CN103102036B - Cellulose ethanol production wastewater treatment method - Google Patents
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Abstract
The present invention relates to a cellulose ethanol production wastewater treatment method, which is used for treatment of high concentration salt-containing organic wastewater during an ethanol production process adopting corn straws and other plant fiber as raw materials. According to the method, cellulose ethanol production wastewater is subjected to a combination process, wherein the combination process comprises press filtration, cooling, anaerobic digestion, upflow type anaerobic sludge bed fermentation, first stage aerobic biochemistry, electrolysis catalysis oxidation, second stage aerobic biochemistry and filtration, and the treated effluent can be subjected to direct standard discharge. The cellulose ethanol production wastewater treatment method has the following advantages that: standard discharge treatment of high concentration salt-containing organic wastewater in one time can be achieved, waste in the wastewater can be effectively recovered and recycled, high concentration organic pollutants can be converted into methane and the like so as to be subjected to resource utilization, and requirements of recycling economy, clean production and the like are met.
Description
Technical field
The present invention relates to a kind for the treatment of process of cellulose ethanol production wastewater, for the processing take vegetable fibres such as maize straws as the treating high-concentration saline organic wastewater of raw material production ethanol process.
Background technology
Along with the general requirement of aggravation, recycling economy and the minimizing carbon emission of the worsening shortages of global fossil energy, environmental pollution, the exploitation of renewable energy source has become the theme in these epoch, and is one of important channel of renewable energy source exploitation take vegetable fibres such as maize straw, Chinese sorghum straws as raw material production cellulose ethanol.
Cellulose ethanol is take vegetable fibres such as maize straw, Chinese sorghum straws as raw material, obtain high purity ethanol by steaming the techniques such as quick-fried pre-treatment, cellulase hydrolysis, saccharifying enzyme fermentation, ethanol rectifying and dehydration, mix again production process of alcohol products in gasoline component, as clean fuel for vehicle.In its production process, because most hemicellulose in raw material (C5 sugar), xylogen can not be utilized, add the by product such as acetic acid, glycerine, lactic acid, furfural of association in process, make the suspended substance and the dissolved organic matter that in the final mash by discharge at the bottom of ethanol distillation tower, contain high concentration.Simultaneously, for improving cellulosic hydrolysis efficiency in stalk, alcohol concn in fermented liquid, alcohol product yield and the process of reduction energy consumption, the consideration of zymin consumption, steam quick-fried pre-treatment carries out often under acidic conditions, after fibrous material being flooded with more than 1% sulfuric acid in advance, steam quick-fried pre-treatment, to reach the object of Mierocrystalline cellulose weave construction in effective destruction stalk, and the sulfuric acid that this process adds and for follow-up hydrolysis, the sodium hydroxide adding with adjusting in fermenting process is present in ethanol distillation tower fermentation liquid with the form of inorganic salt the most at last, cause cellulose ethanol waste water on the basis of containing high-enriched organics, there is again the character of saliferous.Through detecting all sidedly and dissecting, cellulose ethanol production wastewater is mainly derived from ethanol distillation tower fermentation liquid, and its principal character is: insoluble solid object height, be about 5%, and be mainly the xylogen that particle diameter is fine, solid-liquid is not easily separated; Temperature is high, is about 95 ℃; Colourity is large, is acid, and pH value is 5 left and right; COD approximately 130,000 mg/L, are mainly solvability wood sugar, glycerine, acetic acid, volatile phenol, lactic acid, xylogen (poly-ring aromatic compounds), furfural and various fermentation intermediate product; BOD
5/ COD=0.5～0.55, wherein bio-refractory thing is mainly aromatics; Inorganic salt content is higher, is about 2%～4%(take vitriol as main), sulfate radical approximately 1% contains a certain amount of K, Mg, Ca, Fe ion simultaneously; Inorganic salt, sulfate radical, acetic acid, furfural, SS and xylogen etc. in waste water have serious restraining effect to conventional biological process processing.
