CN103466893B - Sewage recycling comprehensive treatment system - Google Patents

Sewage recycling comprehensive treatment system Download PDF

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CN103466893B
CN103466893B CN201310432078.6A CN201310432078A CN103466893B CN 103466893 B CN103466893 B CN 103466893B CN 201310432078 A CN201310432078 A CN 201310432078A CN 103466893 B CN103466893 B CN 103466893B
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entrance
outlet
regeneration
pipeline
water
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CN201310432078.6A
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CN103466893A (en
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金晨光
李林
施明清
王刚
张敬
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金晨光
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Abstract

The invention discloses a sewage recycling comprehensive treatment system which at least comprises a pre-precipitation filter, a biological renewable ammonium ion exchange device, a medium-low pressure reverse osmosis treatment device with an operation pressure of 1-4MPa, an anaerobic biochemical reaction device, a mixed biochemical reaction device and a post-precipitation filter which are connected in sequence. According to the sewage recycling comprehensive treatment system disclosed by the invention, multiple biochemical technologies are combined by use of an improved membrane system with a high recovery rate, and high-quality softened water is produced while removing pollutants. The problems in treating thick water and ammonia nitrogen are solved, and the pollutants such as organic matters, nitrogen, phosphorus, sulfur, magnesium and the like are recycled.

Description

A kind of sewage recycling total system
Technical field
The present invention relates to waste disposal plant, especially a kind of sewage recycling total system.
Background technology
In sewage, contain with organism, nitrogen, phosphorus, heavy metal, the pollutent that bacterium is representative, conventionally by physics, chemistry, biological three kinds of modes, by these pollutant removals, reduce the impact that it enters water surrounding.
Current conventional conventional reverse osmosis treatent method, can only be applicable at present three grades of above middle water treatments that organic content is lower, can obtain the relatively high rate of recovery, design membrane flux is generally below half of standard flux, when obtaining high-recovery, need mensal cleaning frequency, need to increase consumption and the energy waste of film.A large amount of poor dense water treatments of biochemical are relatively problems of headache of reverse osmosis process, contain non oxidizing bactericide, and organic content are low in the dense water of conventional reverse osmosis unit, and salt concn is high, is difficult to biochemistry, is a processing difficult problem for industry always.
1992, Fan Sheng.Tao etc. are proposing to improve the novel method of the reverse osmosis rate of recovery and ratio of desalinization aspect research oil field re-injection water treatment, and with within 1993, obtained US5,250,185 United States Patent (USP)s, but what the dense water treatment that adopts the method adopted is deep-well injection system, still fail to solve dense water treatment and secondary pollution problem at all.
US6,537,456 United States Patent (USP)s, at US5, improve on 250,185 United States Patent (USP) bases, and it reduces the lifting medicament usage quantity of pH and the fouling risk of device by removing the mode of basicity.
Although the method that above-mentioned two patents provide has had ripe engineering application, for the higher problem of purification water outlet ammonia nitrogen that raises and cause because of pH, do not consider and proposition method of disposal.And for the dense water of system, although by improving the rate of recovery, reduced the water yield of discharge, but the method for processing is limited, deep-well injection has produced the liquid contamination of secondary, and evaporative crystallization has just moved on to solid waste by pollutent from liquid rotating, also fails fundamentally to deal with problems.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of sewage recycling total system, to reduce or to avoid problem noted earlier.
Specifically, for solving the problems of the technologies described above, sewage recycling total system of the present invention at least comprises preliminary precipitation strainer, bio-regeneration type ammonium ion exchange device, working pressure is the low pressure RO treatment unit of 1-4 MPa, anaerobic biochemical reaction device, mix biochemical reaction device and postprecipitation strainer, wherein, municipal administration or industrial sewage pipe network are connected with the entrance of described preliminary precipitation strainer by pipeline, the outlet of described preliminary precipitation strainer is connected with the entrance of described bio-regeneration type ammonium ion exchange device by pipeline, the outlet of described bio-regeneration type ammonium ion exchange device is connected with the entrance of described low pressure RO treatment unit by pipeline, the treated water outlet of described low pressure RO treatment unit is connected with indusqtrial water supply pipe network by pipeline, the thickened waste water out of described low pressure RO treatment unit is connected with the entrance of described anaerobic biochemical reaction device by pipeline, the outlet of described anaerobic biochemical reaction device is connected with the entrance of described mixing biochemical reaction device by pipeline, the outlet of described mixing biochemical reaction device is connected with the entrance of described postprecipitation strainer by pipeline, the outlet of described postprecipitation strainer is connected with municipal drainage pipeline.
Preferably, described sewage recycling total system further comprises salt solution thickener and evaporative crystallizer, the outlet of described postprecipitation strainer is connected with the entrance of described salt solution thickener by pipeline, the condensed water outlet of described salt solution thickener is connected with the entrance of described evaporative crystallizer, and the de-salted water outlet of described salt solution thickener is connected with indusqtrial water supply pipe network respectively with the de-salted water outlet of described evaporative crystallizer.
Preferably, described sewage recycling total system further comprises bio-regeneration device, described bio-regeneration type ammonium ion exchange device further comprises a regenerated liquid entrance and a regeneration waste liquid outlet, the regenerated liquid outlet of described bio-regeneration device is connected by pipeline with the regenerated liquid entrance of described bio-regeneration type ammonium ion exchange device, and the regeneration waste liquid entrance of described bio-regeneration device is connected by pipeline with the regeneration waste liquid outlet of described bio-regeneration type ammonium ion exchange device.
Preferably, described sewage recycling total system further comprises organic mud thickener, organic mud digestive organ and inorganic mud water extracter, described preliminary precipitation strainer, described anaerobic biochemical reaction device, mix biochemical reaction device, the mud discharging mouth of bio-regeneration device is connected with the entrance of described organic mud thickener by pipeline respectively, the concentrated mud outlet of described organic mud thickener is connected with the mud inlet of described organic mud digestive organ, the mud discharging mouth of described organic mud digestive organ is connected with the entrance of described inorganic mud water extracter by pipeline, the wastewater outlet of described organic mud thickener is connected with the entrance of described preliminary precipitation strainer by pipeline, the mud discharging mouth of described postprecipitation strainer is connected with the entrance of described inorganic mud water extracter by pipeline, the wastewater outlet of described inorganic mud water extracter is connected with the entrance of described postprecipitation strainer by pipeline.
Preferably, described sewage recycling total system further comprises gas washing desulfurizer, the regenerated liquid outlet of described bio-regeneration device is connected by pipeline with the absorption liquid entrance of described gas washing desulfurizer, the sulphur-bearing waste solution outlet of described gas washing desulfurizer is connected with the sulphur-bearing waste solution entrance of described bio-regeneration device, and the methane outlet of the methane outlet of described organic mud digestive organ and described anaerobic biochemical reaction device is connected with described gas washing desulfurizer inlet mouth respectively.
Preferably, described sewage recycling total system further comprises pre-softening treater, cation bed softening installation, chemical regeneration type ammonium ion exchange device, chemical regeneration device, crystallizing-dephosphorizing device, described pre-softening treater water inlet is connected with described bio-regeneration type ammonium ion exchange device outlet, described pre-softening treater water outlet is connected with described cation bed softening installation water inlet, the mud discharging mouth of described pre-softening treater is connected with the entrance of described inorganic mud water extracter, described cation bed softening installation water outlet is connected with the entrance of described low pressure RO treatment unit, the regeneration waste liquid outlet of described cation bed softening installation is connected with the entrance of described anaerobic biochemical reaction device and the dosing mouth of described crystallizing-dephosphorizing device respectively, described crystallizing-dephosphorizing device entrance is connected with described salt solution thickener condensed water outlet, described crystallizing-dephosphorizing device water outlet is connected with the water inlet of described evaporative crystallizer, it is agricultural as slow release fertilizer that the mud discharging mouth of described crystallizing-dephosphorizing device is got rid of struvite, described low pressure RO device treated water outlet is connected with described chemical regeneration type ammonium ion exchange device portal by pipeline, described chemical regeneration type ammonium ion exchange device treated water outlet is connected with municipal industrial reuse grid by pipeline.Described chemical regeneration type ammonium ion exchange device regenerated liquid and waste liquid inlet/outlet are connected by pipeline with chemical regeneration device regenerated liquid and waste liquid entry and exit respectively, and the ammoniacal liquor outlet of described chemical regeneration device is connected by pipeline with the entrance of described anaerobic biochemical reaction device.
A kind of sewage recycling total system provided by the present invention by utilizing improved high-recovery film device to combine multiple biochemical process, is produced high quality softening water at removal pollutent simultaneously.Not only solve dense water and ammonia nitrogen and processed problem, and by pollutant resources such as organism, nitrogen phosphate and sulfur, magnesium, 90% above sewage high quality reuse further can be reduced pollutant emission equivalent more than 90%, and make system take up an area relative common process saving more than 90%.
Accompanying drawing explanation
The following drawings is only intended to the present invention to schematically illustrate and explain, not delimit the scope of the invention.Wherein,
What Fig. 1 showed is according to the schematic diagram of the sewage recycling total system of a specific embodiment of the present invention;
Fig. 2 has shown an improved embodiment on the basis of Fig. 1;
Fig. 3 has shown an improved embodiment on the basis of Fig. 2;
Fig. 4 has shown an improved embodiment on the basis of Fig. 3;
Fig. 5 has shown an improved embodiment on the basis of Fig. 4;
Fig. 6 has shown an improved embodiment on the basis of Fig. 5;
Fig. 7 is the relation curve schematic diagram of organism solubleness and pH;
Fig. 8 is the relation curve schematic diagram of silicon ion solubleness and pH;
Fig. 9 is the structural representation of the anaerobic biochemical reaction device in Fig. 1.
Embodiment
For technical characterictic of the present invention, object and effect being had more clearly, understand, now contrast accompanying drawing explanation the specific embodiment of the present invention.Wherein, identical parts adopt identical label, and the arrow in figure is for representing the throughput direction of ducted gas, liquid or solidliquid mixture.
What Fig. 1 showed is according to the structural representation of the sewage recycling total system of a specific embodiment of the present invention, shown in Figure 1, sewage recycling total system 1 of the present invention at least comprises preliminary precipitation strainer 11, bio-regeneration type ammonium ion exchange device 12, working pressure is the low pressure RO treatment unit 13 of 1-4 MPa, anaerobic biochemical reaction device 14, mix biochemical reaction device 15 and postprecipitation strainer 16, wherein, municipal administration or industrial sewage pipe network 2 are connected with the entrance 111 of described preliminary precipitation strainer 11 by pipeline, the outlet 112 of described preliminary precipitation strainer 11 is connected with the entrance 121 of described bio-regeneration type ammonium ion exchange device 12 by pipeline, the outlet 122 of described bio-regeneration type ammonium ion exchange device 12 is connected with the entrance 131 of described low pressure RO treatment unit 13 by pipeline, the treated water outlet 132 of described low pressure RO treatment unit 13 is connected with indusqtrial water supply pipe network 3 by pipeline, the thickened waste water out 133 of described low pressure RO treatment unit 13 is connected with the entrance 141 of described anaerobic biochemical reaction device 14 by pipeline, the outlet 142 of described anaerobic biochemical reaction device 14 is connected with the entrance 151 of described mixing biochemical reaction device 15 by pipeline, the outlet 152 of described mixing biochemical reaction device 15 is connected with the entrance 161 of described postprecipitation strainer 16 by pipeline, the outlet 162 of described postprecipitation strainer 16 is connected with municipal drainage pipeline 4,
Described preliminary precipitation strainer 11 can comprise thickness barrier, settling tank etc., and the sewage being mainly used in discharging in municipal administration or industrial sewage pipe network 2 carries out pre-treatment, for example, and the suspended substance that can remove in waste water by described preliminary precipitation strainer 11.Sewage in municipal administration or industrial sewage pipe network 2 enters after described preliminary precipitation strainer 11 by described entrance 111, can pass through coarse rack, fine fack deslagging and eddy current settling pit sediment outflow, so just can remove the rubbish that may affect follow-up biochemical treatment in waste water, sand grains, scum silica frost and oil pollutant, more remaining organic pollutants small granular suspended matters of adhering to can be by adding polyaluminium sulfate (PAC) and polymeric flocculant (PAM) to carry out coagulation in settling tank, the method of flocculation and precipitation, further remove, and can obtain the effluent index that is less than 20 mg/litre suspended substances, thereby be convenient to further waste water be carried out to subsequent processes.
