CN104478167A - Treatment process and treatment system of chromium-containing wastewater in leather wastewater - Google Patents
Treatment process and treatment system of chromium-containing wastewater in leather wastewater Download PDFInfo
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Abstract
The invention provides a treatment process of chromium-containing wastewater in leather wastewater. The treatment process comprises the following steps: firstly filtering impurities of the chromium-containing wastewater in the leather wastewater, subsequently homogenizing and averaging, then reacting and finally precipitating to obtain chromium-containing treatment water and chromium sludge; then homogenizing, averaging and aerating the chromium-containing treatment water obtained by the steps, enabling the chromium-containing treatment water to react with manganese sulfate, then adding a flocculating agent to flocculate and precipitate to obtain mixed treatment water and primary precipitation sludge; firstly carrying out hydrolytic acidification treatment on the mixed treatment water, then carrying out intermediate precipitation treatment to obtain intermediate treatment water and intermediate precipitation sludge; and finally carrying out biological contact oxidization treatment on the intermediate treatment water, and then carrying out secondary precipitation treatment to obtain the treated chromium-containing wastewater and secondary precipitation sludge.
Description
Technical field
The present invention relates to treatment process and the treatment system of chromate waste water in a kind of leather waste water, belong to Industrial Waste Water Treatments field.
Background technology
Along with developing rapidly of leather industry in recent years, leather waste water has become one of important source of pollution.According to statistics, there is family of large, medium and small tannery more than 20000 in current China, year waste discharge amount reach 8000 ~ 12,000 ten thousand tons, account for 0.3% of national trade effluent total amount.The Cr discharged in these waste water about 3500 tons, suspended substance 120,000 tons, COD is 180,000 tons, ammonia nitrogen 100,000 tons.Along with the development of economic society and people are to the raising of environmental requirement, the process of leather waste water more and more receives the concern of people.
The waste water produced in leather production process is mainly from Rou Qian workshop section (comprising immersion fleshing, depilation liming, deashing and softening operation), tanning process (comprising pickling, tanning processes), finishing workshop section (comprising retanning, neutralization, dyeing, stuffing operation).As the liming depilation operation in tanning production, the specific absorption of the lime used, sodium sulphite and Sodium sulfhydrate only has an appointment 10 ~ 30%, and when discharging from rotary drum, sulfide is greater than 3000mg/l, and COD is up to 100,000 more than mg/l; After the undue solution of albumen mass-energy be dissolved down from raw material skin in addition, the ammonia nitrogen concentration discharged is also high especially, causes the ratio of the ammonia-nitrogen content in processed sewage not have ammonia-nitrogen content before treatment also high; After the tensio-active agent used when processing leather is in addition discharged into waste water, not only more difficult removal, has also had influence on microbial growth; In leather making process, also use heavy metal chromium, it is again danger wastes that leather-making mud is discharged in environment, is forbidded strictly etc. by country.
In a word, in leather waste water, pollutant component is various, is usually expressed as the S of high density
2-and Cr
3+, high concentration COD, high strength ammonia nitrogen compound, biodegradability is poor, containing neutral salt such as a large amount of muriates, vitriol.At present, the S in leather waste water
2-and Cr
3+method all by physics, chemistry is removed, and for COD, the ammonia nitrogen substances existed a large amount of in leather waste water, conventional materilization freatment method then seems helpless.The COD of leather waste water and ammonia nitrogen class material adopt biochemical method to be removed usually.The biochemical treatment stage is the metabolism by microorganism, and the conversion realizing Pollutants in Wastewater matter (COD, ammonia nitrogen etc.) is removed.
But, along with the requirement of country to leather discharge water quality is more and more higher, and the composition more complicated of leather waste water, comprise chromate waste water, sulfur-containing waste water, dyeing waste-water and factory effluent, comprehensive treating process difficulty is large, wherein be difficult to chromate waste water process in waste water is clean by single process and meet national standard, especially meet national secondary water quality requirement, and also can be mingled with other processing wastewaters in chromate waste water, the time that process needs is longer, efficiency is lower, does not meet production requirement.
Therefore, how can provide treatment process and the treatment system of chromate waste water in a kind of leather waste water, can reach the secondary standard water quality requirement of national sewage discharge, be the practical problems that leather manufacturer is urgently to be resolved hurrily in the industry always.
