen phosphide is furtherd investigate.
In sewage phosphorus treating processes, first the gaseous phosphine that the generations such as anaerobion discharge will reach adsorption-desorption balance with mud before being discharged into atmosphere, and the excessive gaseous phosphine not being adsorbed is just discharged into the atmosphere.Phosphor in sewage can generate phosphuret-(t)ed hydrogen through the reductive action of microorganism, and the phosphuret-(t)ed hydrogen in sewage is easy to be adsorbed on mud granule, forms matrix-bound phosphine (MBP).Therefore, carry out the desorption of mud mesostroma combined hydrogen phosphide in a deep going way, collection, stable resourcesization research for phosphor in sewage hydrogen, find the approach that improves sewage phosphorus clearance, build the process for reclaiming of phosphor in sewage under anaerobic condition, develop continuable sewage disposal, resource recovery technology all has important meaning, the current domestic and international rarely seen report of research of this respect.
Phosphorus is one of most important element in soil.In China, 74% arable soil lacks phosphorus, and the phosphorus in soil more than 95% is invalid form, and farm crop are difficult to directly absorb, so the bioavailability of phosphorus is the focus that scientific circles pay close attention to always.Phosphuret-(t)ed hydrogen is easy to be adsorbed on soil particle, forms matrix-bound phosphine, and in the research discovery soil such as Han, 0.74% of total phosphorus is converted into phosphuret-(t)ed hydrogen and is stored in soil, and the phosphuret-(t)ed hydrogen of generation is very easily by storage that soil particle adsorbs.In the resource utilization process of sewage dephosphorization coupling phosphorus, if the phosphorus in sewage can be converted into phosphuret-(t)ed hydrogen, height absorption storage by phosphuret-(t)ed hydrogen in adsorption by soil agent, and be administered in soil, phosphuret-(t)ed hydrogen in adsorption by soil agent will change the reactive phosphate easily being absorbed by farm crop into, especially aobvious important for phosphorus restriction soil.For promoting that agriculture Sustainable development is significant, at home and abroad there is no at present the research report of this respect.
Along with the development of Chinese society economy and urbanization, the quantity that municipal effluent produces is in continuous growth, thereby directly causes rolling up of amount of sludge.That municipal sludge refers to that sewage work produces is solid-state, semi-solid state and liquid waste, contains nutrition, heavy metal and the pathogenic bacterium such as a large amount of organism, abundant nitrogen, phosphorus and pathogenic bacteria etc., and usually with foul gas.If do not add, do not process and discharge arbitrarily, can cause serious secondary pollution to environment.The object one that mud is disposed is to reduce sludge volume, reduces the expense of sludge disposal; The 2nd, by processing, can make sludge stabilizing, no longer produce the further degraded of mud, avoid secondary pollution; The 3rd, mud can reach innoxious and sanitisation after disposing; The 4th, reach the object of turning bane into boon, fully utilizing.
Developing rapidly of national economy, the popular feeling and fulfilling of deepening continuously of environment protection fundamental state policy, the universal and in-depth of urban sewage treatment system, causes the quantity of municipal sewage plant increasing, and the output of mud also increases by a wide margin.City sewage and sludge must pass through appropriate processing, could reduce the pollution to environment.The only way that city sewage and sludge is processed makes its minimizing, further resource utilization exactly.Therefore, how to dispose rationally and effectively the mud of Sewage Plant, become the major issue that municipal sewage plant and relevant departments face.
Before the final processing of city sewage and sludge, first should make its minimizing, in this process, must add flocculation agent.The most frequently used flocculation agent is polymerize aluminum chloride (referred to as PAC), though have certain flocculating property, maximum shortcoming is in treating processes, and the water content of mud cake is high, and loose, easily broken, and dehydration rate is low, to aftertreatment, brings difficulty.
The mud that Chinese patent CN1266832A introduces Liao Jiang sewage work mixes with zeolite, the volume ratio that mud mixes with zeolite is 1: 1～3, carry out aerobic fermentation, the high temperature that microbial process produces (general sustainable more than 3 days at more than 55 ℃ high-temperature times) is with decomposing organic matter.The method utilizes zeolite as the expansion amendment of sludge composting, does not participate in microbiological deterioration reaction.Chinese patent CN1354158A has introduced a kind of municipal sludge that utilizes and has carried out composting, the sludge composting that obtains becoming thoroughly decomposed, then add cultured vinelandii, phosphate solubilizing bacteria, potassium solubilizing bacteria microbial inoculum to be produced into the method for biological organic composite fertilizer.Chinese patent CN1359876A has introduced a kind of soil and fertilizer that adds unslaked lime and coal dust ash to manufacture with municipal sludge, their preparation method and application, to reach low-cost by municipal sludge, unslaked lime, coal dust ash being carried out to suitable proportioning, in good time composting, stirring and insulation, effective object.Chinese patent CN1502591A has introduced a kind for the treatment of process of municipal sludge, and it is in mud, to add amendment, and amendment mainly adopts wood chip and the garden lop that proportion is relatively little, carries out compost disposal.