Because cellulose ethanol production process is comparatively complicated, water of productive use and water displacement are all quite high, according to current state of the art analysis, produce one ton of alcohol product fresh water consumption amount and are about 25～30 tons, simultaneously by the factory effluent of discharging approximately 25 tons.The high density having due to such waste water, high saliferous, difficult biochemistry, high temperature, high SS and the characteristic such as not easily separated, make waste water handling problem become the key restraining factors of cellulose ethanol scale operation.The high-concentration sewage problem producing for solving cellulose ethanol production process, the main treatment process adopting is that high-concentration sewage is carried out to anaerobic treatment at present, remove some in sewage has severe inhibition material to Mierocrystalline cellulose or hydrolysis of hemicellulose and liquid glucose fermenting enzyme, as carboxylic acid, furfural, furans, phenol etc., make to process rear water outlet reuse as much as possible.As CN01808115.0 and US6555350 all propose to adopt up-flow anaerobic sludge blanket (UASB) art breading sewage, inhibitory substance carboxylic acid in sewage, furfural, furans, phenol etc. are removed more than 80%, sewage after processing more than at least 5% is recycled, produce methane by anaerobically fermenting, methane recovery is put forward high-octane utilization ratio simultaneously.But the method is only applicable to process neutral (not acid adding) and steams the waste water that quick-fried pre-treating process produces, and water outlet COD after treatment is still up to more than 4000mg/L, and the reuse of depolarization small part does not have follow-up treatment measures up to standard outward.CN200810011463.2 proposes a kind for the treatment of process of cellulose ethanol production wastewater, cellulose ethanol waste water is adopted to flocculating settling-acid out processing-catalytic and oxidative electrolysis technology-anaerobically fermenting combined treatment flow process, process rear effluent reuse and make the process waters such as the washing of cellulose ethanol production, pickling, fermentation; In the situation that damage and sewage can not be implemented reuse, after processing, aerobic biochemical and filtration treatment are carried out in water outlet again, make water outlet meet qualified discharge requirement (COD≤100mg/L).But the method is also mainly applicable to the processing of the neutral or low acid high density hyposaline organic waste water that steams quick-fried pretreatment technology, more importantly be adopted treatment process exist energy consumption and working cost high.And flocculation-acid out process will add flocculation agent and acid in waste water, not only can increase the inorganic salt concentration of waste water, and because the xylogen particle diameter in waste water is fine, flocculating effect is bad.
Based on above analysis, produce in technology, have economically larger advantage although adopt the acid cellulose ethanol that steams quick-fried pre-treating process, but also correspondingly bring larger waste water handling problem, also there is no at present process, economically viable stably reaching standard treatment technology.
Summary of the invention
The present invention is directed to the water quality characteristics of the acid cellulose ethanol base product mash that steams quick-fried pre-treatment route, a kind for the treatment of process of cellulose ethanol production wastewater is proposed, cellulose ethanol production wastewater is adopted to press filtration-cooling-anaerobic digestion-up-flow anaerobic sludge blanket fermentation-one-level aerobic biochemical-catalytic and oxidative electrolysis technology-secondary aerobic biochemical-filtration combination process, through the water outlet qualified discharge of said process processing.It is low that while the inventive method has running cost, organic constituent utilization ratio advantages of higher in waste water.
The treatment process of cellulose ethanol production wastewater of the present invention comprises following eight processing units:
(1) suspended substance filters, and processing waste water is cellulose ethanol base product mash, adopts the suspended substance filter methods such as press filtration to filter.Detailed process is that waste water is delivered to pressure filter and carried out press filtration processing, and pressure filter water outlet is sent into cooling tower and cooled; Filter residues of press filter fully utilizes disposal as Ordinary solid waste.Pressure filter can adopt conventional plate and frame(type)filter press, chamber-type press filter, belt filter press or expeller etc.Cellulose ethanol production wastewater is the acid cellulose ethanol base product mash that steams quick-fried pretreatment process.
(2) cooling process, after suspended substance filters, hot wastewater is cooled to 38～42 ℃.Can adopt conventional cooling tower to carry out cooling process, cooling rear water outlet enters Anaerobic Digestion.Cooling tower adopts conventional levels tube bank induced draft air-cooler, and waste water flows in pipe, air is blown over outside tube bank.
(3), there is one-level digestion reaction under the digestion bacterium effect of the cooled waste water that step (2) obtains in anaerobic digester in Anaerobic Digestion, the methane gas of generation is recycled outward by the pneumatic outlet discharger at top, pond; Processing water outlet enters up-flow anaerobic sludge blanket fermentation by liquid outlet in pond and carries out secondary anaerobic processing.The volumetric concentration of methane gas that this unit obtains is 40%～60%; The residence time of waste water in Anaerobic Digestion reaction tank is 15～20d; Water inlet volumetric loading is 4～6kgCOD/m
3× d; In reactor, the service temperature of waste water is 40～42 ℃.