Summary of the invention
The technical problem that the present invention solves is the treatment process and the treatment system that provide chromate waste water in a kind of leather waste water, uses chromate waste water in the leather waste water of present invention process system process can reach the secondary standard water quality requirement of national sewage discharge.
In view of this, the invention provides the treatment process of chromate waste water in a kind of leather waste water, comprise the following steps:
A) by first for the chromate waste water in leather waste water filtering foreign material, then carry out homogeneous and all measure process, then after reacting with highly basic, finally carry out precipitation process, obtain containing chromium process water and chromium mud;
B) above-mentioned steps is obtained containing chromium process water, carry out homogeneous and all measure process and Air Exposure, and after reacting with manganous sulfate, then add after flocculation agent carries out flocculation sediment process, obtain combination treatment water and primary sludge;
C) combination treatment water above-mentioned steps obtained first carries out acidication process, then after carrying out intermediate precipitation process, obtain middle rank process water and in heavy mud;
D), after middle rank process water above-mentioned steps obtained first carries out biological contact oxidization treatment, then after carrying out two-stage precipitation process, the chromate waste water after processing and secondary sludge is obtained.
Preferably, in described heavy mud in comprising heavy returned sluge and in heavy non-reflow mud; Described secondary sludge comprises two heavy returned sluges and two heavy non-reflow mud;
In described, the reflux ratio of heavy returned sluge is less than or equal to 70%; The reflux ratio of described two heavy returned sluges is less than or equal to 80%.
Preferably, after heavy returned sluge mixes with described combination treatment water in described, then carry out step c) ~ d) process;
Described two heavy returned sluges and described middle rank process after water mixes, then carry out steps d) process.
Preferably, by described primary sludge, described in one or more in heavy non-reflow mud and described two heavy non-reflow mud, after carrying out sludge dewatering, then the water deviate from is carried out step b) ~ d) process.
Preferably, after described chromium mud and sulfuric acid reaction, obtain the basic chromium sulfate produced for leather;
Described highly basic is sodium hydroxide and/or potassium hydroxide.
The present invention also provides the treatment system of chromate waste water in a kind of leather waste water, comprises graticule mesh district, water collecting basin, reaction tank, settling tank, equalizing tank, preliminary sedimentation tank, hydrolysis acidification pool, medium sediment pool, contact-oxidation pool and second pond;
The outlet in described graticule mesh district is connected with the entrance of described water collecting basin, and the outlet of described water collecting basin is connected with the entrance of described reaction tank, and the outlet of described reaction tank is connected with the entrance of described settling tank;
The liquid exit of described settling tank is connected with the entrance of described equalizing tank, the outlet of described equalizing tank is connected with the entrance of described preliminary sedimentation tank, the liquid exit of described preliminary sedimentation tank is connected with the entrance of described hydrolysis acidification pool, the outlet of described hydrolysis acidification pool is connected with the entrance of described medium sediment pool, the liquid exit of described medium sediment pool is connected with the entrance of described contact-oxidation pool, and the outlet of described contact-oxidation pool is connected with the entrance of described second pond.
Preferably, described treatment system also comprises sludge dewatering equipment; The sludge outlet of described preliminary sedimentation tank, the sludge outlet of medium sediment pool are connected with the entrances that are one or more and described sludge dewatering equipment in the sludge outlet of second pond.
Preferably, described graticule mesh district comprises one or more in cross grid, horizontal grid, longitudinal grid, the first gridding grille and the second gridding grille.
Preferably, described treatment system also comprises gas blower; The inlet mouth of described equalizing tank is connected with the air outlet of described gas blower respectively with the inlet mouth of described contact-oxidation pool.
Preferably, also ecological pool is provided with between described medium sediment pool and described contact-oxidation pool; The liquid exit of described medium sediment pool is connected with the entrance of described ecological pool, and the outlet of described ecological pool is connected with the entrance of described contact-oxidation pool; Fresh-water fishes have been put in a suitable place to breed in described ecological pool.