Described bio-regeneration type ammonium ion exchange device 12 is for utilizing selectivity ammonium ion exchange filler to remove ammonium ion from water, it can comprise zeolite filler ion exchange column or the pond of ammonium ion being selected to exchangeability, zeolite filler can be divided into natural and modification type, in the different water yields, under water quality and hydraulic detention time, its operating capacity is generally in the scope of every gram of commutative 1~7 milligram of ammonium nitrogen of zeolite.
Controlled water outlet ammonium nitrogen concentration of making mouth 122 is to meet the ammonia nitrogen demand of follow-up anaerobic biochemical reaction device 14 and mixing biochemical reaction device 15.
Described bio-regeneration type ammonium ion exchange device 12 mesolite ion-exchangers can adopt the mode of the using and the reserved, this configuration can assurance device non-stop run: when ion exchange column ammonia nitrogen concentration is overproof, will be switched to regeneration mode from operating mode, now standby ion exchange column is switched to operating mode, there is an ion exchange column any period under regeneration mode, and another ion exchange column is under operating mode.
Described bio-regeneration type ammonium ion exchange device 12 adopts bio-regeneration mode, compares chemical regeneration, can significantly reduce the salt consumption of zeolite regeneration, the carbonate scale problems causing because pH is higher while simultaneously avoiding chemical regeneration.
It is the characteristic of negatively charged ion nitrite nitrogen and nitric nitrogen by ammonia oxidation that bio-regeneration generally can utilize ammonia oxidation bacteria (AOBs) and nitrobacteria (NOBs) and oxygen, in zeolite ion-exchanger inside or exterior arrangement aerating apparatus form coenocorrelation, thereby can reuse after making in regeneration waste liquid ammonia nitrogen oxidized, improve the utilising efficiency of regenerated liquid, save salt consumption.There are some researches show, by passing into pressurized air or oxygen to bio-regeneration type ammonium ion exchange device 12 inside, and utilize the biomembranous mode cultivate AOBs and NOBs on zeolite, only need to keep 1, the Na ion concentration of 150 mg/litre, just can meet the needs of regeneration, and nitration reaction speed is the rate-limiting step of regeneration, when interpolation meets the sodium carbonate or sodium bicarbonate basicity that nitration reaction carries out, the sodium ion increasing just can meet the needs of ammonium ion exchange completely.
When bio-regeneration, can on zeolite granular, cultivate microbial film or utilize active sludge with reference to CANON technique, in same exchange column/pond, complete regeneration, make from zeolite, to submit containing the microbial film of AOBs bacterium or active sludge and part the ammonia nitrogen generation biological respinse of changing, be oxidized to after nitric nitrogen, further utilize again anaerobic ammonium oxidizing bacteria (ANAMMOXs) microbial film or active sludge to realize denitrogenation, thereby the accumulation problem that can solve conventional bio-regeneration nitrous acid/nitrate, further reduces waste liquid amount.Give off the waste liquid that contains nitric nitrogen, by pipeline (not shown in FIG.), deliver to mix in biochemical reactor 15 and carry out denitrification denitrogenation reaction.
On the other hand, can utilize described postprecipitation strainer 16 outlet 162 saliferous drainings as regenerated liquid, and cultivate microbial film or the active sludge of enrichment AOBs bacterium, utilize itself and the ammonia nitrogen generation biological respinse under exchange to generate nitrite nitrogen, and give off the waste liquid that contains nitrite nitrogen, by pipeline (not shown in FIG.), deliver to the ammonia nitrogen exporting in 142 drainings with described anaerobic biochemical reaction device 14 in mixing biochemical reactor 15 and carry out ANAMMOX denitrification reaction.
Consider the highly effective reaction temperature of each bacterial classification, whole reaction can be controlled in 25~35 degrees Celsius, can realize efficient processing.According to great majority, research is found, control dissolved oxygen (DO) in 0.5~1.5 mg/litre scope, can realize the dominant growth of AOB, be too lowly too highly all unfavorable for its growth and react, and ANAMMOX bacterium need to react under anaerobic environment, the too high meeting of dissolved oxygen produces and suppresses it.
The content of relevant zeolite ammonium ion exchange refers to " the ammonia zeolite ion-exchange summary " that Hedstrom delivered in the 127th 8 phases of volume of < < environmental engineering periodical > > (Journalof Environmental Engineering) August calendar year 2001
The controlling elements research contents of relevant nitrosation reactor refers to " startup of nitrosation reactor and controlling elements research " article of delivering in the 42nd the 6th phase of volume of the journal > > of < < Harbin Institute of Technology in the June, 2010 such as Zhang Jie.About referring to state once, the research of nitrite bacteria (ammonia oxidation bacteria) " separation of nitrite bacteria and the characteristic research " delivered in 15 1 phases of volume of < < biotechnology > > in February, 2005 such as drives.
Relevant CANON technique refers to Peng Xinhong and equals " new development of CANON technical study " at < < water technology > >, delivered in February, 2008.
Relevant anaerobic ammonia oxidation process technology refers to " Anammox industrial research progress " and the Liao little Bing that Zhu Jing equality delivers in 32 8 phases of volume of < < water technology > > in August, 2006 and equals " progress of Anammox in sewage disposal " at < < microbiology circular > >, delivered in November, 2010.
The working pressure of described low pressure RO treatment unit 13 can be 1-4 MPa, utilizes under the effect higher than solution osmotic pressure, and other materials can not see through the principle of semi-permeable membranes, and these materials and water are separated.The membrane pore size of the reverse osmosis membrane of described low pressure RO treatment unit 13 can be very little, aperture is generally in 0.1~4 nanometer, conventionally the ion that 100 molecular substance and hydrated ionic radius are greater than its aperture can be molecular weight cut-off be greater than, to molecule in most of water and ionic level impurity, all more than 99% clearance can be reached.Therefore can effectively remove dissolved salts in water, colloid, microorganism, organism etc.After the processing of described low pressure RO treatment unit 13, the major part of waste water can be treated to the middle water that can be directly used in the industrial use such as cooling, and enters indusqtrial water supply pipe network 3 by treated water outlet 132.
Reverse osmosis membrane can cause losing efficacy because of organic contamination, biological pollution and inorganic salt fouling.The higher meeting of organic concentration is separated out to be deposited in reverse osmosis membrane assembly and is caused organic contamination, is difficult to wash, and should avoid as far as possible, and in addition, high organic dirty concentration also can cause that microorganism grows rapidly, and fast blocking reverse osmosis membrane causes losing efficacy.
Fig. 7 is the relation curve schematic diagram of organism solubleness and pH; As shown in Figure 7, organism solubleness and pH have positive correlation, raise, in pH6~8 o'clock along with the rising of pH, solubleness by total organic carbon (TOC) metering is increased to rapidly 300 mg/litre from 60 mg/litre, and pH is slowly increased to 350 mg/litre from 8~11 solubleness.What suppose the whole oxidations of chemical oxygen demand (COD) is organism, the ratio of corresponding TOC and COD is 2.67, but in actual sewage, organic carbon generally accounts for 40%~80% of COD to the consumption of oxygen, because there being the reduction class inorganics oxygen consumed such as sulfide, therefore TOC/COD actual ratio is all greater than theoretical value, generally in 3~6 scopes, at pH, is 8~11 scopes, COD is 900 mg/litre~2, and 100 mg/litre scopes organism can not occur and separate out problem.
Current business-like reverse osmosis membrane assembly, comprises rolling, and tubular fibre is board-like, butterfly tubular type etc.What unit price was minimum is rolling assembly, be commonly used, the antifouling property of film, by the optimization to the improvement of material and assembly, has improved in rolled film manufacturer in recent years, but due to constructional congenital defect, process containing the organic sewage of higher concentration and generally need to carry out special pre-treatment.Disc tube reverse osmosis (dt-ro) assembly (DTRO) is due to special design, can tolerate dirt-block modulus (SDI) up to 6.5, chemical oxygen demand (COD) (COD) >62,000 mg/litre, biological oxygen demand (BOD) >40,000 mg/litre, suspended substance (SS) >4,000 mg/litre, ammonia nitrogen (NH3-N) >4, moves under the condition of 000 mg/litre.Disc tube reverse osmosis (dt-ro) is applied in the percolate processing of high pollution without concentration and has obtained successfully at present, because cost is higher at present, has limited mass-producing application.
The hardness that in inorganic salt, divalent metals such as calcium, magnesium, strontium, barium forms can with sulfate radical in water, the negatively charged ion such as carbonate form crystallization on film surface, need to just can recover by pickling, and silicon-dioxide ion can be combined with water materials such as forming metasilicic acid and be separated out very little crystallization and can be attracted in fenestra, cause irreversible pollution.The inorganic pollution that hardness forms can improve solubleness or add Scale inhibitors by reducing pH, avoids precipitated metal thing to separate out, and also can adopt the softening pretreated mode such as chemical precipitation, ion-exchange to remove in advance.Silicon-dioxide ion solubleness raises with pH, therefore can reduce crystallization by promoting the mode of pH, also can add the mode of silicon special Scale inhibitors.
Scale inhibitors unit cost is much higher than the general chemistry medicament of adjusting pH, generally should reduce the use of Scale inhibitors as far as possible, promote the fouling that pH can reduce silicon ion, and can improve the fouling tendency that divalent cation hardness causes simultaneously, because of the extremely difficult cleaning of silicon fouling, can cause the irreversible pollution of reverse osmosis membrane, conventionally using the solubleness of silicon ion concentration and corresponding pH as the primary restricted condition of controlling the reverse osmosis membrane rate of recovery.
Fig. 8 is the relation curve schematic diagram of silicon ion solubleness and pH, and as shown in Figure 8, silicon ion concentration is in pH6~8 scope, and solubleness remains on 100 mg/litre top/bottom latitudes; And pH is in 8~10 scopes, solubleness is increased to 300 mg/litre gradually from 100 mg/litre; At pH, be greater than 10 beginnings and rise rapidly, to pH, reach at 11 o'clock, solubleness reaches 1,500 mg/litre.
In this example, the present invention is controlled at 6~8 scopes by pH fluctuation, by dosing and select the mode of corresponding membrane module to realize the high-recovery of reverse osmosis, thereby realizes the concentrated sewage of high magnification.