(4) up-flow anaerobic sludge blanket fermentative processing, waste water after step (3) Anaerobic Digestion enters reactor by the bottom of upflow anaerobic sludge blanket reactor after degassing tower is degassed, under anaerobic mud bed anaerobically fermenting bacterium effect, secondary methanation reaction occurs, methane gas is recycled outward by the pneumatic outlet discharger of reactor head; Process water outlet and discharged by up-flow anaerobic sludge blanket top liquid outlet, send into one-level aerobic treatment after sludge settling, the sludge circulation after sedimentation returns upflow anaerobic sludge blanket reactor.The volumetric concentration of methane gas that this unit obtains is 40%～60%; The residence time of waste water in upflow type anaerobic reaction tank is 20～50h; Water inlet volumetric loading is 5～15kgCOD/m
3× d, return sludge ratio (returned sluge accounts for the volume percent into water) is 100%～200%.
(5) one-level aerobic treatment, aerobic treatment is carried out in the water outlet after step (4) up-flow anaerobic sludge blanket fermentative processing, and after processing, water outlet enters catalytic and oxidative electrolysis technology processing.One-level aerobic biochemical adopts conventional activated sludge method or biomembrance process.
(6) catalytic and oxidative electrolysis technology processing, waste water after step (5) one-level aerobic treatment is sent in the three dimensional particles electrolysis catalyst oxidation reactor that anode, negative electrode and solid catalyst particle composition are housed, by apply volts DS between reactor anode and cathode, and by reactor lower part oxygenic aeration, waste water is carried out to catalytic and oxidative electrolysis technology processing, make difficult for biological degradation organic matter in waste water change into the low-molecular material of biodegradability, reach and improve water quality and decolouring object, after processing, secondary biochemical treatment is carried out in water outlet.Detailed process be after one-level aerobic treatment water outlet with 0.5～2h
-1liquid air speed send in the three dimensional particles electrolysis catalyst oxidation reactor that anode, negative electrode and solid catalyst particle composition are housed, by applying 10～36V volts DS between reactor anode and cathode, and by reactor lower part oxygenic aeration (adopting air), keep air water volume ratio 5～20, the free radical producing by means of water electrolysis and load on the katalysis of the catalytic metal on high activity surface, changes into carbonic acid gas, low molecular organic acids etc. by the organism of the high density difficult for biological degradation in waste water as furfural, aromatic series etc.Catalytic and oxidative electrolysis technology reactor can adopt this area existing apparatus, the catalytic and oxidative electrolysis technology reactor as described in CN200810011463.2 etc.
(7) secondary aerobic treatment, carries out secondary aerobic treatment by the water outlet after treatment of step (6) catalytic and oxidative electrolysis technology, and filtration treatment is carried out in water outlet after treatment.Secondary aerobic biochemical can adopt conventional activated sludge method or biomembrance process, but preferably adopts the biomembrance process that can keep compared with high sludge concentration, as MBR, MBBR, BAF etc.
(8) filtration treatment, filters water outlet qualified discharge.Filtration treatment adopts traditional sand-bed filter, more medium filter, fibrous bundle or fiber ball filter, also can adopt the shifting sand filter etc. of thermopnore form to process the suspended substance in the water outlet of aerobe unit, and after processing, water outlet can qualified discharge.
The inventive method adopts respectively press filtration, cooling, anaerobic digestion, up-flow anaerobic sludge blanket fermentation, one-level aerobic biochemical, catalytic and oxidative electrolysis technology, secondary aerobic biochemical, filters combined treatment flow process cellulose ethanol waste water, and after processing, water outlet can meet qualified discharge requirement discharge.
The method that the present invention proposes has high density saline sewage and can realize refuse material in qualified discharge, waste water and obtained efficient recovery and comprehensive utilization, high concentration organic contaminant and be converted to methane etc. and obtain the utilization of resources, meets the requirement of recycling industries and clean production etc.The inventive method, by the reasonable combination of technical process, greatly reduces operation energy consumption, has reduced operating cost.
Accompanying drawing explanation
Fig. 1 is a kind of concrete cellulose ethanol production wastewater processing technological flow schematic diagram of the present invention;
1-pressure filter; 2-cooling tower; 3-anaerobic digester; 4-up-flow anaerobic sludge blanket; 5-one-level biochemical treatment unit; 6-catalytic and oxidative electrolysis technology system; 7-secondary biochemical treatment unit; 8-strainer.
Embodiment
Below in conjunction with accompanying drawing, the specific embodiment of the inventive method is described.