The invention provides treatment process and the treatment system of chromate waste water in a kind of leather waste water, first by first for the chromate waste water in leather waste water filtering foreign material, then carry out homogeneous and all measure process, then after reacting with highly basic, finally carry out precipitation process, obtain containing chromium process water; Then above-mentioned steps is obtained containing chromium process water, carry out homogeneous and all measure process and Air Exposure, and after reacting with manganous sulfate, then add after flocculation agent carries out flocculation sediment process, obtain combination treatment water and primary sludge; Combination treatment water above-mentioned steps obtained again first carries out acidication process, then after carrying out intermediate precipitation process, obtain middle rank process water and in heavy mud; After the middle rank process water finally above-mentioned steps obtained first carries out biological contact oxidization treatment, then after carrying out two-stage precipitation process, obtain the chromate waste water after processing and secondary sludge.Experimental result shows, through treatment step of the present invention, the chromate waste water of process, wherein COD content is less than or equal to 60mg/L, BOD content is less than or equal to 20mg/L, suspended solid is less than or equal to 20mg/L, and total chrome content is less than or equal to 0.05mg/L, and ammonia-nitrogen content is less than or equal to 8mg/L, sulfide is less than or equal to 0.5mg/L, pH value is 6.5 ~ 8, can meet secondary standard in " People's Republic of China's integrated wastewater discharge standard " (GB8978-1996), and basic close to primary standard.
Accompanying drawing explanation
Fig. 1 is the treatment system schematic diagram of chromate waste water in leather waste water of the present invention.
Embodiment
In order to understand the present invention further, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these describe just for further illustrating the features and advantages of the present invention, instead of limiting to the claimed invention.
The all raw materials of the present invention, be not particularly limited its source, commercially buy or prepare according to ordinary method well known to those skilled in the art.
The all raw materials of the present invention, be not particularly limited its purity, the present invention preferably adopts analytical pure.
The invention provides the treatment process of chromate waste water in a kind of leather waste water, comprise the following steps:
A) by first for the chromate waste water in leather waste water filtering foreign material, then carry out homogeneous and all measure process, then after reacting with highly basic, finally carry out precipitation process, obtain containing chromium process water and chromium mud;
B) above-mentioned steps is obtained containing chromium process water, carry out homogeneous and all measure process and Air Exposure, and after reacting with manganous sulfate, then add after flocculation agent carries out flocculation sediment process, obtain combination treatment water and primary sludge;
C) combination treatment water above-mentioned steps obtained first carries out acidication process, then after carrying out intermediate precipitation process, obtain middle rank process water and in heavy mud;
D), after middle rank process water above-mentioned steps obtained first carries out biological contact oxidization treatment, then after carrying out two-stage precipitation process, the chromate waste water after processing and secondary sludge is obtained.
First the present invention by first for the chromate waste water in leather waste water filtering foreign material, then carries out homogeneous and all measures process, then with react containing ferro-compound, mineral acid and flocculation agent after, finally carry out precipitation process, obtain containing chromium process water and chromium mud; Described highly basic is preferably sodium hydroxide and/or potassium hydroxide, is more preferably sodium hydroxide or potassium hydroxide, most preferably is sodium hydroxide.The process of the present invention to described chromium mud is not particularly limited, with treatment process well known to those skilled in the art, the present invention preferably by after described chromium mud and sulfuric acid reaction, obtains basic chromium sulfate, again it is mixed with leather tanning agent, be back in leather tanning production process.
