CN102775019A - 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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CN102775019A
CN102775019A CN2012102593549A CN201210259354A CN102775019A CN 102775019 A CN102775019 A CN 102775019A CN 2012102593549 A CN2012102593549 A CN 2012102593549A CN 201210259354 A CN201210259354 A CN 201210259354A CN 102775019 A CN102775019 A CN 102775019A
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soil
water
parts
agent
mud
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CN102775019B (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 WWT and recovery field, relate in particular to a kind of manifold type sewage dephosphorization purifying regeneration treatment process.

Background technology

Phosphorus as a kind of on the earth can not natural regenerated limited resources, in the global range ubiquity landing field phosphorus ore produce resource deficient day by day with water surrounding in phosphorus content too high and cause this contradiction of body eutrophication.The 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 the water body is mainly derived from sewage, washing composition and trade effluent, and the phosphorus of how removing effectively in the waste water is the hot issue of countries in the world environmental engineering investigator research always.The investigator has carried out a large amount of research to dephosphorization theory, technology and related process thereof both at home and abroad.But most of with consume ample resources, energy be cost with pollutant removals such as the nitrogen in the sewage, phosphorus, the shortcoming that exists " to consume energy " pollution to marry again.So it is the focus that scientific circles pay close attention to that the sewage dephosphorization technology that breaks traditions, the resource utilization of realization phosphor in sewage become.

In recent years with struvite (MAP:MgNH 4PO 46H 2O) form is recovered as the research focus.The dephosphorization technique that reclaims with the struvite form can be used for treatment of high concentration ammonia nitrogen waste water 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 of some oxynitride types of generation in the waste water.But these research major side overweight the chemical method recycling; The chemical method dephosphorization is not only that medicament costs an arm and a leg, working cost is higher, a large amount of anionic residues are stayed in the water; Cause the salinity of water to increase; Cause secondary pollution, nitrogen, the phosphorus content of water outlet simultaneously all also do not reach emission standard, also need be used as further processing.

And biological phosphate-eliminating coupling phosphor resource process is the technological line of economical rationality, and this technology also becomes possibility gradually.When the total amount migration and variation rule of research sewage work phosphorus, find its total phosphorus first with a toll of 30%-45%, and confirmed that the loss of phosphorus is many with gaseous state phosphuret-(t)ed hydrogen form entering atmosphere.And then all detect phosphuret-(t)ed hydrogen, even in the biosphere in the South Pole, the existence of phosphuret-(t)ed hydrogen is arranged all in places such as wetland, refuse landfill, plants.Existing research shows that the phosphorus in the sewage possibly under the anaerobion effect, be reduced generation phosphuret-(t)ed hydrogen as the precursor of phosphuret-(t)ed hydrogen fully, exists with free state, matrix ADSORPTION STATE phosphuret-(t)ed hydrogen (matrix-bound) form.Early stage the investigation of phosphorus in the anaerobic waste water treating processes is found according to us, wherein total phosphorus loss up 78%.These find to sewage dephosphorization and phosphorus recovery working cycle thinking to be provided, and it shows that not only in the sewage dephosphorization process, phosphorus can be removed with gaseous form, show that also phosphorus can carry out resource utilization with gaseous form and reclaim 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 sewage dephosphorization technology? How does it participate in the removal and the resource utilization circulation of sewage phosphorus? Phosphuret-(t)ed hydrogen produce laggardly go into how water body, atmosphere are collected, resource utilization? Have important scientific meaning and application prospect for the anaerobe removal that discloses sewage phosphorus, resource utilization mechanism, the removal of exploitation sewage phosphorus, round-robin new way.

In the biomass geochemistry circulation of phosphorus, think always that for a long time gaseous state phosphuret-(t)ed hydrogen is non-existent at nature.Up to 1988, the investigator found that first the phosphorus of sewage work's loss is to get into atmospheric with gaseous state phosphuret-(t)ed hydrogen form.Subsequently; In refuse landfill, plant, river and organism, detected the phosphuret-(t)ed hydrogen that exists with the free state form successively; Along with phosphuret-(t)ed hydrogen is detected in varying environment one after another, phosphuret-(t)ed hydrogen finally is confirmed to be a kind of trace gas that extensively is present in the atmosphere.The discovery of phosphuret-(t)ed hydrogen is the important supplement to the phosphorus Cyclical Theory in the physical environment, has changed the phosphorus of thinking in the past in the atmosphere and is by attached to the incorrect view that inorganic phosphate constituted on air participates or the depositing dust particle.Therefore, in the biomass geochemistry circulation of phosphorus, must consider existence and the status and the effect of phosphuret-(t)ed hydrogen.Because phosphuret-(t)ed hydrogen content is very little in the physical environment; Receive condition effect such as sample collecting, preservation, enrichment and detection technique; Early stage analytical procedure and technique means are difficult to realize the quantitatively determined to trace phosphuret-(t)ed hydrogen in the environment, and the research of phosphuret-(t)ed hydrogen behavior is not also extensively carried out in the relevant environment.

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, symptoms such as vomiting, uncomfortable in chest, diarrhoea, can cause pulmonary edema even stupor dead when serious.So the discovery of this compound in environment causes people's common concern at once, setting up sensitive reliable analytical method is the prerequisite of carrying out phosphuret-(t)ed hydrogen research in the environment.

Therefore study phosphorus in sewage dephosphorization anaerobic reactor system and the technology thereof how to change into phosphuret-(t)ed hydrogen, phosphuret-(t)ed hydrogen how about to the waste water water body discharge, how it produces in reactor drum and finally how to stablize problem such as resource utilization; And then in the announcement waste water phosphorus conversion process with remove mechanism; Set up the 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.

