The processing of algin production waste water and the processing method of circulation recover zero discharge
Technical field
The present invention relates to the multiple-stage treatment of waste water or sewage, the processing of the algin production waste water that especially a kind of marine alga produces when processing algin and the processing method of circulation recover zero discharge.
Background technology
Algin is a kind of natural macromolecule amylose polymkeric substance that extracts from phaeophyta marine plants such as sea-tangle, bulk kelp, bladder wrack, sargassun, and it is widely used in medicine, food, chemical industry, agriculture field as raw material.Will produce a large amount of waste water in the algin production process, this waste water mainly comprises: waste Ca water and composite waste.Wherein:
Waste Ca water refers to that mainly sea-tangle is adding yellow soda ash digestion, obtain heavy-gravity sodium alginate mud shape thing, adopt 100-150 water doubly to carry out after rare, by machinery mix gas, floating, leave standstill, impurity such as glue and residue are separated, and glue adopts the CaCl2 flocculation agent to carry out calcium and analyses, and makes sodium alginate change into calcium alginate and separates from solution, a large amount of waste Ca waters that the flocculation back produces, main component has Ca
2+, Mg
2+, C10
-, calcification glue particle etc.
A large amount of washess that composite waste produces when mainly comprising the sea-tangle pre-treatment (containing silt, small sea-tangle skin, carbohydrate gum, polyose colloid, alcohol, methyl alcohol, salt grades); Sea-tangle digestion, towards the floating residue liquid of weakly alkaline rare, floating generation (containing the sea-tangle piece, sea-tangle fiber, carbohydrate gum, sodium alginate solution of not complete digestion etc.); Calcium is analysed the acid-bearing wastewater that the glue decalcification produces; The squeezing waste water that produces during Lalgine press dewatering after the decalcification.
At present, marine alga processing enterprise is to the improvement directly discharging after aeration biochemical is handled mostly of above-mentioned algin production waste water, waste water after the processing does not often reach discharge index, thereby caused environmental pollution, for the waste water that solves discharging causes environmental pollution problems, numerous producers and experts and scholars have also carried out the research of serial purifying treatment, disclosed in the CN1125785C Chinese invention patent specification sheets as on October 29th, 2003 bulletin " a kind of purify the floating residue of algin of algin factory and the method for waste Ca water ", waste Ca water after the waste water that has proposed to contain floating residue in this specification sheets and the flocculation and/or decalcification waste water mix and react, remove by filter the technical scheme of the flocculation mixture of generation, so that the slag and effluent De Taili of discharging meets the environment protection emission requirement.Other has, in the CN1202030C Chinese invention patent specification sheets of announcing on May 18th, 2005 disclosed " a kind of marine alga processing industry sewage water treatment method ", disclose in this specification sheets and a kind ofly the sea-tangle pretreated waste water that is produced before the sea-tangle digestion process is carried out biological chemistry handled (after carrying out aeration oxygen replenishing biochemistry earlier, carrying out pulp water with the air supporting mode again separates) water body that obtains and when collecting clear glue solution after the sea-tangle digestion process remaining floating slag liquid carry out following process and (add after flocculation agent carries out chemical flocculation, carrying out thickness through percolation machine filters) the comprehensive back of waste water that produced adopts the air supporting mode to carry out the pulp water separation, and isolated water liquid carries out filtration treatment.Solved because of comprehensive water body salt content height, complicated component, the organic loading fluctuation is big, and the biochemical treatment difficulty is big, and the unfavorable problem of effect has the advantage that biochemistry is effective, working cost is low.Disclosed purifying treatment method in above-mentioned two specification sheetss all discharges the waste water after handling.At present, if emission treatment to the waste water cyclically utilizing after handling then because of influencing quality product, do not reach service requirements, and can only be selected by numerous manufacturing enterprise.China is a country that Freshwater resources are very in short supply, discharges after the marine alga processing industry sewage disposal at present, though reach environmental requirement, has also caused the waste of Freshwater resources.