Cellulose ethanol production wastewater (from the mash at the bottom of ethanol distillation tower, approximately 95 ℃ of temperature) is entered pressure filter continuously
1in, the insoluble solid refuse in waste water, as xylogen, fermentation residue etc. are trapped within on the filter cloth of pressure filter, depart from and reclaims rear comprehensive utilization from filter cloth subsequently.Pressure filter
1pressing filtering liquid pump into cooling tower through lift pump
2, after air cooling, temperature is down to 40～42 ℃, enters anaerobic digester
3.Anaerobic digester
3under the effect of digestion bacterium, there is one-level digestion reaction in interior waste water, make partial organic substances change into biogas (methane and carbon dioxide), and after biogas desulfurization, enter biogas storage tank (not shown in figure 1) by top, pond vapor pipe and recycle, water outlet flows into up-flow anaerobic sludge blanket (being called for short UASB, as follows) after degassed
4carry out B grade anaerobic fermentation processing.UASB
4there is secondary methanation reaction in interior waste water, make the most of organism in waste water change into methane under the effect of anaerobically fermenting bacterium, and sulfate radical is reduced to hydrogen sulfide; The biogas producing in pond enters biogas storage tank (not shown in figure 1) after desulfurization; After processing, water outlet enters one-level biochemical treatment unit through settling tank sludge settling with after refluxing
5.Waste water is in one-level biochemical treatment unit
5middle generation aerobic biochemical reaction, changes into carbonic acid gas and water by the biodegradability organism in waste water, and catalytic and oxidative electrolysis technology system is sent in water outlet
6process.From one-level biochemical treatment unit
5water outlet in catalytic and oxidative electrolysis technology system
6in the effect of three dimensional particles catalytic and oxidative electrolysis technology under (hydrogen peroxide free radical, manganese titanium catalysis electrode, photocatalytic active carbon particle etc.), the difficult for biological degradation such as furfural, polycyclic aromatic hydrocarbons component in waste water is oxidized to low molecular organic acids, enterprising one-step removal COD and colourity on the basis of improving wastewater biodegradability, water outlet enters secondary biochemical treatment unit
7process.Waste water is in secondary biochemical treatment unit
7interior generation secondary aerobic biochemical reaction, makes waste water realize the de-N of the de-C of the degree of depth and processes, and after processing, strainer is sent in water outlet
8filtration treatment.Waste water is through filter
8remove qualified discharge after suspended substance.
Pressure filter of the present invention
1can adopt conventional plate and frame(type)filter press, chamber-type press filter, belt filter press or expeller etc., its main purpose be remove with recycled fiber alcohol wastewater in high concentration suspended matter, as xylogen, fermentation residue etc., after processing, the moisture control of solid waste is below 80%.Solids after recovery can mix and in coal, do fuel utilization.
Cooling tower of the present invention
2adopt conventional levels tube bank to draw phoenix formula air cooler, waste water flows in pipe, air is blown over outside tube bank.Control leaving water temperature(LWT) at 40～42 ℃.
Anaerobic digester of the present invention
3for the common contact process anaerobic reation pool of one, mainly formed by gas skirt, Chi Gai, pond body, feed-pipe, drainage conduit, whipping device etc.From cooling tower
2processing water outlet enter reaction tank by anaerobic digester underfeed pipe, complete after reaction anaerobically fermenting bacterium, biogas is recycled outward by the pneumatic outlet discharger at reaction tank top; Process water outlet and enter up-flow anaerobic sludge blanket by reaction tank drainage conduit
4carry out subsequent disposal.The volumetric concentration of methane gas that this unit obtains is 40%～60%; The residence time of waste water in anaerobic digester is 15～20d; The water inlet volumetric loading of anaerobic digester is 4～6kgCOD/m
3.d; In reaction tank, the service temperature of waste water is 40～42 ℃.
Up-flow anaerobic sludge blanket of the present invention
4for the common anaerobic reactor structure of one, mainly formed by four parts such as distribution plate, granule sludge treatment zone, bulking sludge breeding blanket, gas-solid-liquid separators.From anaerobic digester
3processing water outlet enter reactor by the bottom of UASB, on anaerobic mud bed, complete after reaction by anaerobically fermenting bacterium, methane gas is recycled outward by the pneumatic outlet discharger of reactor head; Process water outlet and discharged by reactor head liquid outlet, through sludge settling with after refluxing, water outlet enters one-level aerobic treatment unit
5carry out subsequent disposal.The volumetric concentration of methane gas that this unit obtains is 40%～60%; The residence time of waste water in anaerobic reactor is 20～50h, is preferably 35～42h; The water inlet volumetric loading of anaerobic reactor is 5～15kgCOD/m
3.d, be preferably 8～12kgCOD/m
3.d; In reactor, the service temperature of waste water is 38～40 ℃; Return sludge ratio is 100%～200%.
One-level aerobic treatment of the present invention unit
5can be one or more combinations in traditional activated sludge process, intermittent activated sludge process (SBR), contact oxidation method, biomembrance process and any follow-on aerobe method.