Existing research shows that lake, wetland, rice terrace are one of source of gaseous state phosphuret-(t)ed hydrogen in the atmosphere, also is the most important remittance of gaseous state phosphuret-(t)ed hydrogen.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 identical water body does not detect PH after filtering 3The applicant all detects PH in Taihu Lake and filtration of oolong pool and unfiltered water body 3Exist, do not filter lake water than the PH that filters in the lake water 3Content is high 2~14 times, PH in the lake water 3Vertical change very little, also find simultaneously in the concentration ratio lake water of ADSORPTION STATE phosphuret-(t)ed hydrogen in the settling concentration up to 103-105 doubly.These investigators all think PH in the water body 3Mainly the form with matrix combined hydrogen phosphide (MBP) exists.The typical case cultures the matrix combined hydrogen phosphide that detects ng/kg (dry weight) order of magnitude in the settling of marine site to the bright grade of Yu Zhi in 2002 in the Jiaozhou Bay first, and its concentration reaches as high as 685ng/kg.Female clear woods etc. been has also has been investigated and analysed the content and the distribution of Jiaozhou Bay's settling mesostroma combined hydrogen phosphide, and detected result shows that the 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 influence dephosphorization efficiency by using, and directly and its resource utilization process closely related, therefore, necessary mud mesostroma combined hydrogen phosphide is furtherd investigate.

In the sewage phosphorus treating processes, the gaseous state phosphuret-(t)ed hydrogen that generations such as anaerobion discharge at first will reach the adsorption-desorption balance with mud before being discharged into atmosphere, and the excessive gaseous state phosphuret-(t)ed hydrogen that is not adsorbed is just discharged into the atmosphere.Phosphor in sewage can generate phosphuret-(t)ed hydrogen through the reductive action of mikrobe, and the phosphuret-(t)ed hydrogen in the sewage is easy to be adsorbed on the mud granule, forms matrix combined hydrogen phosphide (MBP).Therefore; Carry out the desorption of mud mesostroma combined hydrogen phosphide in a deep going way; For the collection of phosphor in sewage hydrogen, stablize resource utilization research, seek the approach that improves the sewage phosphorus clearance, make up the process for reclaiming of phosphor in sewage under the anaerobic condition; Develop continuable WWT, the resource recovery technology all has important meaning, the present domestic and international rarely seen report of research of this respect.

Phosphorus is one of most important element in the soil.In China, 74% arable soil lacks phosphorus, and the phosphorus in the 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 the soil particle, forms the matrix combined hydrogen phosphide, and Han etc. discover that 0.74% of total phosphorus in the soil is converted into phosphuret-(t)ed hydrogen and is stored in the soil, and the phosphuret-(t)ed hydrogen of generation is very easily by the adsorbed storage of soil particle.In the resource utilization process of sewage dephosphorization coupling phosphorus; If can the phosphorus in the sewage be converted into phosphuret-(t)ed hydrogen; Through the height absorption storage of phosphuret-(t)ed hydrogen in the adsorption by soil agent; And be administered in the soil, the phosphuret-(t)ed hydrogen in the adsorption by soil agent will change the reactive phosphate that is prone to by the crop absorption utilization into, show important especially for phosphorus restriction soil.Sustainable development for promoting agricultural is significant, and the research report of this respect is not arranged at present both at home and abroad as yet.

Along with Chinese society economy and development of urbanization, the quantity that municipal effluent produces is in continuous growth, thereby directly causes rolling up of amount of sludge.That municipal sludge is meant that sewage work produces is solid-state, semi-solid state and liquid waste, contains nutrition, heavy metal and pathogenic bacterium such as a large amount of organism, abundant nitrogen, phosphorus and pathogenic bacteria etc., and usually with foul gas.Do not handle and discharging arbitrarily if do not add, then can cause serious secondary pollution environment.The purpose one that mud is disposed is to reduce sludge volume, reduces the expense of sludge disposal; The 2nd, can make sludge stabilizing through handling, 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 purpose of turning bane into boon, fully utilizing.

Rapid development of national economy, the environment protection fundamental state policy deepen continuously the popular feeling with fulfill, popularizing and in-depth of urban sewage treatment system causes the quantity of municipal sewage plant increasing, 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 handled makes its minimizing, further resource utilization exactly.Therefore, how to dispose the mud of Sewage Plant rationally and effectively, become the major issue that municipal sewage plant and relevant departments face.

Before the final processing of city sewage and sludge, at first should make its minimizing, in this process, must add flocculation agent.The most frequently used flocculation agent is Poly aluminum Chloride (PAC) (abbreviating PAC as), though have certain flocculating property, maximum shortcoming is in the treating processes, and the water cut of mud cake is high, and loose, easy to be broken, and dehydration rate is low, brings difficulty to aftertreatment.