Publication number is the patent application of CN101885538A, a kind of membrane bioreactor process for removing phosphorus without mud discharge is disclosed, it specifically discloses a kind of method of dephosphorization, phosphorus is transformed into phosphuret-(t)ed hydrogen and be blown into atmosphere, but such discharge meeting causes secondary pollution to atmosphere, because phosphuret-(t)ed hydrogen is toxic gas, phosphuret-(t)ed hydrogen is a kind of poisonous and active reducing gas that can be carcinogenic, human body suck just can cause on a small quantity feeling sick, the symptom such as vomiting, uncomfortable in chest, diarrhoea, when serious, can cause the pulmonary edema death of even going into a coma.So the discovery of this compound in environment causes people's common concern at once, setting up sensitive reliable analytical procedure is the prerequisite of carrying out phosphuret-(t)ed hydrogen research in environment.On this basis, the present invention is directed to this technology and improve, phosphuret-(t)ed hydrogen is transformed into fertilizer, filled up blank both domestic and external.
The following problem existing in order to overcome current spoil disposal dephosphorization major technique: sludge discharge is large, it is large that excess sludge is disposed difficulty.The blank that effectively transforms this respect technology for current phosphuret-(t)ed hydrogen, has proposed the present invention, has proposed first nitrogen-ultrasonic wave-ultraviolet combined sterilizing technique simultaneously, has also filled up technological gap.
Summary of the invention
The object of the invention is to overcome prior art above shortcomings, a kind of manifold type sewage dephosphorization purifying regeneration treatment process is provided, concrete technical scheme is as follows.
A manifold type sewage dephosphorization purifying regeneration treatment process, comprises the following steps:
A) preliminary sedimentation
The sewage that sewer line is collected enters sand setting water collecting basin after filtering removal solid sundries by coarse rack, by water pump, sand setting water collecting basin sewage is extracted after lifting is filtered silt particle by fine fack and enters adjustment pond, by water circulating pump and the ejector that is connected with water circulating pump, to adjusting bottom, pond, fill the boring aeration pipe water flowing aeration laying and stir water body, keep water quality relatively stable, by the water outlet of water pump water pipe;
B) anaerobic-aerobic is processed
The water outlet that step a) obtains enters anaerobic pond and stops 1 ~ 2 hour, then enters Aerobic Pond stop 3 ~ 4 hours, then after entering the first settling tank precipitation, supernatant liquor enters coagulation basin, and the sludge part of the first settling tank is back to anaerobic pond, and excess sludge enters mud and deposits pond;
C) in coagulation basin, add coagulating agent, nano level super-fine powder sorbent material, flocculation agent, impel the particle aggregation in water to obtain mixed solution; Then whole mixed solution is introduced to the second settling tank and precipitate, and the supernatant liquor of solid, liquid separation, the solids of precipitation also enters mud and deposits pond; Described coagulating agent adopts Poly Dimethyl Diallyl Ammonium Chloride, polymerize aluminum chloride, the mixture of Tai-Ace S 150, iron(ic) chloride; Described nano level super-fine powder sorbent material is prepared from by described ratio of weight and number by following raw material: 10 ~ 25 parts of TMS cage type polysilsesquioxanes, 5 ~ 10 parts of nano level active carbon powders, 5 ~ 10 parts, nano level diatom soil, 20 ~ 25 parts of active clays, and hybrid reaction is made at normal temperatures; Described flocculation agent adopts magnetic flocculant;
D) nitrogen-ultrasonic wave-ultraviolet combined sterilizing
To above-mentioned steps c) supernatant liquor that obtains carries out nitrogen-ultrasonic wave-ultraviolet combined sterilizing, use UV-irradiation uv sterilisation on one side, pass into nitrogen on one side, ultra-sonic oscillation, are used agitator fully to stir 30-60 minute on one side, carry out pasteurised completely, postprecipitation 1-1.2 hour, essence filter, removes the residual impurity in water, obtains processing purifying waste water of reclaiming.
Further, to step b), c) in, entering mud deposits the excess sludge in pond and carries out advanced treatment, semiclosed mud is deposited pond, toward mud, deposit and in pond, pass into gas phosphuret-(t)ed hydrogen and stir, phosphuret-(t)ed hydrogen is easy to be adsorbed on mud granule, form matrix-bound phosphine MBP, add again adsorption by soil agent, height absorption storage by phosphuret-(t)ed hydrogen in adsorption by soil agent, be administered in soil, phosphuret-(t)ed hydrogen in adsorption by soil agent will change the reactive phosphate easily being absorbed by farm crop into, be phosphate fertilizer, be used for the soil that phosphorus shortage soil or phosphorus exist with invalid form, described adsorption by soil agent is the mixture of the peat composed of rotten mosses and humic acid, and blending ratio is 1:1.