When adopting rolled membrane module, because it easily holds back throw out, the characteristic of breed bacteria, main restricted condition is the organic concentration into water, therefore need be by adding soda acid adjustment water inlet pH to the upper limit 8, thereby make the organism solubleness degree that dense water side represents with COD bring up to 900~1, 800 mg/litre, and the auxiliary Scale inhibitors that adds prevents inorganics fouling, can before described bio-regeneration type ammonium ion exchange device 12, add hypochlorous acid, ozone, or irradiate and carry out germicidal treatment by UV-lamp, oxidized for preventing reverse osmosis membrane, in water inlet, add sodium bisulfite reductive agent, can be by oxidizing substance reduction such as remaining hypochlorous acid, eliminate the impact on follow-up anaerobic biochemical reaction microorganism simultaneously.Eliminated organic contamination, the water inlet of inorganic pollution and biological pollution, has guaranteed coiled reverse osmosis membrane steady operation.Reaction formula is as follows:
NaHSO 3+HClO==NaHSO 4+HCl
NaHSO 3+O 3==NaHSO 4+Cl -+O 2
When adopting disc tube reverse osmosis (dt-ro) assembly, because its tolerance COD is up to 62,000 mg/litre, now silicon ion and hardness become the factor of the major limitation rate of recovery, wherein hardness can be turned down pH value by acid adding and makes unsaturated carbonate salt index (claim again bright lattice rel saturation index, abbreviation LSI) be less than zero, prevent fouling, it is that Scale inhibitors prevents the pollution to reverse osmosis membrane that silicon needs to add special silicon.
By dosing and pre-treatment, can greatly reduce the stifled tendency of dirt of reverse osmosis membrane, but the growth along with working time, reverse osmosis membrane still can pollute slowly, show the pressure reduction of reverse osmosis Inlet and outlet water, see through on the pollutant load and producing water ratio of water, in above-mentioned three kinds of factor generation considerable changes, all need to start to clean, the general fouling that adopts hydrochloric acid or sulfuric acid to form for cleaning inorganic salt, adopt sodium hydroxide clean deposition pollutent with, microorganism, bacterium etc., also need if desired to add special-purpose non oxidizing bactericide to carry out germicidal treatment, for the organic pollutant that is difficult to wash off by chemical process, Cao accounts for flat interest and obtains successfully with biological mode removal.
Described low pressure RO treatment unit 13 can be concentrated into 40 by salinity under maximum working pressure 4.1 MPas, more than 000 mg/litre, but because the tolerance of salinity being had to certain limitation in described anaerobic biochemical reaction device 14, generally should control the concentrated salinity of described low pressure RO treatment unit 13 and in 30,000 mg/litre, ensure below the working efficiency of microorganism.When adopting common coiled reverse osmosis membrane, should control pH as far as possible and approach 8 operations, now organic carbon solubleness is about 300 mg/litre, if surpass this concentration, can there is Precipitation, cause the pollution of normal film, by COD/TOC, than 3~6, calculate, COD concentration limit should be 900~1,800 mg/litre.If adopt disc tube reverse osmosis (dt-ro) membrane module, COD concentration limit can be up to 62,000 mg/litre.Certain density sulfate radical can promote anaerobic reaction, but excessive concentration can cause excess hydrogen sulfide to microorganisms toxic action, generally needs to control sulfate concentration lower than 3,000 mg/litre.
For example, the general total salt of sanitary sewage is in 500 mg/litre left and right, and COD is in 300 mg/litre, sulfate radical 100 mg/litre, controlling reverse osmosis treatment device 13 of the present invention moves with 90% the rate of recovery, total salt 5,000 mg/litre of dense water side 142 draining, COD is 3,000 mg/litre, sulfate radical is 1,000 mg/litre, meets the water inlet requirement of follow-up described anaerobic biochemical reaction device 14.
In the present invention, reverse osmosis membrane used can adopt existing commercially available product, and its structure and principle are known, no longer describes in detail.The technology contents relevant to reverse osmosis membrane can be with reference to US5,250,185A or US6, the description in 537,456B2.About the cleaning of reverse osmosis membrane organic contamination, refer to Cao and account for " reverse osmosis membrane Organic pollutants and microorganism are cleaned research " that equality was delivered in the 24th the 2nd phase of volume of < < water technology > > in February, 2008.
In order effectively to remove the biochemical oxygen demand (BOD) of the concentrated waste water after described low pressure RO treatment unit 13 is processed, take into account removal ammonia nitrogen simultaneously, other pollutents such as phosphorus, can further utilize microbiological deterioration organic pollutant by described anaerobic biochemical reaction device 14 and described mixing biochemical reaction device 15, can make organic pollutant by saprophytic bacteria metabolism, be converted into organic acid, then can be methane and carbon dioxide by the methanogen organic acid of degrading, to remove the biochemical oxygen demand (BOD) in the concentrated waste water after described low pressure RO treatment unit 13 is processed, also can take into account removal ammonia nitrogen simultaneously, other pollutents such as phosphorus.
Described anaerobic biochemical reaction device 14 can be converted into chemical oxygen demand (COD) renewable energy resources methane gas, and described mixing biochemical reaction device 15 can further be removed the pollutents such as chemical oxygen demand (COD), ammonia nitrogen.
Described anaerobic biochemical reaction device 14 can be used the anaerobe of cultivating through salt tolerant, when Anammox temperature of reaction is at 30 degrees Celsius, can reach highest response efficiency, the COD of 1 kilogram can be converted into the methane gas of 0.35-0.4m3, the waste water after described anaerobic biochemical reaction device 14 is processed is delivered to described mixing biochemical reaction device 15 by pipeline.
Compare with aerobic reactor, the volumetric loading of anaerobic biochemical reaction device 14 is that they are more than ten times, corresponding required reactor volume has reduced 90%, biological sludge mean concns be its ten times to decades of times, sludge output is its 1/6~1/10, greatly reduced sludge disposal cost, and the biogas that anaerobic reaction produces is also good biomass energy.
The entrance 141 that the condensed water of the thickened waste water out 133 of described low pressure RO treatment unit 13 is delivered to described anaerobic biochemical reaction device 14 carries out efficient anaerobic biochemical treatment.By concentrating of 13 pairs of sewage of described low pressure RO treatment unit, make organic concentration be increased to the water inlet requirement of described anaerobic biochemical reaction device 14, collaborative work by anaerobion changes organic pollutant into biogas, to organic removal efficiency, can reach more than 90%.In anaerobic biochemical reaction, a small amount of nitrogen phosphorus can participate in the synthetic of cell and consume with mud discharging, but the nitrogen and phosphorus pollutants in organism is released simultaneously, generally shows as anaerobic treatment and water outlet concentration of nitrogen and phosphorus is raise or approach water inlet.Therefore the water outlet of described anaerobic biochemical reaction device 14 need be done to further processing from exporting 142 entrances 151 of delivering to mixing biochemical reaction device 15.
Condensed water from described low pressure RO treatment unit 13 outlets 133, when sulfate concentration is lower, can be formed by homogeneous reaction device, in the situation that water inlet sulphate content is lower, because acid-producing bacteria Competition reduces, pH fluctuation is little, in the single-phase middle also desirable good effect of acidifying and methanation reaction that is hydrolyzed simultaneously.And when sulfate concentration is higher, because the methane-producing bacteria generation cycle is 4~6 days, and the acid-producing bacteria generation cycle is as short as 10~30 minutes, especially when sulfate concentration is higher, reactor acidifying meeting causes pH to drop to below 6.5, and methane-producing bacteria is to ten minutes sensitivities of pH, suitable growth is in the scope of pH6.8~7.2, thereby adopt diphasic anaerobic that acid-producing bacteria is separated with methanogen, can avoid the competition of acid-producing bacteria and methanobacteria, and can guarantee that methanobacteria grows under stable pH.
Fig. 9 is the structural representation of the anaerobic biochemical reaction device in Fig. 1, shown in Figure 9, after concentrated by described low pressure RO treatment unit 13 in the present invention, sulfate concentration is generally higher, therefore in described anaerobic biochemical reaction device 14, can comprise acidication reaction member 14A, the middle desulfurization TPAD mode of hydrogen sulfide removal unit 14B and methanator 14C, the vitriol generation sulfide that reacts under the effect of sulphate reducing bacteria (SRB), wherein concentration of hydrogen sulfide increases and can produce inhibition to SRB and methanogen (MPB), and can there is catabolic reaction in part SRB in the not enough situation of organism, with MPB competition substrate acetic acid.Lower at carbon sulphur (COD/SO4) mass ratio, such as approaching in 0.67 situation, thereby the reduction that carbon source can be vitriol for carbonic acid gas by complete oxidation provides electronics.And in the situation that carbon sulphur mass ratio is greater than 1.5, mainly there is assimilation (incomplete oxidation) effect of carbon source, now SRB is mainly the acetic acid that MPB utilizes by organic matter degradation, shows as the raising of factor of created gase.The research of Liu Yan shows, although factor of created gase raising, the decline of methane in sewage gas ratio, as long as being the reaction that part has SRB to participate in, reason only produces acetic acid, hydrogen producing, does not make methanobacteria lack the required hydrogen of synthesizing methane and causes carbonic acid gas ratio to increase, and methane ratio reduces.The researchs such as Ruan Jun show, when sulfate concentration is 3,000 mg/litre is when following, along with concentration increase meeting has certain promotion to anaerobic grain sludge, specific methanogenic activity (SMA) increases and slowly increases with concentration, mainly there is anabolic reaction in SRB microorganism now, in the time of by sulfate reduction, produces and can be the organic substrate acetic acid that methanogen (MPB) utilizes.When surpassing 3,000 mg/litre, because excessive hydrogen sulfide can produce restraining effect, sulphate reducing bacteria generation catabolic reaction can utilize matrix with methanobacteria contention simultaneously.For guaranteeing the operational efficiency of described anaerobic biochemical reaction device 14, should control that the sulfate concentration that enters described anaerobic biochemical reaction device 14 is lower than 3,000 mg/litre.To the sulfur hydrogen producing in described anaerobic biochemical reaction device 14, can suppress biological respinse, therefore should reduce the content of hydrogen sulfide as far as possible, the present invention is by setting up independently hydrogen sulfide treatment unit 14B to process, in 14B, can pass through physico-chemical process, comprise and promote the ionization that pH increases hydrogen sulfide, or reduction pH increases free hydrogen sulfide, carry out stripping, or cross interpolation molysite, form iron sulphide precipitation and remove; Also can adopt biological method, utilize photosynthetic sulfur bacteria, colorless sulfur bacteria, thiobacillus denitrificans and oxygen are oxidized to by sulfide the sustainable biologic treating technique that elemental sulfur reclaims.Li Lings etc. by increasing Gas-lift reactor mode between two-phase UASB reactor, the in the situation that of reflux ratio 15:1, the 1000 mg/litre sulfate concentrations of intaking, can process sulfate radical volumetric loading and reach 10.5 kilograms of/cubic metre of skies, keep sulfate reduction rate more than 80%, in the situation that Gas-lift reactor water inlet pH is 6.5, can guarantee that hydrogen sulfide stripping rate is more than 90%, when COD load reaches 15 kilograms of/cubic metre of skies, clearance reaches more than 85%.
The sludge types of described anaerobic biochemical reaction device 14 adopts granule sludge, because the granule sludge after domestication adapts to the salinity up to 20 grams per liters than floc sludge, at 10 grams per liters, with interior mud specific methanogenic activity (SMA), also can improve along with the rising of salinity, just there will be slight inhibition being greater than 20 grams per liters, expanded granular sludge bed (EGSB) is as third generation anaerobic biological technique, because of its high volumetric loading, can low temperature, lower concentration operation, from decades in last century, for end, start to become anaerobic biological area research focus, adopt expanded granular sludge (EGSB) technique, may operate at the low temperature environment temperature of tens degrees Celsius, under the environment of the lower concentration of hundreds of milligrams per liter COD, anaerobic biochemical reaction device 14 biological respinse unit (A, C) first-selected expanded granular sludge bed (EGSB) technique for the treatment of the described low pressure RO treatment unit 13 low suspended substance of discharging, lower COD concentration (<3, 000mg/ liter), the concentrated waste water of low temperature (envrionment temperature), studies have found that EGSB technique can be more than 14 degrees Celsius, water inlet volumetric loading is more than 10 kilograms of COD/ cubic meter skies, obtain more than 85% COD clearance.Under extreme environment water temperature (<10 degree Celsius), can, to carrying out heat treatment, guarantee processing efficiency, also can be the in the situation that of periphery used heat abundance, water temperature is further promoted, can improve reaction efficiency like this, obtain higher clearance.The granule sludge of EGSB needs a certain amount of trace element; wherein magnesium ion is important element; can promote the formation of granule sludge and the growth of methanobacteria; if but excessive concentration; metabolism that can block cell; the magnesium ion that contains 5 mg/litre in waste water is found in research, and the calcium ion of 12 mg/litre can accelerate sludge granulating, improves operating performance.Raw waste water hardness can meet the demands after high power is concentrated in the present invention.