Chinese patent CN1266832A has introduced sludge of sewage treatment plants has been mixed with zeolite; Mud and zeolite blended volume ratio are 1: 1~3; Carry out aerobic fermentation, the high temperature that microbial process produces (general sustainable more than 3 days at the high-temperature time more than 55 ℃) is with decomposing organic matter.This method is utilized the expansion amendment of zeolite as sludge composting, does not participate in the microbiological deterioration reaction.Chinese patent CN1354158A has introduced a kind of municipal sludge that utilizes and has carried out composting, and the sludge composting that obtains becoming thoroughly decomposed adds the method that cultured vinelandii, phosphate solubilizing bacteria, potassium solubilizing bacteria microbial inoculum produce biological organic composite fertilizer again.Chinese patent CN1359876A has introduced a kind of soil and fertilizer that adds unslaked lime and the manufacturing of coal dust ash with municipal sludge; Their preparation method and application; Be to reach low-cost through municipal sludge, unslaked lime, coal dust ash being carried out suitable proportioning, in good time composting, stirring and insulation, effective purpose.Chinese patent CN1502591A has introduced a kind of treatment process of municipal sludge, and it is with adding amendment in the mud, and amendment mainly adopts less relatively wood chip of proportion and garden lop, carries out compost and disposes.

Publication number is the patented claim 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 be blown into atmosphere, but such discharging 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, symptoms such as vomiting, uncomfortable in chest, diarrhoea, can cause pulmonary edema even stupor dead when serious.So the discovery of this compound in environment causes people's common concern at once, setting up sensitive reliable analytical method is the prerequisite of carrying out phosphuret-(t)ed hydrogen research in the 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.

In order to overcome the following problem that present spoil disposal dephosphorization major technique exists: sludge discharge is big, and it is big that excess sludge is disposed difficulty.Effectively transform the technological blank of this respect to present phosphuret-(t)ed hydrogen, proposed the present invention, proposed nitrogen-UW-ultraviolet combined sterilizing technology first simultaneously, also filled up technological gap.

Summary of the invention

The objective of the invention is to overcome the above-mentioned deficiency that prior art exists, a kind of manifold type sewage dephosphorization purifying regeneration treatment process is provided, concrete technical scheme is following.

A kind of manifold type sewage dephosphorization purifying regeneration treatment process may further comprise the steps:

A) preliminary sedimentation

The sewage that sewer line is collected passes through to get into the sand setting water collecting basin after coarse rack filters the removal solid sundries; Through water pump sand setting water collecting basin sewage being extracted lifting passes through to get into the adjustment pond after fine fack filters silt particle; Reach the ejector that is connected with water circulating pump through water circulating pump; Boring aeration pipe water flowing aeration and stirring water body to bottom, adjustment pond dress lays keep water quality relatively stable, through the water outlet of water pump water pipe;

B) anaerobic-aerobic is handled

The water outlet that step a) obtains gets into anaerobic pond and stopped 1 ~ 2 hour, gets into Aerobic Pond again and stops 3 ~ 4 hours, gets into the first settling tank post precipitation supernatant again and enters coagulation basin, and the sludge part of first settling tank is back to anaerobic pond, and excess sludge gets into mud and deposits the pond;

C) in coagulation basin, add coagulating agent, nano level super-fine powder sorbent material, flocculation agent, impel the particle aggregation in the water to get mixed solution; Then whole mixed solution is introduced second settling tank and precipitate, and the isolating supernatant of solid, liquid, the precipitated solid thing also gets into mud and deposits the pond; Said coagulating agent adopts Poly Dimethyl Diallyl Ammonium Chloride, Poly aluminum Chloride (PAC), the mixture of Tai-Ace S 150, iron(ic)chloride; Said nano level super-fine powder sorbent material is prepared from by said ratio of weight and number following raw material: 10 ~ 25 parts of TMS cage type polysilsesquioxanes, 5 ~ 10 parts of nano level active carbon powders, 5 ~ 10 parts in nano level diatom soil, 20 ~ 25 parts of active clays, and hybrid reaction is processed at normal temperatures; Said flocculation agent adopts magnetic flocculant;

D) nitrogen-UW-ultraviolet combined sterilizing

To above-mentioned steps c) supernatant that obtains carries out nitrogen-UW-ultraviolet combined sterilizing, Yi Bian promptly use the UV-irradiation uv sterilisation, Yi Bian feed nitrogen; Ultra-sonic oscillation use whisking appliance fully to stir 30-60 minute on one side, carry out pasteurised completely; Postprecipitation 1-1.2 hour; The residual impurity in the water is removed in smart filter, obtains handling purifying waste water of recovery.

Further, to step b), c) in get into mud and deposit the excess sludge in pond and carry out advanced treatment, semiclosed mud is deposited the pond; Deposit feeding gas phosphuret-(t)ed hydrogen and stirring in the pond toward mud, phosphuret-(t)ed hydrogen is easy to be adsorbed on the mud granule, forms matrix combined hydrogen phosphide MBP; Add the adsorption by soil agent again; Through the height absorption storage of phosphuret-(t)ed hydrogen in the adsorption by soil agent, be administered in the soil, the phosphuret-(t)ed hydrogen in the adsorption by soil agent will change the reactive phosphate that is prone to by the crop absorption utilization into; Be phosphate fertilizer, be used for the soil that scarce phosphorus soil or phosphorus exist with invalid form; Said 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 the adsorption by soil agent further, also add soil improvement agent, agent for preserving soil moisture.

Said soil improvement agent is processed by following weight (part) proportion raw material: be selected from one or more 30 parts in the mixture in the peat composed of rotten mosses, weathered coal, zeolite, water glass, rhombspar, vermiculite, kaolin, calcium bentonite, the zeyssatite; 10 ~ 20 parts of terra albas, 5 ~ 8 parts of anhydrous calciumsulphates, 1 ~ 5 part in sulfurous iron ore, 5 ~ 8 parts of oxalic acid, 3 parts in potassium with the abundant levigate mixing of above-mentioned raw materials, are prepared into soil improvement agent, fineness requirement >=110 orders.