When adding further adsorption by soil agent, also add soil improvement agent, agent for preserving soil moisture.
Described soil improvement agent is made by the raw material of following weight (part) proportioning: be selected from one or more 30 parts, the mixture in the peat composed of rotten mosses, weathered coal, zeolite, water glass, rhombspar, vermiculite, kaolin, calcium bentonite, diatomite; 10 ~ 20 parts of terra albas, 5 ~ 8 parts of anhydrous calciumsulphates, 1 ~ 5 part, sulfurous iron ore, 5 ~ 8 parts of oxalic acid, 3 parts, potassium, by abundant levigate the mixing of above-mentioned raw materials, be prepared into soil improvement agent, fineness requirement >=110 order.
Described agent for preserving soil moisture, is made by the raw material of following weight (part) proportioning: 58 ~ 78 parts of acrylic acid or dimethyl propylene diluted acids; 16 ~ 24 parts, sodium hydroxide; 6 ~ 16 parts, potassium hydroxide; 0 ~ 10 part of Potassium Persulphate; 0 ~ 8 part of glycocoll; 5 parts, ferrous sulfate; 2 ~ 5 parts of ammonium chloride or ammonium sulfate or hydrogen peroxide; 20 parts of starch; Account for the aerobic particle mud of above total amount of compound 0 ~ 45 weight part.
Further, the preparation method of described step c) magnetic flocculant is:
Step 1: ferrous salt and trivalent iron salt are mixed according to mol ratio at 2: 3, and heated and stirred is warming up to 55 ℃, slowly adds sodium hydroxide or ammoniacal liquor, and the mol ratio of adjusting total iron and alkali is 1: 4～1: 3, slaking 0.5～5 hour; Add again acid to regulate mother liquor for acid, add 3%～10% hydrogen peroxide of mother liquor weight or blast air ferrous ion is all oxidized to ferric iron, obtain the gluey flocculation agent that contains magnetic; Iron content flco in the sulfuric acid dissolution waste water that is 92%～97% with mass percent concentration, filters, and obtains ferrous salt and molysite; And utilize air to be partly oxidized to ferric sulfate or iron(ic) chloride;
Step 2: by above-mentioned ferric sulfate or iron(ic) chloride and ferrous grade weight percent 55%～70% and granularity at the magnetite powder of 380 order～500 by weight 30-5: 1 mixes, and obtains many group flocculation agents, can be for step c) as magnetic flocculant;
Step 3: process respectively containing iron waste water with above-mentioned many group flocculation agents, the add-on of determining magnetic flocculant according to turbidity and iron-holder is lower than 20(mg/L), stir, adding alkali to regulate pH is 8～10, first rapid stirring is low rate mixing then, then put into the settling tank that Surface field is the permanent magnet of 0.2～1.5T, quiescent setting are housed;
Step 4: after supernatant liquor clarification, water is emitted or utilize vacuum sucking-off; Remove magnetic field device utilization machinery or wind and sweep the flco that recovery precipitates, or shifting magnetic field device does not directly carry out next step;
Step 5: dissolve the iron content flco in waste water with acid, filter, obtain ferrous salt and molysite; Again by step 1)-2) prepare magnetic flocculant;
Step 3) to 5) realize the recirculation utilization of magnetic flocculant.
Compared with prior art, the present invention has following beneficial effect:
The present invention overcome the sludge disposal difficulty that existing routine biochemistry treatment process and membrane biological reactor process exist by spoil disposal dephosphorization large, take up an area large defect, new coagulating agent, sorbent material, the better reclaiming water of flocculation agent have been applied simultaneously, nitrogen-ultrasonic wave-ultraviolet combined sterilizing, and phosphuret-(t)ed hydrogen is changed into phosphate fertilizer, filled up at present the blank of the effective trans-utilization of phosphuret-(t)ed hydrogen both at home and abroad.
Embodiment
Embodiment 1
The present embodiment carries out advanced treatment for the sewage of a certain chemical plant emission in bad V class Guangzhou and reaches surface water III class level (TN < 15mg/L), and day output is 10 tons.
This embodiment micro-polluted water treatment step is as follows:
A manifold type sewage dephosphorization purifying regeneration treatment process, comprises the following steps:
A) preliminary sedimentation
The sewage that sewer line is collected enters sand setting water collecting basin after filtering removal solid sundries by coarse rack, logical
Cross water pump sand setting water collecting basin sewage is extracted after lifting is filtered silt particle by fine fack and enters adjustment pond, by the ejector of water circulating pump and connection, fill the boring aeration pipe water flowing aeration laying and stir water body to bottom, pond, maintenance water quality is relatively stable.