Filtering of the present invention is preferably the multi-direction filtering of Pyatyi, thus thoroughly retains the thing such as foreign material, onal meat, fur in chromate waste water; The multi-direction filtering of described Pyatyi is preferably the filtering of one-level cross, the horizontal filtering of secondary, three grades of longitudinal filterings, the filtering of level Four macrolattice, the filtering of Pyatyi small grid; The horizontal filtering of described secondary is preferably horizontal grid filtering, the spacing of the present invention to grid is not particularly limited, and those skilled in the art can be arranged according to practical situation, and spacing of the present invention is preferably 80 ~ 100mm, be more preferably 85 ~ 95mm, most preferably be 87 ~ 92mm; Described three grades of longitudinal filterings are preferably longitudinal grid filtering, the spacing of the present invention to grid is not particularly limited, and those skilled in the art can be arranged according to practical situation, and spacing of the present invention is preferably 60 ~ 80mm, be more preferably 65 ~ 75mm, most preferably be 67 ~ 72mm; Macroreticular shape of the present invention is not particularly limited, and with conventional shape well known to those skilled in the art, the present invention is preferably square or circular; The present invention is not particularly limited macroreticular size, and those skilled in the art can be arranged according to practical situation, and the macroreticular length of side of the present invention or diameter are preferably 20 ~ 50mm, are more preferably 25 ~ 40mm, most preferably are 30 ~ 35mm; The size of the present invention to small grid is not particularly limited, and those skilled in the art can be arranged according to practical situation, and the length of side or the diameter of small grid of the present invention are preferably 5 ~ 15mm, are more preferably 7 ~ 14mm, are more preferably 8 ~ 12mm, most preferably be 10.5 ~ 13mm; The shape of small grid of the present invention is not particularly limited, and with conventional shape well known to those skilled in the art, the present invention is preferably square or circular; The present invention is not particularly limited macroreticular size, and those skilled in the art can be arranged according to practical situation, and the macroreticular length of side of the present invention or diameter are preferably 20 ~ 50mm, are more preferably 25 ~ 40mm, most preferably are 30 ~ 35mm; The size of the present invention to small grid is not particularly limited, and those skilled in the art can be arranged according to practical situation, and the length of side or the diameter of small grid of the present invention are preferably 5 ~ 15mm, are more preferably 7 ~ 14mm, are more preferably 8 ~ 12mm, most preferably be 10.5 ~ 13mm; The present invention is the effect improving filtering foreign material, and described level Four macrolattice and Pyatyi small grid are preferably crisscross arranged, and namely described macroreticular mesh lines and the mesh lines of described small grid intersect oblique setting; The present invention is not particularly limited the foreign material process that described filtering obtains, and with treatment process well known to those skilled in the art, the present invention preferably transports outward professional treatment.The present invention all measures process to described homogeneous and is not particularly limited, and all measures process or arrange according to the treatment capacity of practical condition with leather waste water homogeneous well known to those skilled in the art; The technique of the present invention to described precipitation process is not particularly limited, with sedimentation processing technology well known to those skilled in the art; The present invention is not particularly limited the precipitation after described precipitation process, with treatment process well known to those skilled in the art.
The present invention by the chromate waste water in factory effluent through collect after, first by delivering to reaction tank again after suitable homogeneous is all measured after Pyatyi filtering foreign material, after fully contacting hybrid reaction with the ferro-compound added, mineral acid and flocculation agent, form solids precipitation thing, gravity flow afterwards enters precipitation process, after the chromium-bearing sludge that precipitation process precipitates is discharged by gravity spoil disposal and impeller pump suction mud mode, outward transport process after dehydration; The supernatant liquor obtained, namely containing chromium process water, gravity flow enters subsequent disposal.The present invention adopts specific filter type, treatment condition and treatment step by the process of chromate waste water advanced row order segmentation, effectively avoids the impact of combination treatment plurality of impurities, decreases the cost of wastewater treatment, add effect and the efficiency of wastewater treatment.
The present invention carries out homogeneous containing chromium process water all measure process and Air Exposure by what obtains through above-mentioned steps, and after reacting with manganous sulfate, then adds after flocculation agent carries out flocculation sediment process, obtains combination treatment water and primary sludge; Described flocculation agent is preferably inorganic polymer flocculant and/or organic polymer coargulator, is more preferably inorganic polymer flocculant or organic polymer coargulator, most preferably is inorganic polymer flocculant.
The present invention all measures process to described homogeneous and is not particularly limited, and all measures process or arrange according to the treatment capacity of practical condition with leather waste water homogeneous well known to those skilled in the art; The present invention is not particularly limited described Air Exposure, and with leather waste water Air Exposure well known to those skilled in the art or the Air Exposure according to practical condition, the present invention is preferably air aeration process; The process of the present invention to primary sludge is not particularly limited, with leather method for sludge treatment well known to those skilled in the art or according to practical condition process, after described primary sludge is preferably carried out sludge dewatering by the present invention, the water obtaining dewatered sludge He deviate from; The treatment process of the present invention to described dewatered sludge is not particularly limited, and with treatment process well known to those skilled in the art, the present invention preferably transports outward professional treatment; The present invention to described deviate from the treatment process of water be not particularly limited, with treatment process well known to those skilled in the art, the present invention preferably to described deviate from water again together carry out subsequent step b with described containing chromium process water) ~ d) and process.The present invention is the effect and the efficiency that improve described sludge dewatering, preferably primary sludge is first carried out sludge condensation before carrying out sludge dewatering, the technique of the present invention to described sludge condensation is not particularly limited, with sludge condensation technique well known to those skilled in the art; The treatment process of the present invention to the condensed water that described sludge condensation obtains is not particularly limited, with treatment process well known to those skilled in the art, the present invention preferably together carries out subsequent step b with described containing chromium process water again to described condensed water, the water deviate from) ~ d) process.