Said agent for preserving soil moisture is processed by following weight (part) proportion raw material: 58 ~ 78 parts of acrylic acid or dimethyl propylene diluted acids; 16 ~ 24 parts in sodium hydroxide; 6 ~ 16 parts in Pottasium Hydroxide; 0 ~ 10 part of Potassium Persulphate; 0 ~ 8 part of glycocoll; 5 parts in 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 said 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; Adding acid again, to regulate mother liquor be acid, and 3%~10% ydrogen peroxide 50 of adding mother liquor weight or blast air ferrous ion all is oxidized to ferric iron obtains containing the gluey flocculation agent of magnetic; Using mass percent concentration is the iron content flco in 92%~97% the sulfuric acid dissolution waste water, filters, and obtains ferrous salt and molysite; And utilize air partly to be oxidized to ferric sulfate or iron(ic)chloride;

Step 2: with above-mentioned ferric sulfate or iron(ic)chloride and ferrous grade weight percent 55%~70% and granularity at the magnetite powder of 380 orders~500 by weight 30-5: 1 mixes, and obtains many group flocculation agents, can both be used for step c) as magnetic flocculant;

Step 3: handle respectively with above-mentioned many group flocculation agents and to contain iron waste water; Confirm that according to turbidity and iron-holder the add-on of magnetic flocculant is lower than 20 (mg/L); Stir, adding alkali adjusting pH is 8~10, stirs then fast earlier and stirs at a slow speed; Put into then the settling tank that Surface field is the permanent magnet of 0.2~1.5T, quiescent setting are housed;

Step 4: after treating the supernatant clarification, the vacuum sucking-off is emitted or utilized to water; Remove magnetic field device utilization machinery or wind and sweep the flco that recovery precipitates, or the shifting magnetic field device does not directly carry out next step;

Step 5: the iron content flco with in the acid dissolving waste water, filter, obtain ferrous salt and molysite; Again set by step 1)-2) preparation magnetic flocculant;

Step 3) to 5) the recirculation utilization of realization magnetic flocculant.

Compared with prior art, the present invention has following beneficial effect:

The present invention overcomes existing routine biochemistry treatment process and membrane biological reactor process is big through the sludge disposal difficulty that the spoil disposal dephosphorization exists, take up an area of big defective; New coagulating agent, sorbent material, the better reclaiming water of flocculation agent have been used simultaneously; Nitrogen-UW-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

Present embodiment carries out advanced treatment to the sewage of a certain chemical plant emission in bad V class Guangzhou and reaches surface water III class level (TN<15mg/L), day output is 10 tons.

This embodiment micro-polluted water treatment step is following:

A kind of manifold type sewage dephosphorization purifying regeneration treatment process may further comprise the steps:

A) preliminary sedimentation

The sewage that sewer line is collected passes through to get into the sand setting water collecting basin after coarse rack filters the removal solid sundries, and is logical

Cross water pump and sand setting water collecting basin sewage extract is promoted get into the adjustment pond after filtering silt particle through fine fack, through the ejector of water circulating pump and connection, the boring aeration pipe water flowing aeration that lays to bottom, pond dress and stir water body keeps water quality relatively stable.

B) anaerobic-aerobic is handled

The water outlet that step a) obtains gets into anaerobic pond and stopped 1 hour, and Aerobic Pond stopped 3 hours, entered coagulation basin through the post precipitation supernatant, and the sludge part of settling tank is back to anaerobic pond, and excess sludge gets into mud and deposits the pond;

C) in coagulation basin, add coagulating agent, nano level super-fine powder sorbent material, flocculation agent, impel the particle aggregation in the water to get mixed solution; Then whole mixed solution is introduced settling tank and precipitate, and the isolating supernatant of solid, liquid, the precipitated solid thing also gets into mud and deposits the pond;

Said coagulating agent adopts Poly Dimethyl Diallyl Ammonium Chloride, Poly aluminum Chloride (PAC), the mixture of Tai-Ace S 150, iron(ic)chloride, and its blending ratio is 3:2:1:1, consumption is 20mg/L;

Said nano level super-fine powder sorbent material; Said nano level super-fine powder sorbent material is prepared from by said ratio of weight and number following raw material: 10 parts of TMS cage type polysilsesquioxanes, 5 parts of nano level active carbon powders, 5 parts in nano level diatom soil, 20 parts of active clays, and hybrid reaction is processed at normal temperatures;

Said flocculation agent adopts the ferromegnetism flocculation agent;

Said 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; It is acid adding acid adjusting mother liquor again, adds 3% ydrogen peroxide 50 or blast air ferrous ion all is oxidized to ferric iron, obtains containing the gluey flocculation agent of magnetic; Using mass percent concentration is the iron content flco in 92% the sulfuric acid dissolution waste water, filters, and obtains ferrous salt and molysite; And utilize air partly to be 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 purpose magnetics: 1 mixes, and obtains many group flocculation agent liquid with molysite and ferrous grade;

Step 3: handle respectively with above-mentioned many group flocculation agents and to contain iron waste water; Confirm that according to turbidity and iron-holder the add-on of magnetic flocculant is lower than 20mg/L; Stir, adding alkali adjusting pH is 8, stirs then fast earlier and stirs at a slow speed; Put into then the settling tank that Surface field is the permanent magnet of 0.2~1.5T, quiescent setting are housed;

Step 4: after treating the supernatant clarification, the vacuum sucking-off is emitted or utilized to water; Remove magnetic field device utilization machinery or wind and sweep the flco that recovery precipitates, or the shifting magnetic field device does not directly carry out next step;

Step 5: the iron content flco with in the acid dissolving waste water, filter, obtain ferrous salt and molysite; 1 prepares magnetic flocculant set by step.