Summary of the invention
Direct discharging algin production waste water can cause environmental pollution in the prior art in order to overcome, direct discharging of waste water after the processing and cyclically utilizing not, can waste the deficiency of Freshwater resources again, the invention provides a kind of processing of algin production waste water and the processing method of circulation recover zero discharge, this method can not only improve waste water treatment efficiency, reduce cost for wastewater treatment, and the water quality after handling can reach the standard of cyclically utilizing, save Freshwater resources.
The technical scheme that technical solution problem of the present invention is adopted is: a kind of processing of algin production waste water and the processing method of circulation recover zero discharge is characterized in that: the following treatment process of process:
The processing of a, waste Ca water
A.1 the pre-treatment of waste Ca water: send waste Ca water to the calcium wastewater equalization pond, waste Ca water is carried out the aeration oxidation pre-treatment;
A.2 decalcification is handled: the pretreated waste Ca water of aeration is risen in the decalcification reaction filter tank with pump, the filling decalcifying agent, carry out aeration agitation, staticly settle then, filter, filter the calcic waste residue recycle, the water after the filtration treatment quantitatively adds an amount of flocculation agent and enters the cyclic oxidation reactor;
The processing of b, composite waste
B.1 the solid-liquid separation of composite waste, oxidation pre-treatment: composite waste sent into carry out solid-liquid separation in the solid-liquid separator, the foreign material of sea-tangle residue and high density are separated, the recyclable utilization of sea-tangle residue, water after the separating treatment flows into aeration oxidation pre-treatment in the composite waste preset pond by solid-liquid separator, drives away the formaldehyde in the water;
B.2 biofiltration oxide treatment: the water after the above-mentioned aeration oxide treatment is sent into biological the adjusting carry out biofiltration in the filter tank and handle, and carry out the aeration oxidation, further COD, the ammonia nitrogen in the degradation water;
B.3 air supporting is handled: the water after the above-mentioned biological treatment is risen in the air flotation pool by pump, and the filling flocculation agent carries out air supporting to be handled, and uses slag scraper, and the isolating scum silica frost of air flotation pool is struck off;
B.4 flocculation, precipitation process: the water after above-mentioned air supporting handled is through the flocculation agent mixing tank, deliver to after the filling flocculation agent carries out efficiently mixing and carry out coagulating in the coagulation reaction tank, water behind the coagulating enters settling tank and precipitates, and the water of post precipitation enters the cyclic oxidation reactor;
The processing of c, integrated water
C.1 the cyclic oxidation of integrated water is handled: composite waste after the above-mentioned settling tank that enters in the cyclic oxidation reactor is handled and the calcium waste water after handle in the decalcification filter tank inject oxygenant and carry out the cyclic oxidation processing, finish the process of sterilization, degraded COD and ammonia nitrogen;
C.2 filtration, bio-oxidation are handled: will send into rapid filter through the integrated water after the cyclic oxidation reactor oxide treatment and filter, to eliminate the residual of ozone and chlorine; Send into again in the biological filter, carry out biofiltration and aeration and handle, remove COD and ammonia nitrogen in the integrated water;
C.3 protein separation is handled: will send the protein separation pond to through the integrated water after the biofiltration oxide treatment, adopt fluidic device to spray proper amount of oxidant and carry out secondary sterilization and oxide treatment, further with colloid, Mierocrystalline cellulose, albumin, the microbial film that comes off with filter separating of the small suspended substance that to remove, make that the water outlet in protein separation pond is glittering and translucent;
C.4 the reverse-osmosis treated of integrated water: will send into the water inlet Buffer Pool of reverse osmosis water treatment unit through the water after the protein separation pond purifies, water in the Buffer Pool supplies water to the reverse osmosis water treatment unit through water pump, utilizes reverse osmosis membrane to remove solubility salt, colloid and organism in the water;
C.5 the reuse of integrated water: the water after the reverse osmosis water treatment unit handled, fail with the water pump base runoff and to get back to the algin production line, for the algin production line provides water of productive use, or deliver to other water water supply units with pipeline;
The processing of d, solid shape waste
D.1 the processing of solid substance: isolating scum silica frost of waste, air flotation pool and the sedimentary mud solid substance of settling tank that solid-liquid separator is isolated except that the sea-tangle residue enter the sludge drying pond, through alternately transporting outward disposal after the mummification;
D.2 the processing of waste water in the solid substance: be provided with no husky bleeding of concrete wall at described sludge drying pond end, with the conjuncted water collecting basin that has of infiltration wall, waste water in the discarded solid substance is collected to water collecting basin through the infiltration wall, is refluxed to the composite waste preconditioning pond by the sump pump pump and handles.