The present invention carries out suitable homogeneous by above-mentioned all measure process containing chromium process water, for reinforcing desulfuration effect, appropriate manganous sulfate is added in equalizing tank, pass into air aeration simultaneously, residual sulfur compound is removed through catalyzed oxidation, afterwards with add after flocculation agent reacts again, redeposition process realizes mud-water separation; After the primary sludge that precipitation process precipitates is discharged by gravity spoil disposal and impeller pump suction mud mode, outward transport process after dehydration; The supernatant liquor obtained, i.e. combination treatment water, gravity flow enters sequential hydrolysis acidification.The present invention adopts specific filter type, treatment condition and treatment step that chromate waste water part is carried out stage process, carry out comprehensive treating process again, effectively avoid the impact of plurality of impurities, decrease the cost of wastewater treatment, add effect and the efficiency of wastewater treatment.
The combination treatment water that above-mentioned steps obtains by the present invention first carries out acidication process, then after carrying out intermediate precipitation process, obtain middle rank process water and in heavy mud; In described heavy mud in preferably including heavy returned sluge and in heavy non-reflow mud; In described, the reflux ratio of heavy returned sluge is preferably less than or equal to 70%, is more preferably and is less than or equal to 60%, most preferably be and be less than or equal to 50%; The definition of the present invention to described reflux ratio is not particularly limited, with usual definition well known to those skilled in the art, reflux ratio of the present invention refer to described in circular treatment again in part backflow waste water treatment process in heavy mud, another part then carries out independent sludge treatment, the mud of described circular treatment again and the mass ratio of mud carrying out separately sludge treatment, be reflux ratio; The process of the present invention to mud heavy in described is not particularly limited, with processing mode well known to those skilled in the art, the present invention is preferably by mud heavy in a part, namely heavy returned sluge in, return after mixing with described combination treatment water in treatment process, again carry out step c) ~ d) process.
The present invention is not particularly limited described acidication treatment process, with well known to those skilled in the art for the acidication treatment process in leather waste water process; The treatment process of the present invention to non-reflow mud heavy in described is not particularly limited, with leather method for sludge treatment well known to those skilled in the art or according to practical condition process, after non-reflow mud heavy in described is preferably carried out sludge dewatering by the present invention, the water obtaining dewatered sludge He deviate from; The treatment process of the present invention to described dewatered sludge is not particularly limited, and with treatment process well known to those skilled in the art, the present invention preferably transports outward professional treatment; The present invention to described deviate from the treatment process of water be not particularly limited, with treatment process well known to those skilled in the art, the present invention preferably to described deviate from water again together carry out subsequent step b with described containing chromium process water) ~ d) and process.The present invention is the effect and the efficiency that improve described sludge dewatering, preferably by heavy non-reflow mud before carrying out sludge dewatering, first carry out sludge condensation, the technique of the present invention to described sludge condensation is not particularly limited, with sludge condensation technique well known to those skilled in the art; The treatment process of the present invention to the condensed water that described sludge condensation obtains is not particularly limited, with treatment process well known to those skilled in the art, the present invention preferably together carries out subsequent step b with described containing chromium process water again to described condensed water, the water deviate from) ~ d) process.
The combination treatment water that above-mentioned steps obtains by the present invention is under the effect of acidication microorganism, the macromolecular compound being difficult in water decompose is hydrolyzed into the substrate being easy to be utilized by microorganism through chain rupture, improve the biodegradability of waste water, also can realize the organic removal of part simultaneously.Combination treatment water after hydrolysis carries out mud-water separation through intermediate precipitation process again, in precipitating heavy mud regularly or continuous backflow to be hydrolyzed acidification, can the systematic microbial biomass of guarantor of maximum, meanwhile, the present invention also preferred by heavy sludge reflux carry out homogeneous and all measure process; The supernatant liquor obtained, namely the gravity flow of middle rank process water enters subsequent touch oxide treatment.The present invention adopts specific filter type, treatment condition and treatment step by the process of chromate waste water advanced row order segmentation, carry out comprehensive treating process again, effectively avoid the impact of plurality of impurities, decrease the cost of wastewater treatment, add effect and the efficiency of wastewater treatment, simultaneously acidication microbiological treatment effectively eliminates the macromolecular compound being difficult to decompose in waste water and partial organic substances.