D) nitrogen-UW-ultraviolet combined sterilizing

To above-mentioned steps c) supernatant that obtains carries out nitrogen-UW-ultraviolet combined sterilizing, Yi Bian promptly use the UV-irradiation uv sterilisation, Yi Bian feed nitrogen; Ultra-sonic oscillation use whisking appliance fully to stir 30 minutes on one side, carry out pasteurised completely; Postprecipitation 1 hour; The residual impurity in the water is removed in smart filter, obtains handling purifying waste water of recovery.

Be employed in " (water and waste water check and analysis method (the 4th edition) ", work such as Wang Xinfang, the China Environmental Science Press publishes the method for describing in (2002), has analyzed the water quality of present embodiment treating water:

1, BOD: dilution inoculation method

2, COD: potassium dichromate process

Many batches of water samples before and after handling 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, and treat effluent has reached 0.015mg/L, has also reached national new emission standard.

Further, to step b), c) in get into mud and deposit the excess sludge in pond and carry out advanced treatment, semiclosed mud is deposited the pond; Deposit feeding gas phosphuret-(t)ed hydrogen and stirring in the pond toward mud, phosphuret-(t)ed hydrogen is easy to be adsorbed on the mud granule, forms matrix combined hydrogen phosphide MBP; Add the adsorption by soil agent again; Through the height absorption storage of phosphuret-(t)ed hydrogen in the adsorption by soil agent, be administered in the soil, the phosphuret-(t)ed hydrogen in the adsorption by soil agent will change the reactive phosphate that is prone to by the crop absorption utilization into; Be phosphate fertilizer, be used for the soil that scarce phosphorus soil or phosphorus exist with invalid form; Said 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 the adsorption by soil agent further, also add soil improvement agent, agent for preserving soil moisture;

Said soil improvement agent is processed by following weight (part) proportion raw material: be selected from one or more 30 parts in the mixture in the peat composed of rotten mosses, weathered coal, zeolite, water glass, rhombspar, vermiculite, kaolin, calcium bentonite, the zeyssatite; 10 parts of terra albas, 5 parts of anhydrous calciumsulphates, 1 part in sulfurous iron ore, 5 parts of oxalic acid, 3 parts in potassium with the abundant levigate mixing of above-mentioned raw materials, are prepared into soil improvement agent, fineness requirement >=110 orders;

Said agent for preserving soil moisture is processed by following weight (part) proportion raw material: 58 parts of acrylic acid or dimethyl propylene diluted acids; 16 parts in sodium hydroxide; 6 parts in Pottasium Hydroxide; 2 parts of Potassium Persulphates; 2 parts of glycocoll; 5 parts in 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 purpose of sterilization and disinfection is that be advisable greater than 45min duration of contact for generation is to the microbiological corrosion of equipment and pipeline in the anti-sealing reuse process, and chlorine dosage is 5mg/L, guarantees that the pipe network residual chlorine amount is 0.1mg/L.

All equipment of using all are product sold, the for example related prods of Jiangsu Runtian Water Industry Equipment Co., Ltd. in the market in the technology of the present invention.

Table 2 is step b), c) after the mud that obtains do not feed PH 3The staple of preceding mud

Table 2

Table 3 is step b), c) after the mud that obtains feed PH 3The back is by the staple of mud behind the soil that applies fertilizer after the oxygenant oxidation in air and the soil

Table 3

Table 4 is step b), c) after the mud that obtains feed PH 3After, add apply fertilizer after by oxygenant oxidation in air and the soil staple of to the soil mud of adsorption by soil agent simultaneously

Table 4

Table 5 is step b), c) after the mud that obtains feed PH 3After, add the adsorption by soil agent index of mixing the soil of staple behind the moisture preserving agent to the soil of applying fertilizer after by oxygenant oxidation in air and the soil simultaneously and change

Table 5 Project Content Organic Greater than 48 N Greater than 7.8 P Greater than 13.6 K 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 following:

1, do not add 0.5 mu of common white vegetable plot of any mud

Chinese cabbage output is: 2600 kilograms

2, with step b), c) after the mud that obtains do not feed mud fertilising before the 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 big, and is little sweet

3, with step b), c) after the mud that obtains applied fertilizer to 0.5 mu of common white vegetable plot by the mud after the oxygenant oxidation in air and the soil after feeding PH3

Chinese cabbage output is: 3500 kilograms, significantly improved quality of vegetable simultaneously, and moisture is big, and is little sweet

4, with step b), c) after after the mud that obtains feeds PH3, by oxygenant oxidation in air and the soil with adding mud fertilising to 0.5 mu of Chinese cabbage of adsorption by soil agent after simultaneously

Chinese cabbage output is: 3950 kilograms, significantly improved quality of vegetable simultaneously, and moisture is big, and is little sweet

Embodiment 2

Present embodiment carries out advanced treatment to the sewage of a certain textile mills in bad V class Guangzhou discharging and reaches surface water III class level (TN<15mg/L), day output is 10 tons.

A kind of manifold type sewage dephosphorization purifying regeneration treatment process is characterized in that this method may further comprise the steps:

A) preliminary sedimentation

The sewage that sewer line is collected passes through to get into the sand setting water collecting basin after coarse rack filters the removal solid sundries, and is logical

Cross and get into the adjustment pond after water pump filters a small amount of silt particle with sand setting water collecting basin sewage extraction lifting through fine fack,, adorn boring aeration pipe water flowing aeration and the stirring water body that lays, keep water quality relatively stable to the bottom, pond through the ejector of water circulating pump and connection.