B) anaerobic-aerobic is processed
The water outlet that step a) obtains enters anaerobic pond and stops 1 hour, and Aerobic Pond stops 3 hours, and supernatant liquor enters coagulation basin after precipitation, and the sludge part of settling tank is back to anaerobic pond, and excess sludge enters mud and deposits pond;
C) in coagulation basin, add coagulating agent, nano level super-fine powder sorbent material, flocculation agent, impel the particle aggregation in water to obtain mixed solution; Then whole mixed solution is introduced to settling tank and precipitate, and the supernatant liquor of solid, liquid separation, the solids of precipitation also enters mud and deposits pond;
Described coagulating agent adopts Poly Dimethyl Diallyl Ammonium Chloride, polymerize aluminum chloride, the mixture of Tai-Ace S 150, iron(ic) chloride, and its blending ratio is 3:2:1:1, consumption is 20mg/L;
Described nano level super-fine powder sorbent material, described nano level super-fine powder sorbent material is prepared from by described ratio of weight and number by following raw material: 10 parts of TMS cage type polysilsesquioxanes, 5 parts of nano level active carbon powders, 5 parts, nano level diatom soil, 20 parts of active clays, and hybrid reaction is made at normal temperatures;
Described flocculation agent adopts ferromegnetism flocculation agent;
Described flocculation agent adopts magnetic flocculant, and its preparation method is:
Step 1: ferrous salt and trivalent iron salt are mixed according to mol ratio at 2: 3, and heated and stirred is warming up to 55 ℃, slowly adds sodium hydroxide or ammoniacal liquor, and the mol ratio of adjusting total iron and alkali is 1: 4: 3, slaking 0.5 hour; Add again acid to regulate mother liquor for acid, add 3% hydrogen peroxide or blast air ferrous ion is all oxidized to ferric iron, obtain the gluey flocculation agent that contains magnetic; Iron content flco in the sulfuric acid dissolution waste water that is 92% with mass percent concentration, filters, and obtains ferrous salt and molysite; And utilize air to be partly oxidized to ferric sulfate or iron(ic) chloride;
Step 2: at 55% magnetite powder, granularity of magnet powder is pressed 30-5 in the ratio of 380 order object magnetics: 1 mixes, and obtains many group flocculation agent liquid by molysite and ferrous grade;
Step 3: process respectively containing iron waste water with above-mentioned many group flocculation agents, the add-on of determining magnetic flocculant according to turbidity and iron-holder is lower than 20mg/L, stir, adding alkali to regulate pH is 8, first rapid stirring is low rate mixing then, then put into the settling tank that Surface field is the permanent magnet of 0.2～1.5T, quiescent setting are housed;
Step 4: after supernatant liquor clarification, water is emitted or utilize vacuum sucking-off; Remove magnetic field device utilization machinery or wind and sweep the flco that recovery precipitates, or shifting magnetic field device does not directly carry out next step;
Step 5: dissolve the iron content flco in waste water with acid, filter, obtain ferrous salt and molysite; By step 1, prepare magnetic flocculant.
D) nitrogen-ultrasonic wave-ultraviolet combined sterilizing
To above-mentioned steps c) supernatant liquor that obtains carries out nitrogen-ultrasonic wave-ultraviolet combined sterilizing, use UV-irradiation uv sterilisation on one side, pass into nitrogen on one side, ultra-sonic oscillation, are used agitator fully to stir 30 minutes on one side, carry out pasteurised completely, postprecipitation 1 hour, essence filter, removes the residual impurity in water, obtains processing purifying waste water of reclaiming.
Employing is at < < (water and waste water determination method (the 4th edition) > >, the work such as Wang Xinfang, China Environmental Science Press publishes the method for describing in (2002), has analyzed the water quality of the present embodiment processing water:
1, BOD: dilution inoculation method
2, COD: potassium dichromate process
Many batches of water samples before and after processing are analyzed, and its analytical results is listed in the table below 1:
Table 1
The total phosphorus concentration of former water is 1000mg/L, processes water outlet and has reached 0.015mg/L, has also reached national new emission standard.
Further, to step b), c) in, entering mud deposits the excess sludge in pond and carries out advanced treatment, semiclosed mud is deposited pond, toward mud, deposit and in pond, pass into gas phosphuret-(t)ed hydrogen and stir, phosphuret-(t)ed hydrogen is easy to be adsorbed on mud granule, form matrix-bound phosphine MBP, add again adsorption by soil agent, height absorption storage by phosphuret-(t)ed hydrogen in adsorption by soil agent, be administered in soil, phosphuret-(t)ed hydrogen in adsorption by soil agent will change the reactive phosphate easily being absorbed by farm crop into, be phosphate fertilizer, be used for the soil that phosphorus shortage soil or phosphorus exist with invalid form, described adsorption by soil agent is the mixture of the peat composed of rotten mosses and humic acid, and blending ratio is 1:1.