Catalytic and oxidative electrolysis technology reactive system of the present invention
6mainly formed by facilities such as electrolytic reaction pond, triphase separator, D.C. regulated power supply, negative plate, positive plate, catalyzed oxidation particle and water distribution, gas distributions.Its Anodic, negative electrode all adopt titanium manganese alloy material; Catalyst particle electrode adopts prior load to have granulated active carbon or the activated carbon fiber of the metal of catalyzed oxidation function, and catalyst particle loadings is 5%～20% of reactor useful volume; If one or more in activated carbon granule or activated carbon fiber-loaded master metal cobalt, copper, iron, manganese, nickel, vanadium, titanium, metal content is counted 1%～15% of gac or activated carbon fiber quality with oxide compound, is preferably 5%～10%; Catalytic metal carrying method in activated carbon granule or activated carbon fiber can be existing various ordinary method, and as pickling process, kneading method etc., method concrete as that describe by US6797184 is prepared etc.The volts DS applying between reactor cathode-anode plate is 10～36V, is preferably 15～30V; Reactor lower part oxygenation mode can adopt common micro-pore aeration and other any effective means, air water volume ratio 5～20; The volume space velocity of composite waste in catalytic and oxidative electrolysis technology reactor is 0.5～2h
-1, be preferably 0.5～1h
-1, service temperature is normal temperature～50 ℃.
Secondary aerobic treatment of the present invention unit
7it can be the one in traditional activated sludge process, intermittent activated sludge process (SBR), contact oxidation method, biomembrance process and any follow-on aerobe method, but preferably adopt the biomembrance process that can have compared with high sludge concentration, as MBR, MBBR, BAF, biological fluidized bed etc.
Strainer of the present invention
8can select traditional sand-bed filter, more medium filter, fibrous bundle or fiber ball filter, shifting sand filter that also can selective flow bed form etc.
Adopt the inventive method to carry out press filtration-cooling-anaerobic digestion-up-flow anaerobic sludge blanket fermentation one-level aerobic biochemical-catalytic and oxidative electrolysis technology-secondary aerobic biochemical-filtration combined treatment to the factory effluent of the quick-fried pretreatment technology producd fibers of acid ethanol, can make pollutent COD main in treating high-concentration saline organic wastewater be reduced to by 130,000 mg/L that 100 mg/L are following, sulfate radical is reduced to below 400 mg/L by 10,000 mg/L, all meet the requirement of sewage qualified discharge.Meanwhile, the non-solubility organism in waste water is all recycled utilization; High density organic constituent major part in waste water is converted to methane recovery utilization, has realized the object of energy-saving and emission-reduction and utilization of waste material.
Further illustrate the inventive method and effect below by embodiment, percentage ratio is wherein massfraction.
Adopt treatment process of the present invention to process the cellulose ethanol production equipment waste water of domestic certain medium-sized test scale.Waste water is the acid cellulose ethanol base product mash that steams quick-fried pretreatment process, and the principal character of waste water is: 95 ℃ of temperature, SS(suspended substance) 50000 mg/L, COD 129050 mg/L(chromium methods, lower with), BOD
568600 mg/L, sulfate radical 9290 mg/L, inorganic salt 2.3%, ammonia nitrogen 38.8 mg/L, phenol 600 mg/L.
Adopt press filtration of the present invention-cooling-anaerobic digestion-up-flow anaerobic sludge blanket fermentation-one-level aerobic biochemical-catalytic and oxidative electrolysis technology-secondary aerobic biochemical-filtration combination process to carry out laboratory treatment test to above-mentioned waste water, wastewater treatment scale is 200 mL/h, and main experimental installation formation, operational conditions and the treatment effect of each processing unit are in table 1.After processing by method of the present invention, COD in cellulose ethanol waste water can be reduced to that 100mg/L, inorganic salt amount are reduced to 1.8%, sulfate radical is reduced to 380 mg/L, ammonia nitrogen, volatile phenol, SS reach respectively 10 mg/L, 0.5 mg/L, below 50 mg/L, can meet the requirement of sewage qualified discharge.
The main processing unit of table 1 embodiment 1 forms and treatment effect.