B) anaerobic-aerobic is handled

The water outlet that step a) obtains gets into anaerobic pond and stopped 1.5 hours, and Aerobic Pond stopped 3.5 hours, entered coagulation basin through the post precipitation supernatant, and the sludge part of settling tank is back to anaerobic pond, and excess sludge gets into mud and deposits the pond;

C) in coagulation basin, add coagulating agent, nano level super-fine powder sorbent material, flocculation agent, impel the particle aggregation in the water to get mixed solution; Then whole mixed solution is introduced settling tank and precipitate, and the isolating supernatant of solid, liquid, the precipitated solid thing also gets into mud and deposits the pond;

Said coagulating agent adopts Poly Dimethyl Diallyl Ammonium Chloride, Poly aluminum Chloride (PAC), the mixture of Tai-Ace S 150, iron(ic)chloride, and its blending ratio is 3:2:1:1, consumption is 80mg/L;

Said nano level super-fine powder sorbent material; Said nano level super-fine powder sorbent material is prepared from by said ratio of weight and number following raw material: 20 parts of TMS cage type polysilsesquioxanes, 8 parts of nano level active carbon powders, 58 parts in nano level diatom soil, 23 parts of active clays, and hybrid reaction is processed at normal temperatures;

Said flocculation agent adopts the ferromegnetism flocculation agent; " single stage method " technology with the acid activation of magnetite powder solid phase stirring ball-milling is adopted in the preparation of magnetic flocculant; It is the grey black pressed powder with nucleocapsid structure; Particle surface generates has the sulfovinic acid ironwork property component of coagulation and adsorption function, and pollutent and the colloidal substances do in the water that can flocculate also makes floc particle have magnetic responsiveness.Magnetic flocculant is used for the coagulating sedimentation water treatment procedure can makes up and load flocculation magnetic separating clarifying pool process, its principle be through the magnetic drum separator reclaim magnetic nuclear part circulation in the post precipitation magnetic flco be added to load settling pond reaction tank as the gravitational settling agent to realize the efficient clarifying function of muddy water.

(1) flco of magnetic flocculant generation is closely knit, settling velocity is fast, adds through magnetic drum separator high efficiente callback magnetic nuclear and circulation, can save the dosage of medicament;

(2) the 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, and is strong to water quality, water yield fluctuation adaptive faculty.

D) nitrogen-UW-ultraviolet combined sterilizing

To above-mentioned steps c) supernatant that obtains carries out nitrogen-UW-ultraviolet combined sterilizing, Yi Bian promptly use the UV-irradiation uv sterilisation, Yi Bian feed nitrogen; Ultra-sonic oscillation use whisking appliance fully to stir 30 minutes on one side, carry out pasteurised completely; Postprecipitation 1 hour; The residual impurity in the water is removed in smart filter, obtains handling purifying waste water of recovery.

Be employed in " (water and waste water check and analysis method (the 4th edition) ", work such as Wang Xinfang, the China Environmental Science Press publishes the method for describing in (2002), has analyzed the water quality of present embodiment treating water:

1, BOD: dilution inoculation method

2, COD: potassium dichromate process

Many batches of water samples before and after handling 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, and treat effluent has reached 0.015mg/L, has also reached national new emission standard.

Further, to step b), c) in get into mud and deposit the excess sludge in pond and carry out advanced treatment, semiclosed mud is deposited the pond; Deposit feeding gas phosphuret-(t)ed hydrogen and stirring in the pond toward mud, phosphuret-(t)ed hydrogen is easy to be adsorbed on the mud granule, forms matrix combined hydrogen phosphide MBP; Add the adsorption by soil agent again; Through the height absorption storage of phosphuret-(t)ed hydrogen in the adsorption by soil agent, be administered in the soil, the phosphuret-(t)ed hydrogen in the adsorption by soil agent will change the reactive phosphate that is prone to by the crop absorption utilization into; Be phosphate fertilizer, be used for the soil that scarce phosphorus soil or phosphorus exist with invalid form; Said 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 the adsorption by soil agent further, also add soil improvement agent, agent for preserving soil moisture;

Said soil improvement agent is processed by following weight (part) proportion raw material: be selected from one or more 30 parts in the mixture in the peat composed of rotten mosses, weathered coal, zeolite, water glass, rhombspar, vermiculite, kaolin, calcium bentonite, the zeyssatite; 20 parts of terra albas, 8 parts of anhydrous calciumsulphates, 5 parts in sulfurous iron ore, 8 parts of oxalic acid, 3 parts in potassium with the abundant levigate mixing of above-mentioned raw materials, are prepared into soil improvement agent, fineness requirement >=110 orders;

Said agent for preserving soil moisture is processed by following weight (part) proportion raw material: 78 parts of acrylic acid or dimethyl propylene diluted acids; 24 parts in sodium hydroxide; 16 parts in Pottasium Hydroxide; 10 parts of Potassium Persulphates; 8 parts of glycocoll; 5 parts in 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 purpose of sterilization and disinfection is that be advisable greater than 45min duration of contact for generation is to the microbiological corrosion of equipment and pipeline in the anti-sealing reuse process, and chlorine dosage is 10mg/L, guarantees that the pipe network residual chlorine amount is 0.5mg/L.

All equipment of using all are product sold, the for example related prods of Jiangsu Runtian Water Industry Equipment Co., Ltd. in the market in the technology of the present invention.