When adding further adsorption by soil agent, also add soil improvement agent, agent for preserving soil moisture;
Described soil improvement agent is made by the raw material of following weight (part) proportioning: be selected from one or more 30 parts, the mixture in the peat composed of rotten mosses, weathered coal, zeolite, water glass, rhombspar, vermiculite, kaolin, calcium bentonite, diatomite; 10 parts of terra albas, 5 parts of anhydrous calciumsulphates, 1 part, sulfurous iron ore, 5 parts of oxalic acid, 3 parts, potassium, by abundant levigate the mixing of above-mentioned raw materials, be prepared into soil improvement agent, fineness requirement >=110 order;
Described agent for preserving soil moisture, is made by the raw material of following weight (part) proportioning: 58 parts of acrylic acid or dimethyl propylene diluted acids; 16 parts, sodium hydroxide; 6 parts, potassium hydroxide; 2 parts of Potassium Persulphates; 2 parts of glycocoll; 5 parts, ferrous sulfate; 2 parts of ammonium chloride or ammonium sulfate or hydrogen peroxide; 20 parts of starch; Account for the aerobic particle mud of above total amount of compound 5 weight parts;
The object of sterilization and disinfection is that be greater than 45min and be advisable duration of contact in order to produce the microbiological corrosion to equipment and pipeline in anti-sealing reuse process, and chlorine dosage is 5mg/L, guarantees that pipe network residual chlorine amount is 0.1mg/L.
In technique of the present invention, all equipment of using is all product sold, for example related products of Jiangsu Runtian Water Industry Equipment Co., Ltd. in the market.
Table 2 is step b), c) after the mud that obtains do not pass into PH 3the main component of front mud
Table 2
Table 3 is step b), c) after the mud that obtains pass into PH 3afterwards by the main component of mud after the soil that applies fertilizer after oxygenant oxidation in air and soil
Table 3
Table 4 is step b), c) after the mud that obtains pass into PH 3after, apply fertilizer after adding adsorption by soil agent by oxygenant oxidation in air and soil to the main component of mud after soil simultaneously
Table 4
Table 5 is step b), c) after the mud that obtains pass into PH 3after, apply fertilizer after adding adsorption by soil agent by oxygenant oxidation in air and soil to the index of mixing the soil of main component after moisture preserving agent after soil simultaneously and change
Table 5
Project Content
Organic Be greater than 48
N Be greater than 7.8
P Be greater than 13.6
K Be greater than 10.6
PH 6.8~7.0
Has done on certain farm in outskirts of a town, Guangzhou is that its test in 1 year is as follows:
1, do not add 0.5 mu of common white vegetable plot of any mud
Chinese cabbage output is: 2600 kilograms
2, by step b), c) after the mud that obtains do not pass into mud fertilising before PH3 to 0.5 mu of common white vegetable plot
Chinese cabbage output is: 3000 kilograms, significantly improved quality of vegetable simultaneously, and moisture is large, micro-sweet
3, by step b), c) after the mud that obtains pass into after PH3 by the mud fertilising after oxygenant oxidation in air and soil to 0.5 mu of common white vegetable plot
Chinese cabbage output is: 3500 kilograms, significantly improved quality of vegetable simultaneously, and moisture is large, micro-sweet
4, by step b), c) after the mud that obtains pass into after PH3, the mud fertilising after simultaneously adding adsorption by soil agent by oxygenant oxidation in air and soil is to 0.5 mu of Chinese cabbage ground
Chinese cabbage output is: 3950 kilograms, significantly improved quality of vegetable simultaneously, and moisture is large, micro-sweet
Embodiment 2
The sewage that the present embodiment discharges for a certain textile mills in bad V class Guangzhou carries out advanced treatment and reaches surface water III class level (TN < 15mg/L), and day output is 10 tons.
A manifold type sewage dephosphorization purifying regeneration treatment process, is characterized in that the method comprises the following steps:
A) preliminary sedimentation
The sewage that sewer line is collected enters sand setting water collecting basin after filtering removal solid sundries by coarse rack, logical
Cross water pump sand setting water collecting basin sewage is extracted after lifting is filtered a small amount of silt particle by fine fack and enters adjustment pond, by the ejector of water circulating pump and connection, fill the boring aeration pipe water flowing aeration laying and stir water body to bottom, pond, maintenance water quality is relatively stable.