Anaerobic reaction methanobacteria appropriate pH is 6.5~7.5(the best 6.8~7.2), the voltaile fatty acid producing at souring stage (VFA) can cause the acidifying of reactor when can not effectively be synthesized methane by methanobacteria, affects the activity of methanobacteria.Basicity is the important parameter in anaerobic biochemical reaction device 14, basicity can be effectively in and VFA increase the hydrogen ion bringing, buffer pH, prevents the acidifying of reactor.
Lime, caustic soda, soda ash, sodium bicarbonate etc. all can be used as and improve basicity medicament, and wherein sodium bicarbonate (sodium bicarbonate) is not because having side effects as first-selected medicament.The researchs such as Dong Chunjuan point out, when usining sodium bicarbonate, be added to the cost that 67 mg/litre are produced can offset the income of bringing that 1,000 mg/litre COD is converted into methane as basicity.So demand of the additional basicity of should taking measures as far as possible to reduce.Because methanation is a reaction that produces basicity, so can reduce alkalinity demand by increasing the mode of internal reflux, simultaneously, cultivate acidproof methanobacteria and also prove feasible, Ling Xuefeng etc. are 2 at influent COD, 000 mg/litre, basicity 250 mg/litre, pH are 6.2, move EGSB reactor under the parameter in 7 kilograms of/cubic metre of skies of volumetric loading, have obtained 96% COD clearance, go out alkalinity of water and are stabilized in 500~600 mg/litre.Research is also found, compares high alkalinity condition, under low basicity condition, can obtain higher clearance and methane production.Therefore by adopting EGSB technique, suitably reflux and aciduric bacteria cultivation, the alkalinity demand of anaerobic biochemical reaction device 14 can be reduced to below 300 mg/litre.In described low pressure RO treatment unit 13 influent alkalinity, as long as meet higher than 30 mg/litre, will survey the basicity producing higher than 300 mg/litre at dense water.
The technology relevant to described anaerobic biochemical reaction device 14 can be referring to following documents and materials:
Relevant TPAD technique relevant technologies content refers to all wide raw " progress of TPAD technique and application thereof " that waits deliver in the first phase at < < energy environment protection > > the 20th volume for 2006, relevant EGSB EGSB (expanded granular sludge bed) and at low temperature, the technology contents of high salt operation, refer to Du Zhanpeng and equal " biological nature of EGSB reactor and the progress " within 2006, at < < industrial safety and environmental protection > >, delivered, " research of High-strength Organic Wastewater Treatment by EGSB at Ambient Temperature " that Zhong Haitao etc. 2006 delivered in < < China's water supply and drainage > the 22nd 19 phases of volume of > and Zou little Ling etc. 2009 are at < < China biogas > > 27(3) in description in " NaCL and KCL salinity are on the domestication of anaerobic sludge and the impact on specific methanogenic activity " delivered, the concrete technology contents of controlling relevant for sulfate concentration refers to Ruan Jun etc. at < < China biogas > > 2008, has delivered " SO in 26(1) 4 2-impact on Activity of Anaerobic Granular Sludges " and Liu Yan " impact of sulfate radical on organic waste water anaerobic biological treatment " delivered in < < environmental science > > the 5th phase of 13 volumes in 1992 in description, treatment technology content about hydrogen sulfide, refer to being coated with precious China in December, 2003 and waiting that volume 4 is interim delivers the content that " control of hydrogen sulfide in to anaerobic digestion " is described at < < pollution prevention technique > > 16, and Li Ling equals in February, 2011 at interim " the two-phase UASB reactor processing high concentration sulfate wastewater " article delivered of < < Environmental science and technology > > the 24th volume the 2nd.About the partial content of methane bio-desulfurization, refer to Wang Gang and equal " the methane bio-desulfurization technical study " within 2008, in < < application energy technology > the 5th phase of >, delivered, relevant alkalinity demand is relevant, please refer to " reducing the effective way that anaerobic waste water is processed required basicity " that Dong Chunjuan equals at < < Techniques and Equipment for Environmental Pollution Control > > the 4th volume, on the 4th phase, to deliver in April, 2003, and Ling Xuefeng equals the articles such as " producing the operation of methane EGSB reactor under pH6.0 acidic conditions " of delivering in the 25th the 1st phase of volume of < < environmental science > > in January, 2004.
Water outlet from the outlet 142 of described anaerobic biochemical reaction device 14 belongs to low carbon-nitrogen ratio sewage, enters described mixing biochemical reaction device 15 carry out denitrogenation dephosphorizing processing by entrance 151.
Aerobic by creating in described mixing biochemical reaction device 15, anaerobism alternate environment, can remove remaining ammonia nitrogen, organism and phosphorus, and under good oxygen condition, ammonia nitrogen is oxidized to nitrous state, nitric nitrogen; Under anaerobic state, nitrite nitrogen and residual organic substances can issue in the effect of denitrifying bacterium solution generation nitrogen estranged and carbonic acid gas is removed, and nitrite nitrogen also reacts with ammonia nitrogen generation autotrophic denitrification (Anammox) simultaneously simultaneously to be removed; Under the effect of denitrogenation thiobacterium, nitric nitrogen also can be with sulfide generation simultaneous denitrification except reaction of Salmon-Saxl.By sludge reflux, make dephosphorization bacterial in mud be in aerobic-anaerobic environment alternately aerobic suction phosphorus and anaerobic phosphorus release metabolism occur, by aerobic section spoil disposal, can realize biological phosphate-eliminating.
Low ratio of carbon to ammonium wastewater treatment is mainly to control nitration denitrification reaction to carry out in short distance, Zhu Guibing etc. have studied the impacts of factor on reaction such as temperature, mud age, operational conditions, dissolved oxygen, pH, substrate concn, inhibitor, find that controlling dissolved oxygen (DO) is successfully to realize the effective ways of short-cut nitrification and denitrification lower than 1.5 mg/litre.
Described mixing biochemical reaction device 15 can adopt biomembrance process, activated sludge process, or by the method for the two combination, current biomembrance process is more representational is biological filter (BAF) technique, and biomembrance process be combined representational with active sludge be moving-bed membrane bioreactor (MBBR) technique, realizing the activated sludge process of short-cut nitrification and denitrification more representational is the Bio-Dopp technique of German Engelbart exploitation in 1988, it reduces concentration gradient by high reflux ratio, the aerating apparatus of particular design has successfully been realized short-cut nitrification and denitrification, biological phosphate-eliminating and precipitation, realized through engineering approaches operation for many years.
The relevant technology of described mixing biochemical reaction device 15 can be referring to following documents and materials:
" short-cut nitrification and denitrification bio-denitrification technology " article that relevant short-cut nitrification and denitrification technique content is shown in the journal > > of < < Harbin Institute of Technology the 10th phase the 40th curly hair in October, 2008 with reference to people such as Zhu Guibing.About the content of Bio-dopp technique with reference to people such as Zhuan Zhongchang in October, 2008 " biological multiplication (Bio-dopp) Process for Treating Municipal " article at < < environmental science and management > > the 10th phase the 33rd curly hair table.The particular content of relative synchronous denitrification and desulfurization refers to He Li and equals " progress of simultaneous desulfurization and denitrification technology " delivered in the 29th the 1st phase of volume of < < renewable energy source > > on January 24th, 2011, Cai Jing and Zheng Ping " new bio denitrification and desulfurization process progress " that in November, 2011, < < science and technology circular > > 27 volumes 6 are delivered, the articles such as " isolation identification of thiobacillus denitrificans and Denitrification Characteristics researchs " that the people such as Che Xuan deliver at < < environmental science > > 29 volumes 10 in October, 2008.
The sewage of processing through described mixing biochemical reaction device 15 flows into described postprecipitation strainer 16 from exporting 152 through entrance 161, carry out therein chemical precipitation, more than adding lime lifting pH to 10, can realize synchronous hard-off dephosphorization, can filter to reduce suspended substance in water to water outlet.Through sedimentation and filtration, by exporting 162, can be connected qualified discharge with described municipal drainage pipeline 4 except the water outlet of hard, dephosphorization and suspended substance.
Realizing the through engineering approaches of synchronous hard-off dephosphorization more representational is the ACTISOFT device of French Veolia waterworks and exploitation in 2008, and it utilizes calcium carbonate crystal sand that precipitation generates to reflux and accelerates precipitation, thereby greatly reduces the consumption to flocculation agent.
The chemical reaction that hard-off dephosphorization occurs is as follows:
5Ca 2++4OH -+3HPO 4 2-==Ca 5(OH)(PO 4) 3↓+3H 2O
Ca 2++HCO 3 -+OH-==CaCO 3↓+H 2O
About chemical dephosphorization content, can equal in May, 2003 at " present situation of boiling water chemical dephosphorization and progress " article of < < Treatment of Industrial Water > > the 5th phases 23 curly hair table with reference to Xu Fengguo.
Fig. 2 has shown an improved embodiment on the basis of Fig. 1, as shown in Figure 2, on basis embodiment illustrated in fig. 1, in sewage recycling total system 1 shown in Fig. 2, described sewage recycling total system 1 further comprises salt solution thickener 17 and evaporative crystallizer 18, the outlet 162 of described postprecipitation strainer 16 is connected with the entrance 171 of described salt solution thickener 17 by pipeline, the condensed water outlet 172 of described salt solution thickener 17 is connected with the entrance 181 of described evaporative crystallizer 18, the de-salted water outlet 173 of described salt solution thickener 17 is connected with indusqtrial water supply pipe network 3 respectively with de-salted water 182 outlets of described evaporative crystallizer 18.
When the recycling rate of the further lifting sewage of needs, the sewage that described postprecipitation strainer 16 is discharged can be to municipal drainage pipeline 4 discharges, but be delivered to described salt solution thickener 17, carry out concentration, described salt solution thickener 17 can be selected high pressure reverse osmosis membrane, also can select vaporizer to concentrate it, more than salt solution can being concentrated into 80,000 mg/litre like this, so that follow-up, carry out evaporative crystallization processing.De-salted water after processing can be delivered to indusqtrial water supply pipe network 3, condensed water is further delivered to described evaporative crystallizer 18, in the interior described condensed water of described evaporative crystallizer 18, can be forced to the flow velocity of 1-3 meter per second circulation, in working cycle, described condensed water is evaporated crystallization, thereby the inorganic salt slurry solid that obtains can be used as industrial chemicals and fully utilized, the de-salted water gathering after evaporation can be delivered to indusqtrial water supply pipe network 3.