Table 7 is step b), c) after the mud that obtains do not feed PH 3The staple of preceding mud

Table 7

Table 8 is step b), c) after the mud that obtains feed PH 3The back is by the staple of mud behind the soil that applies fertilizer after the oxygenant oxidation in air and the soil

Table 8

Table 9 is step b), c) after the mud that obtains feed PH 3After, add apply fertilizer after by oxygenant oxidation in air and the soil staple of to the soil mud of adsorption by soil agent simultaneously

Table 9

Table 10 is step b), c) after the mud that obtains feed PH 3After, add the adsorption by soil agent index of mixing the soil of staple behind the moisture preserving agent to the soil of applying fertilizer after by oxygenant oxidation in air and the soil simultaneously and change

Table 10 Project Content Organic Greater than 48 N Greater than 7.9 P Greater than 13.8 K 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 following:

1, do not add 0.5 mu of common white vegetable plot of any mud

Chinese cabbage output is: 2500 kilograms

2, with step b), c) after the mud that obtains do not feed mud fertilising before the 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 big, and is little sweet

3, with step b), c) after the mud that obtains applied fertilizer to 0.5 mu of common white vegetable plot by the mud after the oxygenant oxidation in air and the soil after feeding PH3

Chinese cabbage output is: 3400 kilograms, significantly improved quality of vegetable simultaneously, and moisture is big, and is little sweet

4, with step b), c) after after the mud that obtains feeds PH3, by oxygenant oxidation in air and the soil with adding mud fertilising to 0.5 mu of Chinese cabbage of adsorption by soil agent after simultaneously

Chinese cabbage output is: 3900 kilograms, significantly improved quality of vegetable simultaneously, and moisture is big, and is little sweet

It should be noted that all numerical value intervals of this invention can be realized, because length is limit, enumerate end points and mid point at this.

What should explain at last is: above embodiment is only in order to explaining technical scheme of the present invention, but not to its restriction; Although with reference to previous embodiment the present invention has been carried out detailed explanation, those of ordinary skill in the art is to be understood that: it still can be made amendment to the technical scheme that aforementioned each embodiment put down in writing, and perhaps part technical characterictic wherein is equal to replacement; And these are revised or replacement, do not make the spirit and the scope of the essence disengaging various embodiments of the present invention technical scheme of relevant art scheme.

Claims (6)