B) anaerobic-aerobic is processed
The water outlet that step a) obtains enters anaerobic pond and stops 1.5 hours, and Aerobic Pond stops 3.5 hours, and supernatant liquor enters coagulation basin after precipitation, and the sludge part of settling tank is back to anaerobic pond, and excess sludge enters mud and deposits pond;
C) in coagulation basin, add coagulating agent, nano level super-fine powder sorbent material, flocculation agent, impel the particle aggregation in water to obtain mixed solution; Then whole mixed solution is introduced to settling tank and precipitate, and the supernatant liquor of solid, liquid separation, the solids of precipitation also enters mud and deposits pond;
Described coagulating agent adopts Poly Dimethyl Diallyl Ammonium Chloride, polymerize aluminum chloride, the mixture of Tai-Ace S 150, iron(ic) chloride, and its blending ratio is 3:2:1:1, consumption is 80mg/L;
Described nano level super-fine powder sorbent material, described nano level super-fine powder sorbent material is prepared from by described ratio of weight and number by following raw material: 20 parts of TMS cage type polysilsesquioxanes, 8 parts of nano level active carbon powders, 58 parts, nano level diatom soil, 23 parts of active clays, and hybrid reaction is made at normal temperatures;
Described flocculation agent adopts ferromegnetism flocculation agent; The preparation of magnetic flocculant adopts " single stage method " technique of magnetite powder solid phase stirring ball-milling acid activation, it is the grey black pressed powder with nucleocapsid structure, particle surface generates the sulfovinic acid iron active ingredient with coagulation and adsorption function, and pollutent and the colloidal substances in water of can flocculating also makes floc particle have magnetic responsiveness.Magnetic flocculant can be built to loading wadding magnetism separation settling pond technique for coagulating sedimentation water treatment procedure, and its principle is the function of efficiently clarifying to realize muddy water as gravitational settling agent to the reaction tank that loads settling pond by the magnetic core part circulating in magnetic flco after magnetic drum separator recovery precipitation.
(1) flco of magnetic flocculant generation is closely knit, settling velocity is fast, by magnetic drum separator high efficiente callback magnetic core circulating, can save the dosage of medicament;
(2) settling pond surface load can reach 12m/h, and deposition efficiency is about 10 times of common settling tank, and floor space is saved more than 4/5;
(3) stable, capacity of resisting impact load is strong, adaptable to the fluctuation of water quality, the water yield.
D) nitrogen-ultrasonic wave-ultraviolet combined sterilizing
To above-mentioned steps c) supernatant liquor that obtains carries out nitrogen-ultrasonic wave-ultraviolet combined sterilizing, use UV-irradiation uv sterilisation on one side, pass into nitrogen on one side, ultra-sonic oscillation, are used agitator fully to stir 30 minutes on one side, carry out pasteurised completely, postprecipitation 1 hour, essence filter, removes the residual impurity in water, obtains processing purifying waste water of reclaiming.
Employing is at < < (water and waste water determination method (the 4th edition) > >, the work such as Wang Xinfang, China Environmental Science Press publishes the method for describing in (2002), has analyzed the water quality of the present embodiment processing water:
1, BOD: dilution inoculation method
2, COD: potassium dichromate process
Many batches of water samples before and after processing are analyzed, and its analytical results is listed in the table below 6:
Table 6
The total phosphorus concentration of former water is 1000mg/L, processes water outlet and has reached 0.015mg/L, has also reached national new emission standard.
Further, to step b), c) in, entering mud deposits the excess sludge in pond and carries out advanced treatment, semiclosed mud is deposited pond, toward mud, deposit and in pond, pass into gas phosphuret-(t)ed hydrogen and stir, phosphuret-(t)ed hydrogen is easy to be adsorbed on mud granule, form matrix-bound phosphine MBP, add again adsorption by soil agent, height absorption storage by phosphuret-(t)ed hydrogen in adsorption by soil agent, be administered in soil, phosphuret-(t)ed hydrogen in adsorption by soil agent will change the reactive phosphate easily being absorbed by farm crop into, be phosphate fertilizer, be used for the soil that phosphorus shortage soil or phosphorus exist with invalid form, described adsorption by soil agent is the mixture of the peat composed of rotten mosses and humic acid, and blending ratio is 1:1.
When adding further adsorption by soil agent, also add soil improvement agent, agent for preserving soil moisture;
Described soil improvement agent is made by the raw material of following weight (part) proportioning: be selected from one or more 30 parts, the mixture in the peat composed of rotten mosses, weathered coal, zeolite, water glass, rhombspar, vermiculite, kaolin, calcium bentonite, diatomite; 20 parts of terra albas, 8 parts of anhydrous calciumsulphates, 5 parts, sulfurous iron ore, 8 parts of oxalic acid, 3 parts, potassium, by abundant levigate the mixing of above-mentioned raw materials, be prepared into soil improvement agent, fineness requirement >=110 order;
Described agent for preserving soil moisture, is made by the raw material of following weight (part) proportioning: 78 parts of acrylic acid or dimethyl propylene diluted acids; 24 parts, sodium hydroxide; 16 parts, potassium hydroxide; 10 parts of Potassium Persulphates; 8 parts of glycocoll; 5 parts, ferrous sulfate; 5 parts of ammonium chloride or ammonium sulfate or hydrogen peroxide; 20 parts of starch; Account for the aerobic particle mud of above total amount of compound 45 weight parts;
The object of sterilization and disinfection is that be greater than 45min and be advisable duration of contact in order to produce the microbiological corrosion to equipment and pipeline in anti-sealing reuse process, and chlorine dosage is 10mg/L, guarantees that pipe network residual chlorine amount is 0.5mg/L.
In technique of the present invention, all equipment of using is all product sold, for example related products of Jiangsu Runtian Water Industry Equipment Co., Ltd. in the market.