Fig. 3 has shown an improved embodiment on the basis of Fig. 2, as shown in Figure 3, on basis embodiment illustrated in fig. 2, described sewage recycling total system 1 shown in Fig. 3 further comprises bio-regeneration device 19, described bio-regeneration type ammonium ion exchange device 12 further comprises a regenerated liquid entrance 123 and a regeneration waste liquid outlet 124, the regenerated liquid outlet 191 of described bio-regeneration device 19 is connected by pipeline with the regenerated liquid entrance 123 of described bio-regeneration type ammonium ion exchange device 12, the regeneration waste liquid entrance 192 of described bio-regeneration device 19 is connected by pipeline with the regeneration waste liquid outlet 124 of described bio-regeneration type ammonium ion exchange device 12.
By described bio-regeneration device 19 is set, biological denitrificaion and ammonium ion exchange are separated, the water outlet by biological denitrificaion is looped back in described bio-regeneration type ammonium ion exchange device 12 again regenerates.
Described bio-regeneration device 19 can be by utilizing nitrite bacteria, anaerobic ammonium oxidizing bacteria, and the feature of thiobacillus denitrificans, realizes simultaneous denitrification sulphur removal, at utmost reduces the discharge of waste liquid.
Described bio-regeneration device 19 can comprise a nitrosation reactor, an anaerobic ammonium oxidation vessel and a sulphur removal Analysis, in bio-regeneration process, after sodium ion in regenerated liquid and the ammonium ion on zeolite exchange, the ammonium ion regenerated liquid that contains eluting enters in described bio-regeneration device 19, will be completely converted as nitrogen and removes, and regenerated liquid can be recycled simultaneously.
First the regeneration waste liquid that contains ammonia nitrogen in high density enters nitrosation reactor from regeneration waste liquid entrance 192 and carries out nitrosation reaction, main cultivation ammonia oxidizing bacteria (AOB) in nitrosation reactor, by mineralized nitrogen, it is nitrite nitrogen, control mineralized nitrogen rate 50%~60%, to meet the condition that enters subsequent reactor.In the present invention, can keep that in described nitrosation reactor, dissolved oxygen concentration is in 0.2~1.5 mg/litre, pH remains on 8 left and right, so just can guarantee nitrosation reaction.In described nitrosation reactor, the main nitrosation reaction formula occurring is as follows:
2NH 4 ++3O 2→2NO 2 -+2H 2O+4H +
Ammonia nitrogen and nitrite nitrogen mixed solution through nitrosation reaction, control ratio is in 1:1~1.5 scope, enter anaerobic ammonium oxidation vessel and under the effect of anaerobic ammonium oxidizing bacteria (ANAMMOX), carry out autotrophic denitrification reaction, the present invention maintains the pH value of anaerobic ammonia oxidation reactor by directly adding sodium bicarbonate, in addition, because nitrosation reactor produces the water outlet pH impact on the low side that acid causes, also can reflux and volumetric loading is effectively alleviated by increase.The Anammox reaction formula formula that comprises microbial metabolism is as follows:
1NH 4 ++1.32NO 2 -+0.066HCO 3 -+0.13H +→1.02N 2+0.26NO 3 -+0.066CH 2O 0.5N 0.15+2.03H 2O
Described sulphur removal Analysis unit carries out simultaneous denitrification except sulphuring treatment by anaerobic ammonium oxidation vessel water outlet, thereby the recycle that realizes gas washing desulfurization absorption liquid is also eliminated to the accumulation of nitrate radical simultaneously.It is as follows that the denitrification denitrogenation of consideration microbial metabolism removes reaction of Salmon-Saxl formula:
14.5HS -+5NO 3 -+0.2NH 4 ++HCO3 -+20.3H +=CH 1.8O 0.5N 0.2+2.5N 2+14.5S 0+27.4H 2O
Comprehensive above nitrosification, denitrification denitrogenation sulphur removal and three formula of Anammox, can draw bio-regeneration device 19 biochemical reaction aggregative formulas:
1.004NH 3+0.32HS -+0.05HCO 3 -+0.375H +→0.55N 2+0.32S 0+0.028CH 2O 0.5N 0.15+0.022CH 1.8O 0.5N 0.2+1.48H 2O
According to the biochemical reaction aggregative formula of bio-regeneration device 19, every mole of ammonia nitrogen needs the hydrogen sulphur root of 0.32 mole to participate in reaction, the mass ratio that is scaled sulfate radical and ammonia nitrogen is 2.2, general sanitary sewage ammonia nitrogen approximately 30 mg/litre, sulfate radical is about 100 mg/litre, calculates thus as long as the transformation efficiency of sulfate radical generation hydrogen sulfide reaches 60% and both can meet.
In described bio-regeneration device 19, comprise three kinds of micropopulation reactions, thiobacillus denitrificans group (TDs), ammonia oxidation flora (AOBs) and Anammox flora (ANAMMOXs), suitable temperature of reaction is respectively at 28~30,29~35,32~37 degrees Celsius, and minimum stable temperature of reaction is respectively 10,15,20 degrees Celsius.Consider, control the temperature of reaction of whole bio-regeneration device at 25~30 degrees Celsius.
For nitrosation reaction, the researchs such as Jin Ren village are found can be by improving the mode of salinity gradually, the salinity that bio-regeneration device 19 is adapted to up to 25 grams per liters, Er Zeng state the research such as drives and finds, ammonia oxidizing bacteria has higher salt resistance ability, can be issued in the salinity of 50 grams per liters 90% ammonia nitrogen removal frank; For Anammox reaction, Liu Chengliang utilizes the research of UASB reactor to find, can make anaerobic ammonia oxidation reactor adapt to the salinity up to 30 grams per liters by progressively improving the mode of salinity.For simultaneous denitrification, except reaction of Salmon-Saxl, on the sulfate radical that thiobacillus denitrificans adapts to, be limited to 250 mmoles, amount to the salinity of approximately 30 grams per liters.Therefore the present invention controls bio-regeneration device 19 salinity lower than 30 grams per liters.
By improving volumetric loading, can greatly dwindle required bio-regeneration reactor volume, described nitrosation reaction with by cultivation aerobic particle mud (AGS) be expected to reactor ammonia nitrogen volumetric loading to be increased to 3~6 kilograms of/cubic metre of skies, and anaerobic ammonium oxidation granular sludge can be up to the total nitrogen volumetric loading in 50~70 kilograms of/cubic metre of skies, and in conventional biological treatment, on activated sludge process is general, be limited to 0.1 kilogram of ammonia nitrogen/cubic meter day, the highest 1 kilogram of ammonia nitrogen of biomembrance process/cubic meter day, granule sludge processing is conventional activated sludge and biomembrance process several times to tens times.Due to certain salinity, and the rich or poor alternately even variation of matrix is extremely conducive to the cultivation of granule sludge, the research of aforementioned Liu Cheng Liang etc. is found in UASB reactor salinity lower than 30, in the situation of 000 mg/litre, Anammox biological activity increases along with the increase of salinity, the present invention controls salinity that the reaction of nitrosification and Anammox normally carries out 30, below 000 mg/litre, in bio-regeneration process, the concentration of ammonia nitrogen is along with reduce swap time gradually, create natural rich or poor concentration and alternately changed, be extremely conducive to the cultivation of granule sludge.
The correlation technique that described bio-regeneration device 19 relates to can be referring to following documents and materials:
The controlling elements research contents of relevant nitrosation reactor refers to " startup of nitrosation reactor and controlling elements research " article of delivering in the 42nd the 6th phase of volume of the journal > > of < < Harbin Institute of Technology in the June, 2010 such as Zhang Jie.About referring to state once, the research of nitrite bacteria (ammonia oxidation bacteria) " separation of nitrite bacteria and the characteristic research " delivered in 15 1 phases of volume of < < biotechnology > > in February, 2005 such as drives.
Relevant bicarbonate ion refers on the research of Anammox reaction impact the article " HCO that Li Xiang etc. delivered in < < ACTA Scientiae Circumstantiae > the 32nd volume second phase of > in February, 2012 3 -the impact of concentration on anaerobic ammonia oxidation reactor denitrification efficiency ".Relevant pH solves and refers to " impact of low pH on high-load anaerobic ammonia oxidation reactor performance " article that Chen Jianwei etc. delivered in the 24th the 2nd phase of volume of the chemical engineering journal > of < < colleges and universities > in April, 2010 impact of anaerobic ammonia oxidation reactor.About referring to Tang Chongjian, the substrate inhibition problem of Anammox equals " substrate inhibition of anaerobic ammonia oxidation process and recovery policy thereof " article of delivering in < < application foundation and the 18th 4 phases of volume of engineering science journal > > in August, 2010.
The particular content of relative synchronous denitrification and desulfurization refers to He Li and equals " progress of simultaneous desulfurization and denitrification technology " delivered in the 29th the 1st phase of volume of < < renewable energy source > > on January 24th, 2011, Cai Jing and Zheng Ping " new bio denitrification and desulfurization process progress " that in November, 2011, < < science and technology circular > > 27 volumes 6 are delivered, the articles such as " isolation identification of thiobacillus denitrificans and Denitrification Characteristics researchs " that the people such as Che Xuan deliver at < < environmental science > > 29 volumes 10 in October, 2008.
The control information of relevant various microbial reaction bulk temperature refers to He Li and equals " progress of simultaneous desulfurization and denitrification technology " delivered in the 29th the 1st phase of volume of < < renewable energy source > > on January 24th, 2011; Wang Sha equals 2006 " research of high-concentration ammonia nitrogenous wastewater short distance nitration " in the 2nd phase of < < Shanghai environmental science > >, delivered; " startup of nitrosation reactor and the controlling elements research " that Zhang Jie etc. deliver in the 42nd the 6th phase of volume of the journal > > of < < Harbin Institute of Technology in June, 2010; Li Xiang equals the articles such as " impact of temperature on anaerobic ammonia oxidation reactor denitrification efficiency stability " of delivering in the 33rd the 4th phase of volume of < < environmental science > > in April, 2012.
About salinity nitrosifying impact is referred to Jin Ren village equals at < < ACTA Scientiae Circumstantiae > >, to deliver in March, 2010 " sodium acetate and inorganic salt on partial nitrification reactor operating performance affect > > and once state " the separated and characteristic research of the nitrite bacteria " article of delivering in 15 1 phases of volume of < < biotechnology > > in February, 2005 such as drive.Relevant salinity refers on the impact of Anammox reaction " the impact research of salinity on denitrification of anaerobic ammonium oxidation efficiency " article that Liu Chengliang equals to deliver at < < ACTA Scientiae Circumstantiae > > in September, 2011.About denitrification and desulfurization Effects of Salinity, refer to Zhang Zhongzhi and equal chemical " ecosystem characterization of thiobacillus denitrificans and application thereof " article of delivering with the biotechnology > > second phase of < < in 2005.
" operation of high-load anaerobic ammonia oxidation EGSB reactor and the ECP characteristic of granule sludge thereof " article that relevant EGSB granule sludge detailed content is delivered in the 61st the 3rd phase of volume of < < Journal of Chemical Industry and Engineering > > in March, 2010 with reference to Tang Chongjian etc.
Fig. 4 has shown an improved embodiment on the basis of Fig. 3, as shown in Figure 4, on basis embodiment illustrated in fig. 3, described sewage recycling total system 1 shown in Fig. 4 further comprises organic mud thickener 20, organic mud digestive organ 21 and inorganic mud water extracter 22, described preliminary precipitation strainer 11, described anaerobic biochemical reaction device 14, mix biochemical reaction device 15, the mud discharging mouth 113 of bio-regeneration device 19, 143, 153, 194 are connected with the entrance 201 of described organic mud thickener 20 by pipeline respectively, the concentrated mud outlet 202 of described organic mud thickener 20 is connected with the mud inlet 211 of described organic mud digestive organ 21, the mud discharging mouth 212 of described organic mud digestive organ 21 is connected with the entrance 221 of described inorganic mud water extracter 22 by pipeline, the wastewater outlet 203 of described organic mud thickener 20 is connected with the entrance 111 of described preliminary precipitation strainer 11 by pipeline, the mud discharging mouth 163 of described postprecipitation strainer 16 is connected with the entrance 221 of described inorganic mud water extracter 22 by pipeline, the wastewater outlet 222 of described inorganic mud water extracter 22 is connected with the entrance 161 of described postprecipitation strainer 16 by pipeline.