After the middle rank process water obtained through above-mentioned steps is first carried out biological contact oxidization treatment by the present invention, then after carrying out two-stage precipitation process, obtain the chromate waste water after processing and secondary sludge; Described secondary sludge preferably includes two heavy returned sluges and two heavy non-reflow mud; The reflux ratio of described two heavy returned sluges is preferably less than or equal to 80%, is more preferably and is less than or equal to 70%, most preferably be and be less than or equal to 60%; The definition of the present invention to described reflux ratio is not particularly limited, with usual definition well known to those skilled in the art, reflux ratio of the present invention refer to described in circular treatment again in part backflow waste water treatment process in heavy mud, another part then carries out independent sludge treatment, the mud of described circular treatment again and the mass ratio of mud carrying out separately sludge treatment, be reflux ratio; The process of the present invention to described secondary sludge is not particularly limited, with processing mode well known to those skilled in the art, the present invention preferably by a part of secondary sludge, i.e. two heavy returned sluges, return in treatment process and process with described middle rank after water mixes, again carry out steps d) process.
The present invention is not particularly limited described biological contact oxidization treatment method, with well known to those skilled in the art for the biological contact oxidization treatment method in leather waste water process, the present invention preferably carries out described biological contact oxidization treatment under the condition of oxygen enrichment; The treatment process of the present invention to described two heavy non-reflow mud is not particularly limited, with leather method for sludge treatment well known to those skilled in the art or according to practical condition process, after described two heavy non-reflow mud are preferably carried out sludge dewatering by the present invention, the water obtaining dewatered sludge He deviate from; The treatment process of the present invention to described dewatered sludge is not particularly limited, and with treatment process well known to those skilled in the art, the present invention preferably transports outward professional treatment; The present invention to described deviate from the treatment process of water be not particularly limited, with treatment process well known to those skilled in the art, the present invention preferably to described deviate from water again together carry out subsequent step b with described containing chromium process water) ~ d) and process.The present invention is the effect and the efficiency that improve described sludge dewatering, preferably two heavy non-reflow mud are first carried out sludge condensation before carrying out sludge dewatering, the technique of the present invention to described sludge condensation is not particularly limited, with sludge condensation technique well known to those skilled in the art; The treatment process of the present invention to the condensed water that described sludge condensation obtains is not particularly limited, with treatment process well known to those skilled in the art, the present invention preferably together carries out subsequent step b with described containing chromium process water again to described condensed water, the water deviate from) ~ d) process.
Dissolved organic matter, under the condition of heterotrophic microorganism and oxygen enrichment, is converted into CO by the middle rank process water that above-mentioned steps obtains by the present invention
2and H
2o, realizes effective removal of COD, and also some ammonia nitrogen is converted into microorganism cells simultaneously.When the COD of waste water low to certain value time, nitrobacteria starts to preponderate, and under the condition of collecting oxygen, nitrifier is by NH
3-N is oxidized to NO
2-N and NO
3-N, thus effectively reduce COD content and realize biological ammonia nitrogen removal effect.The present invention is also preferred to be hydrolyzed acidification through the middle rank process water cycle of biological contact oxidization treatment again by part, Hydrolysis Acidification the anaerobic denitrifying bacterium that grows can utilize NO
2-N and NO
3-N, and by its denitrification, be converted into N2 and remove from water.Middle rank process water after catalytic oxidation process carries out mud-water separation through two-stage precipitation process again, the secondary sludge precipitated regularly or continuous backflow carry out catalytic oxidation process, can the systematic microbial biomass of guarantor of maximum, meanwhile, the present invention's also preferred acidification that secondary sludge backflow is hydrolyzed; The supernatant liquor obtained, the chromate waste water namely after process, can reach the secondary standard water quality requirement of national sewage discharge, and after can entering IV class waters, then through conventional purification process, its water quality can be drunk for resident's orthobiosis.The present invention adopts specific filter type, treatment condition and treatment step by the process of chromate waste water advanced row order segmentation, collect again and carry out comprehensive treating process, effectively avoid the impact of combination treatment plurality of impurities, decrease the cost of wastewater treatment, add effect and the efficiency of wastewater treatment, biological contact oxidization treatment effectively goes reduce COD content and realize biological ammonia nitrogen removal effect simultaneously.