| processing unit title | treatment unit scale and chief component | main operational conditions and control parameter | process water outlet or |
| 1 press filtration | filter, treatment capacity 10L/h | periodical operation, vacuumizes, membrane filtration | water outlet COD11.7 ten thousand mg/L; Filter residue water ratio 80%; |
| 2 is cooling | glass cools device, inside fills out Stainless Steel Helices | 40 ℃ of leaving water temperature(LWT)s | - |
| 3 anaerobic digestions | adopt contact process technique, material synthetic glass, reactor volume 100L.Mainly comprise the formations such as gas skirt, Chi Gai, pond body, feed-pipe, drainage conduit, whipping device. | bottom intakes continuously; Water inlet flow velocity 200mL/h; Retention time of sewage 20d; Water inlet volumetric loading 5.0kgCOD/m 3.d; 40 ℃ of service temperatures; The methane gas average-volume concentration 45% of collecting. | water outlet COD 26000mg/L, BOD 510300mg/L, volatile phenol 100mg/L, sulfate radical 1400mg/L, pH7.8. |
| 4 up-flow anaerobic sludge blanket fermentations | adopt UASB, material synthetic glass, reactor volume 10L.Mainly comprise the formations such as bottom water distribution board, granule sludge bed, mud buffer layer, Gas-solid-liquid separater, vapor pipe, water shoot, screen cloth. | bottom is water inlet continuously; Water inlet flow velocity 200mL/h; Retention time of sewage 40h; Water inlet volumetric loading 12kgCOD/m 3.d; 39 ℃ of service temperatures; The methane gas average-volume concentration 55% of collecting. | water outlet COD 4000mg/L, BOD 51500mg/L, volatile phenol 15mg/L, sulfate radical 380mg/L, inorganic salt 1.8%, sulfide 20 mg/L, pH 9. |
| 5 one-level aerobic biochemical unit | adopt traditional SBR, material synthetic glass, reactor volume 20L.Mainly comprise bottom micro-hole aerator oxygenic aeration, machine mixer, with entering of magnetic valve, the useless water and air of programmable logic controller (PLC) sequence control system control. | be interrupted Inlet and outlet water; Two cycles of day operation; Periodic duty time 12h, water inlet 4h, aeration 10h, sedimentation 0.5h, draining 1h, idle 0.5h; Period treatment water yield 2.4L, water inlet flow velocity 0.6L/h; Blast volume 100mL/min. | water outlet COD 1000mg/L, BOD 5150mg/L, ammonia nitrogen 25mg/L, volatile phenol 10mg/L, sulfide 1mg/L, pH 7-9. |
| 6 catalytic and oxidative electrolysis technology unit | the cell body that top mouthful unlimited pmma material is made, cubic capacity 0.5L.Two sidewalls of cell body are installed respectively a titanium Mn alloy plate, and access respectively on the negative pole and positive pole of D.C. regulated power supply.Micro-hole aerator and water-in are laid respectively in cell body bottom, supply air with air compressor machine; Cell body side wall upper part is laid water outlet, fills the activated carbon granule of a kind of year active cobalt metal, loadings 30g in cell body. | bottom is water inlet continuously; Water inlet flow velocity 200mL/h; Reactor two ends apply voltage 18V, electric current 1.0A; The air amount of blasting 50mL/min; 38 ℃ of service temperatures; Carry the method preparation that metallic absorbent charcoal particle is described according to US6797184, metallic copper oxide content is |
water outlet COD 500mg/L, BOD 5200mg/L, ammonia nitrogen 25mg/L, volatile phenol 5mg/L, sulfide 0.5mg/L, pH 6-9. |
| 7 secondary aerobic biochemical unit | adopt MBBR technique.The cylindrical shell that pmma material is made, total useful volume 2L, centre is divided into reaction zone and fluidization regions by dividing plate by cylindrical shell.Cylinder body bottom is laid respectively micro-hole aerator and water-in, supplies air with air compressor machine; Water outlet is laid on cylinder lateral wall top, fills a kind of elastic solid filler of routine, packing material size 3mm, loadings 400mL in cylindrical shell. | middle part is water inlet continuously; Water inlet flow velocity 200mL/h; Retention time of sewage 10h; Influent COD volumetric loading 1.2kgCOD/m 3.d. | water outlet COD 100mg/L, BOD 520mg/L, ammonia nitrogen 10mg/L, volatile phenol 0.5mg/L, SS 100mg/L, sulfide 0.5mg/L; PH 6-9 |
| 8 filter | quartz sand filtration post, diameter 20mm, high 50mm | ? | water outlet COD 100mg/L, BOD 520mg/L, ammonia nitrogen 10mg/L, volatile phenol 0.5mg/L, SS 50mg/L, sulfide 0.5mg/L; PH 6-9 |
Adopt the treatment unit of embodiment 1, process the sewage identical with embodiment 1, the water treatment effect that the operational conditions of change each processing unit obtains is in table 2.