In the solid-liquid separation pre-treatment step of above-mentioned b.1 composite waste, described solid-liquid separator is the arc solid-liquid separator.
Biology in the above-mentioned b.2 biofiltration oxidation treatment step is regulated the filter tank and is adopted two-stage biological to regulate the filter tank, the biological adjusting of one-level filter tank is the immersion filter tank, by the water inlet of bottom, pond, two stage biological is regulated the filter tank and is adopted the dribble-feed filter tank, strains hydrophone water outlet to two stage biological by the biological adjusting of one-level top, filter tank and regulates the filter tank.
Coagulation reaction tank described in the above-mentioned b.4 flocculation sediment treatment step adopts reciprocating type partition plate coagulation reaction tank, in first dividing plate, Aeration stirrer is set, to increase the initial reaction flow velocity, make the colloidal solid in the water that collision absorption fully take place, to increase the effect of coagulating.
Described settling tank adopts radical sedimentation basin, the center water inlet of settling tank, and peripheral effluent, the spoil disposal gradient is 10% at the bottom of the pond, center driving coupling mud scraper.
The oxygenant that is adopted in the cyclic oxidation treatment step of above-mentioned c.1 integrated water is an ozone, and this ozone is supplied with by ozone perfusion circulation device, and described ozone perfusion circulation device provides the ozonizer of oxygen source and supporting component to form by oxygenerator.
Filtrate in the above-mentioned c.2 rapid filter described in filtration, the bio-oxidation treatment step adopts gac,
Reverse osmosis water treatment unit described in the reverse-osmosis treated step of above-mentioned c.4 integrated water is made up of sandfiltration pot, interchanger, Scale inhibitors throwing device, security personnel's filtration unit, high-pressure hydraulic pump, reverse osmosis unit and chemically-cleaning device.
Top, described buffering pond is provided with upflow tube, and this upflow tube end is provided with clean water basin.Surplus water is in this overflow during less than service discharge when reverse osmosis water treatment unit treatment capacity, and overflow water flows into clean water basin as deposit or non-ly wash the glue reuse.
Can carry out back flushing to the filtrate in the rapid filter, filtrate in the sandfiltration pot, this back flushing water source is provided by the settling tank described in the flocculation sediment treatment step b.4, and the back flushing drainage water enters to reflux in the biological regulating reservoir in the biofiltration oxidation treatment step b.2 and handles.
The present invention carries out oxidation, decalcification processing with waste Ca water; composite waste carries out solid, liquid to be separated and biological treatment; both mixed integrated water are dispelled and are smelt through the oxidation of ozone efficient circulation, decolouring; after bio-oxidation is handled after filtration again; carry out reverse-osmosis treated by the reverse osmosis water treatment unit; the water quality of the water after the processing is higher than drinking water standard; can directly drink; the water of productive use standard that also is higher than algin far away; help improving the algin quality product; farthest save Freshwater resources, accomplished zero release or few discharging of sewage, helped the protection of environment.