Table 7 is step b), c) after the mud that obtains do not pass into PH 3the main component of front mud
Table 7
Table 8 is step b), c) after the mud that obtains pass into PH 3afterwards by the main component of mud after the soil that applies fertilizer after oxygenant oxidation in air and soil
Table 8
Table 9 is step b), c) after the mud that obtains pass into PH 3after, apply fertilizer after adding adsorption by soil agent by oxygenant oxidation in air and soil to the main component of mud after soil simultaneously
Table 9
Table 10 is step b), c) after the mud that obtains pass into PH 3after, apply fertilizer after adding adsorption by soil agent by oxygenant oxidation in air and soil to the index of mixing the soil of main component after moisture preserving agent after soil simultaneously and change
Table 10
Project Content
Organic Be greater than 48
N Be greater than 7.9
P Be greater than 13.8
K Be greater than 10.5
PH 6.8~7.0
Has done on certain farm in outskirts of a town, Guangzhou is that its test in 1 year is as follows:
1, do not add 0.5 mu of common white vegetable plot of any mud
Chinese cabbage output is: 2500 kilograms
2, by step b), c) after the mud that obtains do not pass into mud fertilising before PH3 to 0.5 mu of common white vegetable plot
Chinese cabbage output is: 2900 kilograms, significantly improved quality of vegetable simultaneously, and moisture is large, micro-sweet
3, by step b), c) after the mud that obtains pass into after PH3 by the mud fertilising after oxygenant oxidation in air and soil to 0.5 mu of common white vegetable plot
Chinese cabbage output is: 3400 kilograms, significantly improved quality of vegetable simultaneously, and moisture is large, micro-sweet
4, by step b), c) after the mud that obtains pass into after PH3, the mud fertilising after simultaneously adding adsorption by soil agent by oxygenant oxidation in air and soil is to 0.5 mu of Chinese cabbage ground
Chinese cabbage output is: 3900 kilograms, significantly improved quality of vegetable simultaneously, and moisture is large, micro-sweet
It should be noted, this is invented all numerical value intervals and can realize, and because length is limit, at this, enumerates end points and mid point.
Finally it should be noted that: above embodiment only, in order to technical scheme of the present invention to be described, is not intended to limit; Although the present invention is had been described in detail with reference to previous embodiment, those of ordinary skill in the art is to be understood that: its technical scheme that still can record aforementioned each embodiment is modified, or part technical characterictic is wherein equal to replacement; And these modifications or replacement do not make the essence of appropriate technical solution depart from the spirit and scope of various embodiments of the present invention technical scheme.

Claims (4)

1. a manifold type sewage dephosphorization purifying regeneration treatment process, is characterized in that comprising the following steps:
A) preliminary sedimentation:
The sewage that sewer line is collected enters sand setting water collecting basin after filtering removal solid sundries by coarse rack, by water pump, sand setting water collecting basin sewage is extracted after lifting is filtered silt particle by fine fack and enters adjustment pond, by water circulating pump and the ejector that is connected with water circulating pump, to adjusting bottom, pond, fill the boring aeration pipe water flowing aeration laying and stir water body, by the water outlet of water pump water pipe;
B) anaerobic-aerobic is processed
The water outlet that step a) obtains enters anaerobic pond and stops 1 ~ 2 hour, then enters Aerobic Pond stop 3 ~ 4 hours, then after entering the first settling tank precipitation, supernatant liquor enters coagulation basin, and the sludge part of the first settling tank is back to anaerobic pond, and excess sludge enters mud and deposits pond;
C) in coagulation basin, add coagulating agent, nano level super-fine powder sorbent material, flocculation agent, impel the particle aggregation in water to obtain mixed solution; Then whole mixed solution is introduced to the second settling tank and precipitate, and the separated supernatant liquor that obtains of solid, liquid, the solids of precipitation also enters mud and deposits pond; Described coagulating agent adopts Poly Dimethyl Diallyl Ammonium Chloride, polymerize aluminum chloride, the mixture of Tai-Ace S 150, iron(ic) chloride; Described nano level super-fine powder sorbent material is prepared from by described ratio of weight and number by following raw material: 10 ~ 25 parts of TMS cage type polysilsesquioxanes, 5 ~ 10 parts of nano level active carbon powders, 5 ~ 10 parts, nano level diatom soil, 20 ~ 25 parts of active clays, and hybrid reaction is made at normal temperatures; Described flocculation agent adopts magnetic flocculant; The preparation method of described magnetic flocculant is:
Step 1: ferrous salt and trivalent iron salt are mixed according to mol ratio at 2: 3, and heated and stirred is warming up to 55 ℃, slowly adds sodium hydroxide or ammoniacal liquor, and the mol ratio of adjusting total iron and alkali is 1: 4～1: 3, slaking 0.5～5 hour; Add again acid to regulate mother liquor for acid, add 3%～10% hydrogen peroxide of mother liquor weight or blast air ferrous ion is all oxidized to ferric iron, obtain the gluey flocculation agent that contains magnetic; Iron content flco in the sulfuric acid dissolution waste water that is 92%～97% with mass percent concentration, filters, and obtains ferrous salt and molysite; And utilize air to be partly oxidized to ferric sulfate or iron(ic) chloride;
Step 2: by above-mentioned ferric sulfate or iron(ic) chloride and ferrous grade weight percent 55%～70% and granularity at the magnetite powder of 380 order～500 by weight 30-5: 1 mixes, and obtains many group flocculation agents, can be for step c) as magnetic flocculant;
Step 3: process respectively containing iron waste water with above-mentioned many group flocculation agents, the add-on of determining magnetic flocculant according to turbidity and iron-holder is lower than 20mg/L, stir, adding alkali to regulate pH is 8～10, first rapid stirring is low rate mixing then, then put into the settling tank that Surface field is the permanent magnet of 0.2～1.5T, quiescent setting are housed;
Step 4: after supernatant liquor clarification, water is emitted or utilize vacuum sucking-off; Remove magnetic field device utilization machinery or wind and sweep the flco that recovery precipitates, or shifting magnetic field device does not directly carry out next step;
Step 5: dissolve the iron content flco in waste water with acid, filter, obtain ferrous salt and molysite; Again by step 1)-2) prepare magnetic flocculant;
Step 3) to 5) realize the recirculation utilization of magnetic flocculant;
D) nitrogen-ultrasonic wave-ultraviolet combined sterilizing:
To above-mentioned steps c) supernatant liquor that obtains carries out nitrogen-ultrasonic wave-ultraviolet combined sterilizing, use UV-irradiation uv sterilisation on one side, pass into nitrogen on one side, ultra-sonic oscillation, are used agitator fully to stir 30-60 minute on one side, carry out pasteurised completely, postprecipitation 1-1.2 hour, essence filter, removes the residual impurity in water, obtains processing purifying waste water of reclaiming;
To step b), c) in, entering mud deposits the excess sludge in pond and carries out advanced treatment, semiclosed mud is deposited pond, toward mud, deposit and in pond, pass into gas phosphuret-(t)ed hydrogen and stir, phosphuret-(t)ed hydrogen is adsorbed on mud granule, form matrix-bound phosphine MBP, add again adsorption by soil agent, by phosphuret-(t)ed hydrogen, in the absorption of adsorption by soil agent, store, be administered in soil, phosphuret-(t)ed hydrogen in adsorption by soil agent will change the reactive phosphate being absorbed by farm crop into, wherein the oxygenant in soil can be oxidized to phosphoric acid salt by phosphuret-(t)ed hydrogen, be phosphate fertilizer, be used for the soil that phosphorus shortage soil or phosphorus exist with invalid form, described adsorption by soil agent is the mixture of the peat composed of rotten mosses and humic acid.
2. a kind of manifold type sewage dephosphorization purifying regeneration treatment process according to claim 1, is characterized in that described Poly Dimethyl Diallyl Ammonium Chloride, polymerize aluminum chloride, and the weight ratio ratio of Tai-Ace S 150, iron(ic) chloride is 3:2:1:1; Described dosage of PAC is 20～150mg/L step b) gained supernatant liquor.
3. a kind of manifold type sewage dephosphorization purifying regeneration treatment process according to claim 1, is characterized in that in described adsorption by soil agent, the weight ratio blending ratio of the peat composed of rotten mosses and humic acid is 1:1.
4. a kind of manifold type sewage dephosphorization purifying regeneration treatment process according to claim 2, is characterized in that: described in when adding adsorption by soil agent, also add soil improvement agent and agent for preserving soil moisture;
Described soil improvement agent is made by the raw material of following weight parts: 30 parts, the mixture of one or more in the peat composed of rotten mosses, weathered coal, zeolite, water glass, rhombspar, vermiculite, kaolin, calcium bentonite, diatomite; 10 ~ 20 parts of terra albas, 5 ~ 8 parts of anhydrous calciumsulphates, 1 ~ 5 part, sulfurous iron ore, 5 ~ 8 parts of oxalic acid, 3 parts, potassium, make described soil improvement agent, fineness >=110 order by abundant levigate the mixing of above-mentioned raw materials;
Described agent for preserving soil moisture is made by the raw material of following weight parts: 58 ~ 78 parts of acrylic acid or dimethyl propylene diluted acids; 16 ~ 24 parts, sodium hydroxide; 6 ~ 16 parts, potassium hydroxide; 0 ~ 10 part of Potassium Persulphate; 0 ~ 8 part of glycocoll; 5 parts, ferrous sulfate; 2 ~ 5 parts of ammonium chloride or ammonium sulfate or hydrogen peroxide; 20 parts of starch; Account for the aerobic particle mud of above total amount of compound 0 ~ 45 weight part.
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