The present invention is the function improving water treatment purity further and realize process synchronous detection, preferably before middle rank process water carries out biological contact oxidization treatment, first through Ecological Disposal; Thus can in a small amount of waste water of filtering be difficult to decompose macromolecular compound and partial organic substances while, the Real-Time Monitoring of previous processed process water can also be realized; Described Ecological Disposal preferably adopts limnobios to process, and the present invention is not particularly limited described limnobios, with limnobios well known to those skilled in the art, the present invention be preferably in fresh-water fishes, shrimp, freshwater snails and pasture and water one or more.The present invention be improve further water treatment purity and realize process after leather waste water discharge synchronous detection function, preferably after treatment leather waste water discharge before, first discharge again through Ecological Disposal; Thus while reduce further COD content and realizing biological ammonia nitrogen removal effect, can also realize the Real-Time Monitoring of the leather waste water after previous processed; Described Ecological Disposal preferably adopts limnobios to process, the present invention is not particularly limited described limnobios, with limnobios well known to those skilled in the art, the present invention be preferably in fresh-water fishes, shrimp, freshwater snails and pasture and water one or more, be more preferably fresh-water fishes or shrimp, most preferably be fresh-water fishes.
Chromate waste water after process detects by the present invention, experimental result shows, through the above-mentioned treatment process of the present invention, the chromate waste water of process, wherein COD content is less than or equal to 60mg/L, BOD content is less than or equal to 20mg/L, suspended solid is less than or equal to 20mg/L, total chrome content is less than or equal to 0.05mg/L, ammonia-nitrogen content is less than or equal to 8mg/L, and sulfide is less than or equal to 0.5mg/L, and pH value is 6.5 ~ 8, secondary standard in " People's Republic of China's integrated wastewater discharge standard " (GB8978-1996) can be met, and basic close to primary standard.
The present invention also provides the treatment system of chromate waste water in a kind of leather waste water, comprises graticule mesh district, water collecting basin, reaction tank, settling tank, equalizing tank, preliminary sedimentation tank, hydrolysis acidification pool, medium sediment pool, contact-oxidation pool and second pond;
The outlet in described graticule mesh district is connected with the entrance of described water collecting basin, and the outlet of described water collecting basin is connected with the entrance of described reaction tank, and the outlet of described reaction tank is connected with the entrance of described settling tank;
The liquid exit of described settling tank is connected with the entrance of described equalizing tank, the outlet of described equalizing tank is connected with the entrance of described preliminary sedimentation tank, the liquid exit of described preliminary sedimentation tank is connected with the entrance of described hydrolysis acidification pool, the outlet of described hydrolysis acidification pool is connected with the entrance of described medium sediment pool, the liquid exit of described medium sediment pool is connected with the entrance of described contact-oxidation pool, and the outlet of described contact-oxidation pool is connected with the entrance of described second pond.
In order to make the chromate waste water in leather waste water be fully used, chromate waste water after above-mentioned waste water system process, enables the chromate waste water after process meet Standard by the present invention.See the treatment system schematic diagram that Fig. 1, Fig. 1 are chromate waste water in leather waste water of the present invention.
Processing condition in system for processing chrome-containing wastewater of the present invention are identical with above-mentioned treatment process parameter with processing parameter, repeat no longer one by one below.