The invention has the beneficial effects as follows that processing method is reasonable, advanced technology is reliable, production wastewater treatment efficient height, and working cost is low, anti-shock loading, the recycle to extinction recover zero discharge has been saved Freshwater resources, has stopped environmental pollution.
Description of drawings
The present invention will be further described below in conjunction with drawings and Examples.
Accompanying drawing is a process flow sheet of the present invention.
Embodiment
One ton of algin produces about 690 tons waste Ca water and about 390 tons composite waste is an example to produce below, further specifies processing method of the present invention.
As shown in drawings, produce waste Ca water and the following treatment process of composite waste process that algin produces:
The processing of a, waste Ca water
A.1 the pre-treatment of waste Ca water: about 690 tons waste Ca water gravity flow is entered calcium wastewater equalization pond, the main effect of calcium wastewater equalization pond: the one, regulate the temporary water yield of buffering, because the paddy peak of draining is bigger, and the low (80m of decalcification reaction processing capacity of design
3/ h); The 2nd, with the bottom type Aeration stirrer waste Ca water is carried out the aeration oxidation pre-treatment, water quality is carried out modifier treatment, drive away the chlorine residue in the water and prevent the pollutent precipitation;
A.2 decalcification is handled: the pretreated waste Ca water of aeration is quantitatively alternately risen in the decalcification reaction filter tank with submersible sewage pump, the filling decalcifying agent, carry out aeration agitation, staticly settle then, filter, filter the calcic waste residue recycle (can make material of construction), water after the filtration treatment quantitatively adds an amount of flocculation agent and enters the cyclic oxidation reactor, carries out oxidizing reaction;
The processing of b, composite waste
B.1 the solid-liquid separation of composite waste, oxidation pre-treatment: about 390 tons composite waste that will produce is sent into and is carried out solid-liquid separation in the arc solid-liquid separator, the foreign material of sea-tangle residue and high density are separated in real time, the recyclable utilization of sea-tangle residue, water after the separating treatment flows into aeration oxidation pre-treatment in the composite waste preset pond by solid-liquid separator, carrying out water quality for next step biofiltration prepares, when the aeration oxidation pre-treatment, can feed an amount of ozone gas, with the formaldehyde in the quick decomposition expeling waste water;
B.2 biofiltration oxide treatment: the water after the above-mentioned aeration oxide treatment is sent into biological the adjusting in the filter tank, by the elastic biological filtrate that is provided with in the pond, carrying out biofiltration handles, and the aeration tube that is provided with by the bottom, pond carries out the aeration oxidation, biological regulating reservoir is regulated the filter tank by two-stage biological and is formed, the one-level biological filter is the immersion filter tank, water is entered by the bottom, pond, after filtration, aeration is after the hydrophone water outlet is strained to the two stage biological equalizing tank in top, filter tank, two stage biological is regulated the filter tank and is adopted the dribble-feed filter tank, the one, play to regulate to cushion being temporarily stored in the water yield, because the paddy peak of draining is bigger, and the low (100m of composite waste processing power of design
3/ h); The 2nd, the COD in the further degradation water, ammonia nitrogen;
B.3 air supporting is handled: the water that two stage biological is regulated after handle in the filter tank is risen in the air flotation pool by the submersible sewage pump in the pond, the filling flocculation agent adopts dissolved air flotation to carry out air supporting and handles, this air floating method can remove deleterious organic granular in the water fast, prevent that organic granular from decomposing in water body, can be directly from water adsorbing and removing fall colloid, Mierocrystalline cellulose, albumin, and employing slag scraper, the isolating scum silica frost of air flotation pool is struck off, with solid-liquid separator can't isolating suspended substance and the colloid albumen fine impurities separate, reach rapid minimizing BOD
5, COD
CrPurpose with SS;