Described organic mud thickener 20 can comprise the mechanisms such as gravity concentration tank, separating centrifuge or pressure filter.It is mainly used in mud to carry out concentration, and mud is concentrated into and more than 3% delivers to described organic mud digestive organ 21 again.
Described organic mud digestive organ 21 is for carrying out Anaerobic Digestion to mud, anaerobic sludge digestion (fermentation) is mainly to utilize to produce acid and methanogen decomposing organic matter, thereby reach, make sludge reduction, innoxious object, owing to producing the susceptibility of methane engineering bacteria to temperature, temperature or two kinds of operation scheme of high temperature in generally adopting, according to the optimum activity research of methanobacteria, mesophilic digestion temperature range should be controlled at 35 degrees Celsius of left and right, thermophilic digestion requires temperature to be controlled at 55 degrees Celsius of left and right, therefore most mud needs to carry out hyperthermic treatment before entering Digestive tract, and slaking apparatus is incubated.Research shows, in the scope of 0~100 degree Celsius of temperature, have the methane flora that can grow for many years in the world, therefore can turn out corresponding flora reduction energy consumption and investment for envrionment temperature and reaction requirement.In operation scheme, anaerobically fermenting can adopt partition running, adopts the modes such as high-temperature-hot-water solution, soda acid, ultrasonic wave to carry out pre-treatment, to improve sludge biogas production amount.
The content of relevant anaerobic sludge digestion can equal 2008 at < < China biogas > > 26(1 with reference to Pei Xiaomei) " China's Researche Development of Anaerobic Fermentation Treating Residual Sludge from City Sewage Plant " article of delivering.The related data of relevant methanobacteria can equal " progress of methanogen " article of delivering in < < brewing science and technology > the 5th phase of > for 2009 with reference to Li Meiqun.
From the spoil disposal of described organic mud digestive organ 21 and the spoil disposal of described postprecipitation strainer 16, deliver to respectively described inorganic mud water extracter 22 and carry out processed, after processed, discharge dewatered sludge, general solid content is more than 20%, can be used as synthetic agriculture fertile, also can be used for improving the comprehensive utilizations such as soil, brickmaking.
Fig. 5 has shown an improved embodiment on the basis of Fig. 4, as shown in Figure 5, on basis embodiment illustrated in fig. 4, described sewage recycling total system 1 shown in Fig. 5 further comprises gas washing desulfurizer 23, the regenerated liquid outlet 191 of described bio-regeneration device 19 is connected by pipeline with the absorption liquid entrance 231 of described gas washing desulfurizer 23, the sulphur-bearing waste solution outlet 232 of described gas washing desulfurizer 23 is connected with the sulphur-bearing waste solution entrance 193 of described bio-regeneration device, the methane outlet of the methane outlet of described organic mud digestive organ 21 and described anaerobic biochemical reaction device 14 is connected with the inlet mouth 233 of described gas washing desulfurizer 23 respectively.
The preferred air lift of the present invention is as the desulfurization process of hydrogen sulfide removal functional unit 14B in described anaerobic biochemical reaction device 14, in 14B, Exhaust Gas mixes and delivers to gas washing desulfurization 23 with the aerogenesis of acidifying unit 14A and methanation unit 14C, the absorption liquid entrance 231 that the alkaline water of the regenerated liquid outlet 191 of described bio-regeneration device 19 is sent to described gas washing desulfurizer 23 is for absorbing hydrogen sulphide, mainly after desulfurization containing methane and carbon dioxide mix gas, partly return and drain into the supplementary air lift air inlet of 14B, remainder can be delivered to fuel gas generation, the device such as gas fired-boiler is used as fuel gas, the waste water that described gas washing desulfurizer 23 produces can also be discharged and is delivered to described bio-regeneration device 19, carry out being recycled use after the processing of desulfurization nitrogen.
From the biogas of described anaerobic biochemical reaction device 14 and described organic mud digestive organ 21, deliver to described gas washing desulfurizer 23 and carry out gas washing desulfurization processing, the regenerated liquid outlet 191 of described bio-regeneration device 19 is connected by pipeline with the absorption liquid entrance 231 of described gas washing desulfurizer 23, the sulphur-bearing waste solution outlet 232 of described gas washing desulfurizer 23 is connected with the sulphur-bearing waste solution entrance 193 of described bio-regeneration device, and hydrogen sulfide absorption liquid just can be realized recycle like this.The mode that the absorption liquid of gas washing desulfurization can be selected to promote pH and increase circular flow improves the elution efficiency of hydrogen sulfide.Biogas after described gas washing desulfurizer 23 desulfurization can be delivered to municipal gas distributing system, also can deliver to the device comprehensive utilizations such as heat supply, power supply.
Described gas washing desulfurizer 23 comprises a scrubber tower, generally hydrogen sulfide is passed into from scrubber tower bottom, absorption liquid sprays from top, in tower, filler can be housed, to increase gas-to-liquid contact, the biogas that contains the hydrogen sulfide of 1000 mg/litre can remove more than 90%, can adopt the scrubber tower of two sections of series connection to process sulfide hydrogen 2000 mg/litre in engineering, the biogas of 40 cubes ms/h, decreasing ratio can reach 99%.
Because small part elemental sulfur in denitrification and desulfurization unit (approximately 3.5%) can further react and generate sulfuric acid consumption basicity, conventionally need to add the pH that alkali maintains system, need regularly to discharge certain solution simultaneously and prevent the salinity accumulation causing because of sulfate radical.
In special sewage system, the very unbalance situation of sulfate radical and ammonia nitrogen ratio that has occurs, when sulfate radical mass ratio is higher, can produce excess hydrogen sulfide on the one hand, increase basicity consumption, and cause the accumulation of described bio-regeneration device 19 hydrogen sulphur roots, avoid this situation to occur, can be by the effluent recycling of the described gas washing desulfurizer 23 of part to the nitrosation reactor entrance of described bio-regeneration device 19, in nitrosation reactor, cultivate desulfurizing bacteria, increase the method for the aeration rate in nitrosation reactor in described bio-regeneration device 19, excessive nitrite nitrogen and oxygen are reacted with excessive hydrogen sulphur root and generate elemental sulfur recovery.Formula is as follows:
2HS -+O 2=2S 0+2OH -
2HS -+NO 2 -=2S 0+0.5N 2+2OH -
Excessive hydrogen sulphur root also produces the basicity of equivalent when generating elemental sulfur as seen from the above equation, just in time balance for and the basicity consumption of hydrogen sulfide.
Lower at former water sulfate concentration, in the lower situation of molar sulphur nitrogen, elemental sulfur can be further oxidized to sulfate radical as electron donor by thiobacillus denitrificans and complete denitrogenation, now can consume basicity.Formula is as follows:
5S 0+6NO 3 -+8H 20=5SO 4 2-+4H ++3N 2+6H 2O
According to above formula, by adding the mode of sulphur and basicity, also excessive nitric nitrogen can be removed to reaction of Salmon-Saxl by simultaneous denitrification and remove.
According to bio-regeneration device 19 biochemical reaction aggregative formulas, showing that every mole of influent ammonia nitrogen (ammonium ion) enters in described bio-regeneration device 19 will consume 0.375 moles of hydrogen ion and produce the basicity of 0.375 mole, wherein 0.32 mole of hydrogen sulphur radical ion that participates in reaction is to be ionized by alkali liquor absorption from hydrogen sulfide, following formula:
H 2S+OH -→HS -+H 2O
H 2S+HCO 3 -→HS -+H 2O+CO 2
Therefore 0.375 mole of used up 0.32 mole of basicity can be produced by device total alkalinity is supplemented, remainder basicity also can with exchanged ammonium ion generation neutralization reaction of getting off in described bio-regeneration type ammonium ion exchange device 12:
NH4 ++OH -=NH 3+H 2O
NH4 ++HCO 3 -=NH 3+H 2O+CO 2
As can be seen here, the present invention is by utilizing nitrosification, Anammox, and three kinds of biochemical process combinations of simultaneous denitrification sulphur removal can complete denitrification and desulfurization in the situation that not needing to add extra basicity.
From the get off ammonia nitrogen of 1 mole of described bio-regeneration type ammonium ion exchange device 12 every exchanges, can should there is mutually the sodium ion consumption of 1 mole, by the entrance at described bio-regeneration type ammonium ion exchange device 12 and to supplement caustic soda and a small amount of soda ash and lime at the entrance of described gas washing desulfurizer 23 be reasonable selection, the sodium ion of caustic soda is mainly used in supplementing and consumes, hydroxide ion increases can suitably increase pH value, be conducive to the absorption of hydrogen sulfide and removing ammonia nitrogen, and only can be combined with hydrogen ion and generate water, can not produce the ion accumulation problem that causes salinity to raise, thereby greatly reduce the waste liquid output of device.
Fig. 6 has shown an improved embodiment on the basis of Fig. 5, as shown in Figure 6, on basis embodiment illustrated in fig. 5, described sewage recycling total system 1 shown in Fig. 6 further comprises pre-softening treater 24, cation bed softening installation 25, chemical regeneration type ammonium ion exchange device 26, chemical regeneration device 27, crystallizing-dephosphorizing device 28, described pre-softening treater 24 entrances 241 are connected with described bio-regeneration type ammonium ion exchange device 12 outlets 122, described pre-softening treater 24 outlets 242 are connected with described cation bed softening installation 25 entrances 251, the described pre-softening mud discharging mouth 243 of treater 24 and the entrance 221 of described inorganic mud water extracter 22 are connected, described cation bed softening installation 25 water outlets 252 are connected with the entrance 131 of described low pressure RO treatment unit 13, the regeneration waste liquid outlet 253 of described cation bed softening installation 25 is connected with the entrance 141 of described anaerobic biochemical reaction device 14 and the dosing mouth 281 of described crystallizing-dephosphorizing device 28 respectively, described crystallizing-dephosphorizing device 28 entrances 282 are connected with described salt solution thickener 17 condensed water outlets 172, described crystallizing-dephosphorizing device 28 water outlets 283 are connected with the water inlet 181 of described evaporative crystallizer 18, it is agricultural as slow release fertilizer that the mud discharging mouth (not shown) of described crystallizing-dephosphorizing device 28 is discharged struvite, described low pressure RO treatment unit 13 treated water outlets 132 are connected with the entrance 261 of described chemical regeneration type ammonium ion exchange device 26 by pipeline, described chemical regeneration type ammonium ion exchange device 26 treated water outlets 262 are connected with indusqtrial water supply pipe network 3 by pipeline.The regenerated liquid of described chemical regeneration type ammonium ion exchange device 26 and waste liquid entrance 263, outlet 264 are connected by pipeline with the regenerated liquid of described chemical regeneration device 27 and waste liquid outlet 272, entrance 273 respectively.The ammoniacal liquor outlet 271 of described chemical regeneration device 27 is connected by pipeline with the entrance 141 of described anaerobic biochemical reaction device 14.
Described pre-softening treater 24 can comprise the functional units such as coagulative precipitation tank and strainer, can in coagulative precipitation tank, add alkali by corresponding 10~11 scopes that are adjusted at of pH value, to precipitate, removes most of calcium hardness, magnesium hardness and carbonate alkalinity.Water outlet is delivered to further removal hardness of described cation bed softening installation 25 from exporting 242, and spoil disposal drains into described inorganic mud water extracter 22 from described mud discharging mouth 243 and further processes.