1. manifold type sewage dephosphorization purifying regeneration treatment process is characterized in that may further comprise the steps:
A) preliminary sedimentation:
The sewage that sewer line is collected passes through to get into the sand setting water collecting basin after coarse rack filters the removal solid sundries; Through water pump sand setting water collecting basin sewage being extracted lifting passes through to get into the adjustment pond after fine fack filters silt particle; Reach the ejector that is connected with water circulating pump through water circulating pump; Adorn the boring aeration pipe water flowing aeration that lays and stir water body to bottom, adjustment pond, through the water outlet of water pump water pipe;
B) anaerobic-aerobic is handled
The water outlet that step a) obtains gets into anaerobic pond and stopped 1 ~ 2 hour, gets into Aerobic Pond again and stops 3 ~ 4 hours, gets into the first settling tank post precipitation supernatant again and enters coagulation basin, and the sludge part of first settling tank is back to anaerobic pond, and excess sludge gets into mud and deposits the pond;
C) in coagulation basin, add coagulating agent, nano level super-fine powder sorbent material, flocculation agent, impel the particle aggregation in the water to get mixed solution; Then whole mixed solution is introduced second settling tank and precipitates, and solid, liquid separate supernatant, the precipitated solid thing also gets into mud and deposits the pond; Said coagulating agent adopts Poly Dimethyl Diallyl Ammonium Chloride, Poly aluminum Chloride (PAC), the mixture of Tai-Ace S 150, iron(ic)chloride; Said nano level super-fine powder sorbent material is prepared from by said ratio of weight and number following raw material: 10 ~ 25 parts of TMS cage type polysilsesquioxanes, 5 ~ 10 parts of nano level active carbon powders, 5 ~ 10 parts in nano level diatom soil, 20 ~ 25 parts of active clays, and hybrid reaction is processed at normal temperatures; Said flocculation agent adopts magnetic flocculant;
D) nitrogen-UW-ultraviolet combined sterilizing:
To above-mentioned steps c) supernatant that obtains carries out nitrogen-UW-ultraviolet combined sterilizing, Yi Bian promptly use the UV-irradiation uv sterilisation, Yi Bian feed nitrogen; Ultra-sonic oscillation use whisking appliance fully to stir 30-60 minute on one side, carry out pasteurised completely; Postprecipitation 1-1.2 hour; The residual impurity in the water is removed in smart filter, obtains handling purifying waste water of recovery.
2. a kind of manifold type sewage dephosphorization purifying regeneration treatment process according to claim 2 is characterized in that said Poly Dimethyl Diallyl Ammonium Chloride, Poly aluminum Chloride (PAC), and the weight ratio ratio of Tai-Ace S 150, iron(ic)chloride is 3:2:1:1; Said coagulating agent consumption is 20~150 (mg/L) step b) gained supernatant.
3. according to the described a kind of manifold type sewage dephosphorization purifying regeneration treatment process of claim 1-3, it is characterized in that: step b), c) in get into mud and deposit the excess sludge in pond and carry out advanced treatment, semiclosed mud is deposited the pond; Deposit feeding gas phosphuret-(t)ed hydrogen and stirring in the pond toward mud; Phosphuret-(t)ed hydrogen is adsorbed on the mud granule, forms matrix combined hydrogen phosphide MBP, adds the adsorption by soil agent again; Through the absorption storage of phosphuret-(t)ed hydrogen in the adsorption by soil agent; Be administered in the soil, the phosphuret-(t)ed hydrogen in the adsorption by soil agent will change the reactive phosphate that is utilized by crop absorption into, and wherein the oxygenant in the soil can be oxidized to phosphoric acid salt with phosphuret-(t)ed hydrogen; Be phosphate fertilizer, be used for the soil that scarce phosphorus soil or phosphorus exist with invalid form; Said adsorption by soil agent is the mixture of the peat composed of rotten mosses and humic acid.
4. a kind of manifold type sewage dephosphorization purifying regeneration treatment process according to claim 3 is characterized in that the weight ratio blending ratio of the peat composed of rotten mosses and humic acid is 1:1 in the said adsorption by soil agent.
5. a kind of manifold type sewage dephosphorization purifying regeneration treatment process according to claim 2 is characterized in that: in the time of said adding adsorption by soil agent, also add soil improvement agent and agent for preserving soil moisture;
Said soil improvement agent is processed by the raw material of following weight parts: 30 parts in the mixture of one or more in the peat composed of rotten mosses, weathered coal, zeolite, water glass, rhombspar, vermiculite, kaolin, calcium bentonite, the zeyssatite; 10 ~ 20 parts of terra albas, 5 ~ 8 parts of anhydrous calciumsulphates, 1 ~ 5 part in sulfurous iron ore, 5 ~ 8 parts of oxalic acid, 3 parts in potassium are processed said soil improvement agent with the abundant levigate mixing of above-mentioned raw materials, fineness >=110 orders;
Said agent for preserving soil moisture is processed by the raw material of following weight parts: 58 ~ 78 parts of acrylic acid or dimethyl propylene diluted acids; 16 ~ 24 parts in sodium hydroxide; 6 ~ 16 parts in Pottasium Hydroxide; 0 ~ 10 part of Potassium Persulphate; 0 ~ 8 part of glycocoll; 5 parts in 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.
6. a kind of manifold type sewage dephosphorization purifying regeneration treatment process according to claim 1, it is characterized in that: the preparation method of said 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; Adding acid again, to regulate mother liquor be acid, and 3%~10% ydrogen peroxide 50 of adding mother liquor weight or blast air ferrous ion all is oxidized to ferric iron obtains containing the gluey flocculation agent of magnetic; Using mass percent concentration is the iron content flco in 92%~97% the sulfuric acid dissolution waste water, filters, and obtains ferrous salt and molysite; And utilize air partly to be oxidized to ferric sulfate or iron(ic)chloride;
Step 2: with above-mentioned ferric sulfate or iron(ic)chloride and ferrous grade weight percent 55%~70% and granularity at the magnetite powder of 380 orders~500 by weight 30-5: 1 mixes, and obtains many group flocculation agents, can both be used for step c) as magnetic flocculant;
Step 3: handle respectively with above-mentioned many group flocculation agents and to contain iron waste water; Confirm that according to turbidity and iron-holder the add-on of magnetic flocculant is lower than 20 (mg/L); Stir, adding alkali adjusting pH is 8~10, stirs then fast earlier and stirs at a slow speed; Put into then the settling tank that Surface field is the permanent magnet of 0.2~1.5T, quiescent setting are housed;
Step 4: after treating the supernatant clarification, the vacuum sucking-off is emitted or utilized to water; Remove magnetic field device utilization machinery or wind and sweep the flco that recovery precipitates, or the shifting magnetic field device does not directly carry out next step;
Step 5: the iron content flco with in the acid dissolving waste water, filter, obtain ferrous salt and molysite; Again set by step 1)-2) preparation magnetic flocculant;
Step 3) to 5) the recirculation utilization of realization magnetic flocculant.
CN201210259354.9A 2012-07-25 2012-07-25 Coupling type sewage de-phosphorization purification regeneration treatment technique CN102775019B (en)

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CN103333694B (en) * 2013-06-05 2015-10-28 华南理工大学 A kind of by soil inavailable phosphorus microbiobacterial agent being converted into available phosphorus and its preparation method and application
CN103333694A (en) * 2013-06-05 2013-10-02 华南理工大学 Microbial agent capable of converting unavailable phosphorus into available phosphorus in soil, and preparation method and applications thereof
CN104163497A (en) * 2014-05-05 2014-11-26 浙江省环境保护科学设计研究院 Low-dissolved-oxygen magnetic biochemical treatment system and process
CN104163497B (en) * 2014-05-05 2016-03-02 浙江省环境保护科学设计研究院 A kind of low dissolved oxygen magnetic biochemical treatment system and technique
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CN105174664B (en) * 2015-10-30 2017-08-11 曹炜 A kind of handling process of rural sewage
CN107055730A (en) * 2017-01-18 2017-08-18 四川东江化工有限公司 A kind of high efficiency composition dephosphorization agent and preparation method thereof
CN107055730B (en) * 2017-01-18 2019-06-11 四川东江化工有限公司 A kind of composite dephosphorizing agent and preparation method thereof
CN107032549A (en) * 2017-04-01 2017-08-11 安徽普氏生态环境工程有限公司 A kind of sewerage advanced treatment process
CN107089739A (en) * 2017-06-19 2017-08-25 北京中科康仑环境科技研究院有限公司 The enhanced coagulation technique and its device of a kind of biochemical postindustrial waste water
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