B.4 flocculation sediment is handled: the water after air supporting is handled is through the flocculation agent mixing tank, flow automatically to after the filling flocculation agent carries out efficiently mixing and carry out coagulating in the coagulation reaction tank, coagulation reaction tank adopts reciprocating type partition plate coagulation reaction tank, in first dividing plate, Aeration stirrer is set, to increase the initial reaction flow velocity, make the colloidal solid in the water that collision absorption fully take place, to increase the effect of coagulating;
Water behind the coagulating enters settling tank and precipitates, and settling tank adopts radical sedimentation basin, the water inlet of employing center, the form of peripheral effluent, design bottom spoil disposal gradient is 10%, adopts transmission mud scraper in center to scrape mud, and the water of post precipitation enters the cyclic oxidation reactor;
The processing of c, integrated water
C.1 the cyclic oxidation of integrated water is handled: the integrated water that composite waste after will entering settling tank in the cyclic oxidation reactor and handling and the calcium waste water after handle in the decalcification filter tank form is injected ozone and is carried out cyclic oxidation and handle, and finishes sterilization, the process of degrade COD and ammonia nitrogen.This ozone is supplied with by ozone perfusion circulation device, and ozone perfusion circulation device provides the processing annex of the ozonizer of oxygen source and air compressor machine, air to form by oxygenerator.Adopt ozone to have the following advantages as oxygenant: a, have very strong oxidation capacity, be the most active oxygenant, microorganism, virus, gemma etc. are all had very strong lethality, sterilisation effect is good, duration of contact short (<1min), drug residue free; B, have very strong removing and smell except that materials such as look (bleaching) and removal ferric oxide, manganese; C, can remove phenol, no chlorophenol flavor; D, can not generate organic chloride; E, to add dosage control simple, adopts oxidizing potential control method to get final product; F, do not need chemical feedstocks, only electricity consumption can prepare ozone; G, ozone can decolour to remove and smell processing waste Ca water, thereby improve the quality and the class of algin product.
C.2 filtration, bio-oxidation are handled: will send into rapid filter through the integrated water after the cyclic oxidation reactor oxide treatment and filter through gac, to eliminate the residual of ozone and chlorine; Send in the biological filter, the biological elastic filter material in the filter tank carries out biofiltration again, carries out aeration by the bottom type Aeration stirrer and handles, and removes COD and ammonia nitrogen in the integrated water;
Gac in the rapid filter can carry out back flushing, and the back flushing water source is provided by radical sedimentation basin, and the back flushing drainage water enters the biological one-level biological filter of regulating the filter tank and carries out the processing again of recirculation water.
C.3 protein separation is handled: will send the protein separation pond to through the integrated water after the biofiltration oxide treatment and carry out colloid, Mierocrystalline cellulose, albumin, the microbial film that comes off and filter separating of the small suspended substance that can't remove, in the protein separation pond, adopt fluidic device to spray an amount of ozone simultaneously and carry out secondary sterilization and oxidation, utilize the microcoacervation effect of ozone to strengthen the separating effect in protein separation pond greatly, make that the water outlet in protein separation pond is more glittering and translucent;
C.4 the reverse-osmosis treated of integrated water: will send into the water inlet Buffer Pool of reverse osmosis water treatment unit through the water after the protein separation pond purifies, water in the Buffer Pool supplies water to the reverse osmosis water treatment unit through water pump, utilizes reverse osmosis membrane to remove solubility salt, colloid and organism in the water; At the upflow tube that buffering top, pond is provided with, this upflow tube end is provided with clean water basin.Surplus water is in this overflow during less than service discharge when reverse osmosis water treatment unit treatment capacity, and overflow water flows into clean water basin as deposit or non-ly wash the glue reuse.
The reverse osmosis water treatment unit is made up of sandfiltration pot, interchanger, Scale inhibitors throwing device, security personnel's filtration unit, high-pressure hydraulic pump, reverse osmosis unit and chemically-cleaning device.