The main processing unit of table 2 embodiment 2 forms and treatment effect.
| processing unit title | treatment unit scale and chief component | main operational conditions and control parameter | process water outlet or |
| 1 press filtration | filter, treatment capacity 10L/h | periodical operation, vacuumizes, membrane filtration. | water outlet COD11.7 ten thousand mg/L; Filter residue water ratio 80%; |
| 2 is cooling | glass cools device, inside fills out Stainless Steel Helices | 40 ℃ of leaving water temperature(LWT)s. | - |
| 3 anaerobic digestions | adopt contact process technique, material synthetic glass, reactor volume 100L.Mainly comprise the formations such as gas skirt, Chi Gai, pond body, feed-pipe, drainage conduit, whipping device. | bottom intakes continuously; Water inlet flow velocity 200mL/h; Retention time of sewage 20d; Water inlet volumetric loading 5.0kgCOD/m 3.d; 40 ℃ of service temperatures; The methane gas average-volume concentration 45% of collecting. | water outlet COD 26000mg/L, BOD 510300mg/L, volatile phenol 100mg/L, sulfate radical 1400mg/L, pH7.8. |
| 4 up-flow anaerobic sludge blanket fermentations | adopt UASB, material synthetic glass, reactor volume 10L.Mainly comprise the formations such as bottom water distribution board, granule sludge bed, mud buffer layer, Gas-solid-liquid separater, vapor pipe, water shoot, screen cloth. | bottom is water inlet continuously; Water inlet flow velocity 150mL/h; Retention time of sewage 52h; Water inlet volumetric loading 9kgCOD/m 3.d; 39 ℃ of service temperatures; The methane gas average-volume concentration 55% of collecting. | water outlet COD 3500mg/L, BOD 51200mg/L, volatile phenol 15mg/L, sulfate radical 350mg/L, inorganic salt 1.78%, sulfide 20 mg/L, pH 9. |
| 5 one-level aerobic biochemical unit | adopt traditional SBR, material synthetic glass, reactor volume 20L.Mainly comprise bottom micro-hole aerator oxygenic aeration, machine mixer, with entering of magnetic valve, the useless water and air of programmable logic controller (PLC) sequence control system control. | be interrupted Inlet and outlet water; Two cycles of day operation; Periodic duty time 12h, water inlet 4h, aeration 10h, sedimentation 0.5h, draining 1h, idle 0.5h; Period treatment water yield 2.4L, water inlet flow velocity 0.6L/h; Blast volume 100mL/min. | water outlet COD 950mg/L, BOD 5150mg/L, ammonia nitrogen 25mg/L, volatile phenol 9mg/L, sulfide 1mg/L, pH 7-9. |
| 6 catalytic and oxidative electrolysis technology unit | the cell body that top mouthful unlimited pmma material is made, cubic capacity 0.5L.Two sidewalls of cell body are installed respectively a titanium Mn alloy plate, and access respectively on the negative pole and positive pole of D.C. regulated power supply.Micro-hole aerator and water-in are laid respectively in cell body bottom, supply air with air compressor machine; Cell body side wall upper part is laid water outlet, fills the activated carbon granule of a kind of year active cobalt metal, loadings 30g in cell body. | bottom is water inlet continuously; Water inlet flow velocity 150mL/h; Reactor two ends apply voltage 18V, electric current 1.0A; The air amount of blasting 50mL/min; 38 ℃ of service temperatures; Carry the method preparation that metallic absorbent charcoal particle is described according to US6797184, metallic copper oxide content is gac 4% (wt), and metal vanadium oxide content is gac 6% (wt). | water outlet COD 420mg/L, BOD 5180mg/L, ammonia nitrogen 25mg/L, volatile phenol 5mg/L, sulfide 0.5mg/L, pH 6-9. |
| 7 secondary aerobic biochemical unit | adopt MBBR technique.The cylindrical shell that pmma material is made, total useful volume 2L, centre is divided into reaction zone and fluidization regions by dividing plate by cylindrical shell.Cylinder body bottom is laid respectively micro-hole aerator and water-in, supplies air with air compressor machine; Water outlet is laid on cylinder lateral wall top, fills a kind of elastic solid filler of routine, packing material size 3mm, loadings 400mL in cylindrical shell. | middle part is water inlet continuously; Water inlet flow velocity 150mL/h; Retention time of sewage 13h; Influent COD volumetric loading 0.8kgCOD/m 3.d. | water outlet COD 90mg/L, BOD 520mg/L, ammonia nitrogen 10mg/L, volatile phenol 0.5mg/L, SS 100mg/L, sulfide 0.5mg/L; PH 6-9 |
| 8 filter | quartz sand filtration post, diameter 20mm, high 50mm | ? | water outlet COD 100mg/L, BOD 520mg/L, ammonia nitrogen 10mg/L, volatile phenol 0.5mg/L, SS 50mg/L, sulfide 0.5mg/L; PH 6-9 |
Comparative example
Press the operational path of CN200810011463.2, i.e. " flocculating settling-acid out processing-catalytic and oxidative electrolysis technology-anaerobically fermenting-aerobic treatment-filtration treatment " process, while making water outlet meet qualified discharge requirement (COD≤100mg/L), operation energy consumption is 3 times of left and right of embodiment 1.