Can be by adding successively lime in coagulative precipitation tank, soda ash and flocculation agent coagulant aids, make suspended substance in sewage, hardness and carbonate alkalinity form calcium carbonate and flco, and in the settling tank that inclined tube or swash plate are housed, precipitation is removed.In water inlet hardness, be less than in 1,000 mg/litre situation, generally can control settling tank and go out the water hardness below 50 mg/litre, suspended substance is less than 3 mg/litre, also can control hardness and be less than 10 mg/litre further combined with ultrafiltration membrance filter, suspended substance is less than 1 mg/litre.
Lime softening method and lime soda ash tenderizer associated viscera can be referring to the 4th industrial water supply > > of < < water supply and drainage handbook.
Described cation bed softening installation 25 can comprise strong acid or weakly acidic cationic exchanger resin tank and resin regeneration functional unit, the cationic exchange that selection exchangeability by ion exchange resin by the calcium in water, magnesium is etc. is removed, and water outlet calcium ions and magnesium ions concentration can be reduced to and be less than 1 mg/litre.
The strong-acid cation-exchange resin generally strong brine of needs 3%~8% is regenerated, and weakly acidic cationic exchanger resin need to be with hydrochloric acid or regeneration of sulfuric acid, therefore described cation bed softening installation 25 is provided with regenerated liquid entrance (not shown) for adding regenerated liquid, in the time of regeneration, also play the effect that acid is cleaned, the sediment undergoes washing of adhering on resin can be fallen, and then with caustic soda, Hydrogen weakly acidic cationic exchanger resin is converted into sodium type Zeo-karb, so not only can make water outlet pH keep stable, also can make weak acid resin use the in the situation that salt concn being higher in water simultaneously.In addition, it is to be noted, when pH is greater than 8.5, bicarbonate radical starts major part and is converted into carbonate, until pH is increased at 10.5 o'clock, 50% the bicarbonate radical of having an appointment is converted into carbanion, when therefore on resin, calcium ion concn is higher, have part and react generation precipitation with carbonate in water, for strong-acid cation-exchange resin, need to consider regular acid cleaning.Therefore in the situation that soda acid is easier to obtain, recommend adoption weakly acidic cationic exchanger resin is as the groundwork medium of described cation bed softening installation 25.
With the regenerated liquid of crossing, because of being rich in calcium, magnesium ion, the regeneration waste liquid by described cation bed softening installation 25 exports 253 can be delivered to respectively the entrance 141 of described anaerobic biochemical reaction device 14 and the dosing mouth 281 of described crystallizing-dephosphorizing device 28 to be further used.
In described bio-regeneration device 19, sulphur removal Analysis and anaerobic ammonium oxidation vessel will operate in anaerobic grain sludge state, and nitrosation reactor operates in aerobic particle mud state, the normal operation that maintains aerobic/anaerobic granule sludge need to have sufficient carbon, nitrogen, the nutritive substances such as phosphorus, wherein nitrogen nutrition material mainly comes from the regeneration waste liquid of described bio-regeneration type ammonium ion exchange device 12, and carbon, the nutritive substances such as phosphorus are by utilizing the carbon that is rich in of described low pressure RO treatment unit 13 outlets, the concentrated waste water of phosphorus and trace element adds, in addition, research to EGSB granule sludge shows, a small amount of calcium (12 mg/litre), magnesium (5 mg/litre) ion can be conducive to formation and the sedimentation of granule sludge, therefore using the partial regeneration waste liquid of described cation bed softening installation 25 as calcium ions and magnesium ions, originate and add in described bio-regeneration device 19.More than be arranged so that the present invention utilizes existing resource in system just can realize the nutritive equilibrium of whole system, and do not need additional nutrition source.
In the present invention, can in the pipeline between the water outlet 252 of described cation bed softening installation 25 and the entrance 131 of described low pressure RO treatment unit 13, add Scale inhibitors or dispersion agent to weaken the fouling tendency of waste water, Scale inhibitors can add with the concentration of 3~6 mg/litre.
In the present invention, by described bio-regeneration type ammonium ion exchange device 12, remove after most ammonia-nitrogen, in described pre-softening treater 24, add alkali pH is adjusted to 10~11 scopes removal hardness, by described cation bed softening installation 25, further remove divalent cation successively, avoid scale problems entering the front interpolation Scale inhibitors of described low pressure RO treatment unit 13.Thereby can effectively guarantee the steady running of follow-up anaerobic biological device 14.
The quality proportioning of anaerobic biochemical reaction device 14 general requirement influent CODs and ammonia nitrogen and phosphorus is that 200~300:5:1 just can meet the requirement of biochemical reaction, and influent COD is 3,000 mg/litre, in requisition for ammonia nitrogen 50 mg/litre, and phosphorus 10 mg/litre.According to general life raw waste water ammonia nitrogen concentration, be 30 mg/litre, total phosphorus is that 5 mg/litre enter system of the present invention, and after described pre-softening treater 24 is processed, total phosphorus can remove 50%, remains approximately 2.5 mg/litre, after concentrated 10 times, reaches 25 mg/litre; After softening processing, sewage is 10.5 at pH, now ammonia nitrogen 90% is molecular state, through described cation bed softening installation 25, process and be only adsorbed on a small quantity, major part will enter described low pressure RO treatment unit 13, wherein the ammonia nitrogen of 10% ionic state approximately 3 mg/litre can be concentrated 10 times, make the thickened waste water out 132 discharge water ammonia nitrogen concentrations of described low pressure RO treatment unit 13 increase by 30 mg/litre, ammonia nitrogen total concn is increased to 60 mg/litre.Now ammonia nitrogen and phosphorus concentration all can meet the nutritional needs of described anaerobic biochemical reaction device 14.
Under high pH condition, strengthened the ionization of negatively charged ion and weak ionization material in water, thereby to make reverse osmosis membrane compare conventional operation to removing of these materials more effective.Make such as organism, the ratio of desalinization of nitrate is brought up to more than 99% from 90~95%, and especially light current is brought up to more than 98% from 60%~70% from the ratio of desalinization of low molecular weight substance boron.Reverse osmosis membrane water inlet pH is greater than under 10 operational conditionss, strengthened organic acid ionization, make to be difficult to wash organism solubleness greatly improve, film is always in alkali cleaning state, thus the organic contamination that greatly alleviates film, and existing engineering practice shows, under high pH condition, the dense water of reverse osmosis membrane survey can the chemical oxygen demand (COD) (COD) that characterizes organic content up to 15,000 mg/litre conditions under steady running, can make reverse osmosis membrane move under high organism flow condition; The silicon class inorganic substance solubleness that film is formed to irrecoverable contact scar also improves greatly, at pH, it is 11 o'clock, dense water is surveyed dissolves silicon (existing with metasilicic acid form) content can reach 1,500 mg/litre, alleviated the irrecoverable inorganic pollution of film, reverse osmosis membrane can be moved under the condition of the siliceous water inlet of height; Bacterium is difficult in high pH survival, the biological pollution that has alleviated film; The wake boundary attenuation of reverse osmosis membrane water entry, make particulate matter be difficult for being attached to surface, the particulate matter that has reduced film pollutes, reverse osmosis membrane can be moved under the condition of pollution index (SDI) <5, and the water inlet of common reverse osmosis unit require SDI<1; Because of the use of hardness removal and Scale inhibitors, reverse osmosis membrane fouling tendency is reduced greatly, reduced the demand of pickling.
Utilize the special performance of the reverse osmosis unit of high pH operation, low pressure RO treatment unit 13 generally can be processed water inlet solvability COD 50~2, the sewage of 500 mg/litre, producing water ratio is controlled at 80%~99% time steady running, when producing high quality softening water, by concentrated 5~100 times of sewage volume, thereby by heat up 5~100 times of costs of sewage, be convenient to described anaerobic biochemical reaction device 14 in optimal temperature operation, thereby make organic pollutant change methane and the carbonic acid gas of recoverable into.
The reverse osmosis unit technology contents of high pH operation can refer at Fan Sheng TAO in 1992 in US Patent No. 5250, and 185A or Debasish Mukhopadhyay in 1997 are published in US Patent No. 6,537, in 456B2 description.The concrete technology contents of controlling relevant for sulfate concentration refers to Ruan Jun etc. at < < China biogas > > 2008, " the SO delivering in 26(1) 4 2-impact on Activity of Anaerobic Granular Sludges " and Liu Yan " impact of sulfate radical on organic waste water anaerobic biological treatment " delivered in < < environmental science > > the 5th phase of 13 volumes in 1992 in description.About the cleaning of reverse osmosis organic contamination, refer to Cao and account for " reverse osmosis membrane Organic pollutants and microorganism are cleaned research " that equality was delivered in the 24th the 2nd phase of volume of < < water technology > > in February, 2008.
Described chemical regeneration type ammonium ion exchange device 26 can comprise zeolite filler ion exchange column or the pond of ammonium ion being selected to exchangeability, zeolite filler can be divided into natural and modification type, in the different water yields, under water quality and hydraulic detention time, its operating capacity generally can be in the scope of 1~7 milligram of ammonia nitrogen of every gram of zeolite.
Under high pH condition, ammonia is most of in water to be existed with molecular state, under known 25 degrees Celsius, the ionization equilibrium constant pkb1 of ammonia in water is 4.74, and now ammonia and ammonium ion respectively account for 50% concentration, and corresponding pH is 9.26, when pH is increased to 10.25, amino molecule accounts for more than 90%.Because reverse osmosis membrane does not have removal effect to gas molecule, therefore there is more than 90% ammonia nitrogen will be stored in through in water, make water outlet ammonia nitrogen concentration too high, affect reuse water quality.
In the present invention, seeing through in water of described low pressure RO treatment unit 13 can be added to carbonic acid gas, by pH regulator to 6~8 scope, thereby ammonium ion degree of ionization is improved, 90% ammonia nitrogen ionization is effectively removed to carry out ion-exchange by zeolite for ammonium ion form.
Described bio-regeneration type ammonium ion exchange device 12 is by after 90% ammonia nitrogen removal, and after pH is promoted to 10~11,90% above ammonia nitrogen exists with gas form, and the COD that enters so described anaerobic biochemical reaction device 14 is original 100 times to the ratio of ammonia nitrogen.By described chemical regeneration type ammonium ion exchange device 26, water outlet ammonia nitrogen can be reclaimed, can make ratio reduce to 10 times.
For instance, suppose raw waste water COD300 mg/litre, ammonia nitrogen 60 mg/litre, while entering anaerobic biochemical reaction device 14, COD and ammonia nitrogen become 500:1, far below the proportion requirement of 200~300:5 in anaerobic biochemical reaction device 14, as chemical regeneration ammonia nitrogen is reclaimed and supplemented, become 250:5, just in time meet the proportion requirement of anaerobic biochemical reaction device 14.
Described chemical regeneration device 27 can comprise the cooling unit, absorption tower in an air stripping or steam air lift deammoniation tower unit and ammonia pickling or steam, can, by ammonia nitrogen by air stripping or steam air lift, then by the method for acid absorption or vapor condensation, extract.Ammonia separation efficiency generally can reach 90~99%, and the regeneration waste liquid after stripping can be recycled by described chemical regeneration type ammonium ion exchange device 26.By adding caustic soda, can promote the pH sodium ion that compensation regeneration consumes simultaneously.Reclaim ammoniacal liquor and can be supplemented to anaerobic biochemical reaction device 14.