Sandfiltration pot: its filtrate is a quartz sand, and this filtrate also can carry out back flushing, and the back flushing water source is also provided by radical sedimentation basin, and the back flushing drainage water also enters the biological one-level biological filter of regulating the filter tank and carries out the processing again of recirculation water.
Interchanger: water source temperature variation throughout the year is big, because reverse osmosis water treatment unit water production rate is directly proportional with temperature, under the higher situation of temperature, the reverse osmosis membrane flux is big, and the power of required pump is little, and pretreating effect is good, adds dose and economizes; When water temperature was low, water production rate reduced, the corresponding increase of energy consumption, so vapor-water heat exchanger adjusting inflow temperature is set in the system and device, the control reverse osmosis system is in steady temperature (25 ℃ ± 2 ℃) work down.When summer temp was higher, interchanger can be stopped using.
Scale inhibitors throwing device:, insoluble salt [Mg (OH) occurs in order to prevent the dense water end (W.E.) of reverse osmosis water treatment unit
2, CaCO
3, CaSO
4Deng] crystallization separates out the bright Greer index of dense water LSI 1.8, form the dirt layer on the reverse osmosis membrane surface, thus damage membrane element performance should be arranged, so the Scale inhibitors throwing device is set in system.
Security personnel's filtration unit: mainly be in the trap water〉mechanical impurity of 5 μ m, enter reverse osmosis membrane to prevent large particulate matter, its filter core adopts wire wound filter core, and under normal operation, filter core can be kept the work-ing life in 4~June,
High-pressure pump: high-pressure pump is the power of reverse osmosis water treatment unit.
The CPA3 film that reverse osmosis membrane can adopt Hydranautics to produce, single film ratio of desalinization 〉=99.7%.
Chemically-cleaning device: when reverse-osmosis membrane element is subjected to boiler contamination, when system performance index dropped to a certain degree, available its carried out matting to reverse osmosis membrane, to recover its due premium properties.
C.5 the reuse of integrated water: the water quality of the water after the processing of reverse osmosis water treatment unit is higher than drinking water standard, can directly drink, the water of productive use standard that also is higher than algin far away, the defeated algin production line of getting back to of available water pump base runoff, for the algin production line provides water of productive use, or deliver to other water water supply units with pipeline, supply water to plant area by the variable frequency water supply unit.
The processing of d, solid shape waste
D.1 the processing of solid substance: isolating scum silica frost of waste, air flotation pool and the sedimentary mud solid substance of settling tank that the arc solid-liquid separator is isolated except that the sea-tangle residue enter the sludge drying pond, through alternately transporting outward disposal after the mummification;
D.2 the processing of waste water in the solid substance: be provided with no husky bleeding of concrete wall at sludge drying pond end, with the conjuncted water collecting basin that has of infiltration wall, waste water in the discarded solid substance is collected to water collecting basin through the infiltration wall, is refluxed to the composite waste equalizing tank by the sump pump pump and handles.
Record through chemical examination, by above-mentioned treating processes, the principal pollutant in each stage of wastewater treatment and expection treatment effect see attached list 1, subordinate list 2.
Waste Ca water treatment process design treatment effect table look-up (mg/l) table 1
Composite waste treatment process design treatment effect table look-up (mg/l) table 2
Reuse water index (being higher than drinking water standard) after the reverse-osmosis treated:
PH value |
COD
cr |
Total hardness is (with CaCO
3Meter)
|
Colourity |
Opacity (NTU) |
Muriate |
7-8.5 |
≤3 |
≤250 |
≤10 |
≤1 |
≤150 |
(above data are except that pH value, colourity and opacity, and other is mg/l)
Show through above data; the water quality of being carried out the water after the reverse-osmosis treated by the reverse osmosis water treatment unit is higher than drinking water standard; can directly drink; the water of productive use standard that also is higher than algin far away; help improving the algin quality product; save Freshwater resources to greatest extent, accomplished zero release or few discharging of sewage, helped the protection of environment.