Claims (11)
1. a treatment process for cellulose ethanol production wastewater, is characterized in that comprising following process:
(1) suspended substance filters, and processing waste water is the acid cellulose ethanol base product mash that steams quick-fried pretreatment process;
(2) cooling process, the hot wastewater after suspended substance filters is cooled to 38～42 ℃;
(3) Anaerobic Digestion, step (2) obtains cooled waste water and under the effect of anaerobic digestion bacterium, methanation reaction occurs in pond, and methane gas is recycled outward by the pneumatic outlet discharger at top, pond;
(4) up-flow anaerobic sludge blanket fermentative processing, waste water after step (3) anaerobic digestion enters reactor by the bottom of upflow anaerobic sludge blanket reactor after degassing tower is degassed, under anaerobically fermenting bacterium effect on anaerobic mud bed, secondary methanation reaction occurs, methane gas is recycled outward by the pneumatic outlet discharger of reactor head;
(5) one-level aerobic treatment, carries out aerobic treatment by the water outlet after the anaerobic mud bed fermentative processing of step (4);
(6) catalytic and oxidative electrolysis technology processing, waste water after step (5) aerobic treatment is sent in the three dimensional particles electrolysis catalyst oxidation reactor that anode, negative electrode and solid catalyst particle composition are housed, by apply volts DS between reactor anode and cathode, and by reactor lower part oxygenic aeration, waste water is carried out to catalytic and oxidative electrolysis technology processing;
(7) secondary aerobic treatment, carries out aerobic treatment by the water outlet after treatment of step (6) catalytic and oxidative electrolysis technology;
(8) filtration treatment, the secondary aerobic treatment of step (7) goes out water filtration and reaches emission standard.
2. in accordance with the method for claim 1, it is characterized in that: during step (1) is filtered, adopt plate and frame(type)filter press, chamber-type press filter, belt filter press or expeller.
3. in accordance with the method for claim 1, it is characterized in that: during step (2) is cooling, cooling employing is air-cooled directly cooling.
4. in accordance with the method for claim 1, it is characterized in that: in step (3) Anaerobic Digestion, the residence time of waste water in anaerobic reactor is 15～20d, and water inlet volumetric loading is 4～6kgCOD/m
3d, in reactor, the service temperature of waste water is 40～42 ℃.
5. in accordance with the method for claim 1, it is characterized in that: in step (4) up-flow anaerobic sludge blanket fermentative processing, the residence time of waste water in anaerobic reactor is 20～50h, and water inlet volumetric loading is 5～15kgCOD/m
3d, return sludge ratio 100%～200%.
6. it is characterized in that in accordance with the method for claim 1: step (5) one-level aerobic treatment is activated sludge process or embrane method aerobic treatment process.
7. in accordance with the method for claim 1, it is characterized in that: the described catalytic and oxidative electrolysis technology treating processes of step (6) is, by waste water after treatment up-flow anaerobic sludge blanket with 0.5～2h
-1liquid air speed send in the three dimensional particles electrolysis catalyst oxidation reactor that anode, negative electrode and solid catalyst particle composition are housed, by applying 10～36V volts DS between reactor anode and cathode, and by reactor lower part oxygenic aeration, keep air water volume ratio 5～20.
8. according to the method described in claim 1 or 7, it is characterized in that: the anode of the catalytic and oxidative electrolysis technology reactor described in step (6), negative electrode all adopt titanium manganese alloy steel material; Solid catalyst particle adopts load to have activated carbon granule or the activated carbon fiber of the metal of catalyzed oxidation function, and solid catalyst particle loadings is 5%～20% of reactor useful volume; Activated carbon granule or activated carbon fiber-loaded metal are one or more in cobalt, copper, iron, manganese, nickel, vanadium, titanium, and metal content is counted 1%～15% of activated carbon granule or activated carbon fiber quality with oxide compound.
9. according to the method described in claim 1 or 7, it is characterized in that: the volts DS that catalytic and oxidative electrolysis technology reactor adopts is 15～30V; The volume space velocity of waste water in catalytic and oxidative electrolysis technology reactor is 0.5～2h
-1.
10. it is characterized in that in accordance with the method for claim 1: step (7) secondary aerobic treatment is activated sludge process or embrane method aerobic treatment process.
11. in accordance with the method for claim 1, it is characterized in that: the filtration treatment of step (8) adopts sand-bed filter, more medium filter, fibrous bundle or fiber ball filter, or adopt the shifting sand filter of thermopnore form.
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