On the chemical regeneration of in Hedstrom in 2001 August in the journal "Environmental Engineering" (Journal ofEnvironmental Engineering) 127th volume summary of ammonia zeolite ion exchange 8 period published "(" Ion Exchangeof Ammonium in Zeolites:A literature Review) and Feng Lingzhi in 2009 in the "water purification technology" twenty-eighth Vol. 2 period published "clinoptilolite regeneration chemicals experimental study on", chemical regeneration liquid recycling see Rahmani equal in 2009 in the "environmental health science and Engineering" (Iranian Journal of Environmental Health Science& Engineering) sixth volumes of gas natural clinoptilolite 3 period published "study on the removal of ammonia stripping regeneration" (INVESTIGATION OFCLINOPTILOLITE NATURAL ZEOLITE REGENERATION BY AIR STRIPPINGFOLLOWED BY ION EXCHANGE FOR REMOVAL OF AMMONIUM FROM AQUEOUSSOLUTIONS).
In described crystallizing-dephosphorizing device 28, by regulating pH in 8.5~9.5 scope, utilize magnesium ammonium phosphate crystallization process (MAP), phosphorus can be extracted and be converted into high-quality slow release fertilizer---struvite, and then reclaim agricultural.Adopt crystallizing-dephosphorizing generally can guarantee 90% dephosphorizing rate.
Nitrogen, phosphorus, magnesium under certain condition, crystallizable generation six water magnesium ammonium phosphates (MgNH4PO46H2O), " struvite " (MAP), is the high-quality slow release fertilizer of high-quality, reaction formula as follows:
Mg 2++NH 4 ++PO 4 3-+6H 2O-->MgNH 4PO 4·6H2O
From formula, in theory magnesium nitrogen phosphorus is pressed to 1:1:1 molar ratio reaction, crystallizablely go out " struvite ", but practical study is found, phosphorus concentration is under theory ratio, to generate the call parameter of struvite with pH, at pH, is 8.5~9.5 o'clock, and phosphorus concentration could meet higher than 110 mg/litre; And under 10~70 mg/litre, need to meet N/P ratio 2~4:1; Below 10 mg/litre, need N/P ratio could meet formation condition up to 32:1.Under pH9.5, magnesium phosphorus ratio should be controlled and be less than 2, because excessive magnesium phosphorus is than the generation that can cause by product trimagnesium phosphate, affects the purity of struvite.The concentration that improves phosphorus can reduce the required N∶P ratio of generation MAP effectively.Can utilize accordingly the concentrated concentrated water outlet containing higher phosphorous concentration of described salt solution thickener 17 as crystallizing-dephosphorizing water, thereby reduce the requirement of magnesium and ammonia nitrogen, alleviate the burden of aftertreatment device.
Carbonic acid gas is soluble in water, and reaction as follows occurs:
CO 2+H 2O→H 2CO 3
H 2CO 3→H ++HCO 3 -
HCO 3 -→H ++CO 3 2-
H ++OH -→H 2O
Therefore by adding carbon dioxide generating carbonic acid, first stage ionization will produce equivalent hydrogen ion and bicarbonate ion, hydrogen ion reacts the carbanion in water and hydroxide ion, thereby the colleague of reduction pH increases bicarbonate alkalinity.Supercarbonate is the important buffer substance of anaerobic reaction.In general biogas, institute's carbonated accounts for 1/3, can be similar to and be interpreted as organism approximately 1/3 conversion, supposes that degraded COD total amount is 300 mg/litre, has 100 mg/litre COD to be converted into carbonic acid gas, and being scaled CO2 mass concentration is 137 mg/litre.Carbonic acid be diprotic acid, under 25 degrees Celsius of standard state, Pka1=6.36, Pka2=10.25, the scope that is 10~12 at pH, show as carbonic acid all ionization be bicarbonate radical and carbanion.If pH is down to 8.5 from 11, whole carbanions will be converted into bicarbonate ion, and hydroxide ion is also neutralized completely, the hydrogen ion that need add nearly 1 mM/l, be converted into carbonic acid gas dosage approximately 44 mg/litre, the amount of carbon dioxide that the 100 mg/litre COD that namely degrade generate just can meet neutralization requirement, with the water inlet that maintains described anaerobic biochemical reaction device 14 and described bio-regeneration type ammonium ion exchange device 12 in ideal pH scope, the bicarbonate alkalinity increasing provides good buffering for the acidification reaction carrying out in described anaerobic biochemical reaction device 14.The biogas that the present invention produces is as gas fired-boiler described in supply of fuel and fuel gas generation, the carbonic acid gas being produced in tail gas after burning can be reclaimed, a part is adjusted as the pH entering before anaerobic biochemical reaction device 14, another part utilization of can purifying, the final zero release that realizes " carbonic acid gas ".
Due to the shortage of water resources and the raising of tap water cost, a lot of areas adopt sewage second-level discharge water (water in inferior quality) to substitute tap water and use as recirculated cooling water, owing to containing large amount of organic in water, microorganism and calcium magnesium hardness, need a large amount of add slow-release scale inhibitor, acid, and sterilant is guaranteed water quality, conventionally cycles of concentration, below 2 times, needs a large amount of middle water consumptions on the one hand, has on the other hand half the sewage that contains a large amount of medicaments to be discharged and causes secondary pollution.Utilize institute of the present invention industry to cross desalination, hard-off degree, removes organism, ammonia nitrogen, removes bacterium, microorganism, and the water that increases carbonate alkalinity is the desirable water source of process water.Chlorine root is removed in desalination, and hardness, and the reuse water of carbonate containing basicity can greatly reduce electrochemical metal corrosion, are extremely conducive to pipeline transportation and use as cooling-cycle device moisturizing.Wherein as cooling recirculation system moisturizing, cycles of concentration can be increased to more than 10 times, thereby greatly reduce, new water is used and the water yield of cooling tower blowdown, greatly reduce corresponding slow-release scale inhibitor simultaneously, sterilant, the interpolation of the medicaments such as soda acid, reduce the secondary pollution of knowing clearly to environment, play the dual function of water-saving and emission-reducing.
A kind of sewage recycling total system provided by the present invention by utilizing improved high-recovery film device to combine multiple biochemical process, is produced high quality softening water at removal pollutent simultaneously.Not only solve dense water and ammonia nitrogen and processed problem, and by pollutant resources such as organism, nitrogen phosphate and sulfur, magnesium, 90% above sewage high quality reuse further can be reduced pollutant emission equivalent more than 90%, and make system take up an area relative common process saving more than 90%.
The foregoing is only the schematic embodiment of the present invention, not in order to limit scope of the present invention.Any those skilled in the art, not departing from equivalent variations, modification and the combination of doing under the prerequisite of design of the present invention and principle, all should belong to the scope of protection of the invention.

Claims (2)

1. a sewage recycling total system, it is characterized in that, it at least comprises preliminary precipitation strainer, bio-regeneration type ammonium ion exchange device, working pressure is the low pressure RO treatment unit of 1-4 MPa, anaerobic biochemical reaction device, mix biochemical reaction device and postprecipitation strainer, wherein, municipal administration or industrial sewage pipe network are connected with the entrance of described preliminary precipitation strainer by pipeline, the outlet of described preliminary precipitation strainer is connected with the entrance of described bio-regeneration type ammonium ion exchange device by pipeline, the outlet of described bio-regeneration type ammonium ion exchange device is connected with the entrance of described low pressure RO treatment unit by pipeline, the treated water outlet of described low pressure RO treatment unit is connected with indusqtrial water supply pipe network by pipeline, the thickened waste water out of described low pressure RO treatment unit is connected with the entrance of described anaerobic biochemical reaction device by pipeline, the outlet of described anaerobic biochemical reaction device is connected with the entrance of described mixing biochemical reaction device by pipeline, the outlet of described mixing biochemical reaction device is connected with the entrance of described postprecipitation strainer by pipeline, the outlet of described postprecipitation strainer is connected with municipal drainage pipeline,
Described sewage recycling total system further comprises salt solution thickener and evaporative crystallizer, the outlet of described postprecipitation strainer is connected with the entrance of described salt solution thickener by pipeline, the condensed water outlet of described salt solution thickener is connected with the entrance of described evaporative crystallizer, and the de-salted water outlet of described salt solution thickener is connected with indusqtrial water supply pipe network respectively with the de-salted water outlet of described evaporative crystallizer;
Described sewage recycling total system further comprises bio-regeneration device, described bio-regeneration type ammonium ion exchange device further comprises a regenerated liquid entrance and a regeneration waste liquid outlet, the regenerated liquid outlet of described bio-regeneration device is connected by pipeline with the regenerated liquid entrance of described bio-regeneration type ammonium ion exchange device, and the regeneration waste liquid entrance of described bio-regeneration device is connected by pipeline with the regeneration waste liquid outlet of described bio-regeneration type ammonium ion exchange device;
Described sewage recycling total system further comprises organic mud thickener, organic mud digestive organ and inorganic mud water extracter, described preliminary precipitation strainer, described anaerobic biochemical reaction device, mix biochemical reaction device, the mud discharging mouth of bio-regeneration device is connected with the entrance of described organic mud thickener by pipeline respectively, the concentrated mud outlet of described organic mud thickener is connected with the mud inlet of described organic mud digestive organ, the mud discharging mouth of described organic mud digestive organ is connected with the entrance of described inorganic mud water extracter by pipeline, the wastewater outlet of described organic mud thickener is connected with the entrance of described preliminary precipitation strainer by pipeline, the mud discharging mouth of described postprecipitation strainer is connected with the entrance of described inorganic mud water extracter by pipeline, the wastewater outlet of described inorganic mud water extracter is connected with the entrance of described postprecipitation strainer by pipeline,
Described sewage recycling total system further comprises gas washing desulfurizer, the regenerated liquid outlet of described bio-regeneration device is connected by pipeline with the absorption liquid entrance of described gas washing desulfurizer, the sulphur-bearing waste solution outlet of described gas washing desulfurizer is connected with the sulphur-bearing waste solution entrance of described bio-regeneration device, and the methane outlet of the methane outlet of described organic mud digestive organ and described anaerobic biochemical reaction device is connected with described gas washing desulfurizer inlet mouth respectively.
2. sewage recycling total system as claimed in claim 1, it is characterized in that, described sewage recycling total system further comprises pre-softening treater, cation bed softening installation, chemical regeneration type ammonium ion exchange device, chemical regeneration device, crystallizing-dephosphorizing device, described pre-softening treater water inlet is connected with described bio-regeneration type ammonium ion exchange device outlet, described pre-softening treater water outlet is connected with described cation bed softening installation water inlet, the mud discharging mouth of described pre-softening treater is connected with the entrance of described inorganic mud water extracter, described cation bed softening installation water outlet is connected with the entrance of described low pressure RO treatment unit, the regeneration waste liquid outlet of described cation bed softening installation is connected with the entrance of described anaerobic biochemical reaction device and the dosing mouth of described crystallizing-dephosphorizing device respectively, described crystallizing-dephosphorizing device entrance is connected with described salt solution thickener condensed water outlet, described crystallizing-dephosphorizing device water outlet is connected with the water inlet of described evaporative crystallizer, it is agricultural as slow release fertilizer that the mud discharging mouth of described crystallizing-dephosphorizing device is got rid of struvite, described low pressure RO device treated water outlet is connected with described chemical regeneration type ammonium ion exchange device portal by pipeline, described chemical regeneration type ammonium ion exchange device treated water outlet is connected with municipal industrial reuse grid by pipeline, described chemical regeneration type ammonium ion exchange device regenerated liquid and waste liquid inlet/outlet go out with chemical regeneration device regenerated liquid and waste liquid respectively, entrance connects by pipeline, the ammoniacal liquor outlet of described chemical regeneration device is connected by pipeline with the entrance of described anaerobic biochemical reaction device.
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