The present invention by the chromate waste water in leather waste water first through graticule mesh district filtering foreign material, then enter water collecting basin to carry out homogeneous and all measure process, then enter reaction tank, add after reacting containing highly basic, finally enter settling tank and carry out precipitation process, obtain containing chromium process water and chromium mud; Graticule mesh district of the present invention is preferably the multi-direction filtering graticule mesh of Pyatyi, thus thoroughly retains the thing such as foreign material, onal meat, fur in chromate waste water; Described graticule mesh district preferably include in cross grid, horizontal grid, longitudinal grid, the first gridding grille and the second gridding grille one or more; Described cross grid is preferably one-level cross filtering graticule mesh, described horizontal grid is preferably the horizontal filtering graticule mesh of secondary, described longitudinal grid is preferably three grades of longitudinal filtering graticule mesh, described first gridding grille is preferably level Four macrolattice filtering graticule mesh, and described second gridding grille is preferably Pyatyi small grid filtering graticule mesh; The spacing of the present invention to grid is not particularly limited, and those skilled in the art can be arranged according to practical situation, and spacing of the present invention is preferably 80 ~ 100mm, is more preferably 85 ~ 95mm, most preferably is 87 ~ 92mm; Described three grades of longitudinal filtering graticule mesh are preferably longitudinal grid filtering graticule mesh, the spacing of the present invention to grid is not particularly limited, and those skilled in the art can be arranged according to practical situation, and spacing of the present invention is preferably 60 ~ 80mm, be more preferably 65 ~ 75mm, most preferably be 67 ~ 72mm; The shape of macrolattice filtering graticule mesh of the present invention is not particularly limited, and with conventional shape well known to those skilled in the art, the present invention is preferably square or circular; The size of the present invention to macrolattice filtering graticule mesh is not particularly limited, and those skilled in the art can be arranged according to practical situation, and the length of side or the diameter of macrolattice filtering graticule mesh of the present invention are preferably 20 ~ 50mm, are more preferably 25 ~ 40mm, most preferably are 30 ~ 35mm; The size of the present invention to small grid filtering graticule mesh is not particularly limited, those skilled in the art can be arranged according to practical situation, and the length of side or the diameter of small grid filtering graticule mesh of the present invention are preferably 5 ~ 15mm, are more preferably 7 ~ 14mm, be more preferably 8 ~ 12mm, most preferably be 10.5 ~ 13mm; The shape of small grid of the present invention is not particularly limited, and with conventional shape well known to those skilled in the art, the present invention is preferably square or circular; The size of the present invention to macrolattice filtering graticule mesh is not particularly limited, and those skilled in the art can be arranged according to practical situation, and the macroreticular length of side of the present invention or diameter are preferably 20 ~ 50mm, are more preferably 25 ~ 40mm, most preferably are 30 ~ 35mm; The size of the present invention to small grid filtering graticule mesh is not particularly limited, those skilled in the art can be arranged according to practical situation, and the length of side or the diameter of small grid of the present invention are preferably 5 ~ 15mm, are more preferably 7 ~ 14mm, be more preferably 8 ~ 12mm, most preferably be 10.5 ~ 13mm; The present invention is the effect improving filtering foreign material, and described level Four macrolattice filtering graticule mesh and Pyatyi small grid filtering graticule mesh are preferably crisscross arranged, and namely mesh lines and the mesh lines of described small grid filtering graticule mesh of described macrolattice filtering graticule mesh intersect oblique setting; The present invention is not particularly limited the foreign material process that described filtering obtains, and with treatment process well known to those skilled in the art, the present invention preferably transports outward professional treatment.
The present invention by the chromate waste water in factory effluent after collection tube, first by delivering to reaction tank again after suitable homogeneous is all measured after graticule mesh district filtering foreign material, after fully contacting hybrid reaction with the highly basic added, form the throw out of larger particles, gravity flow afterwards enters precipitation process, after the mud that precipitation process precipitates is discharged by gravity spoil disposal and impeller pump suction mud mode, outward transport process after dehydration; The supernatant liquor obtained, namely containing chromium process water, gravity flow enters subsequent disposal.The present invention adopts specific filter type, treatment condition and treatment step that chromate waste water is carried out stage process, effectively avoids the impact of process plurality of impurities, decreases the cost of wastewater treatment, add effect and the efficiency of wastewater treatment.
The present invention will obtain containing chromium process water through above-mentioned steps, pass into equalizing tank and carry out homogeneous and all measure process and Air Exposure, and after adding manganous sulfate reaction, then pass into preliminary sedimentation tank, add after flocculation agent carries out flocculation sediment process, obtain combination treatment water and primary sludge; The air source of the present invention to described Air Exposure is not particularly limited, and with air source well known to those skilled in the art, the present invention is preferably gas blower, is more preferably Root's blower.
The combination treatment water that then above-mentioned steps obtains by the present invention first passes into hydrolysis acidification pool and to be hydrolyzed acidification, then enters after medium sediment pool carries out intermediate precipitation process, obtain middle rank process water and in heavy mud; Middle rank process water above-mentioned steps obtained again first passes into after contact-oxidation pool carries out biological contact oxidization treatment, then enters after second pond carries out two-stage precipitation process, obtains the chromate waste water after processing and secondary sludge.
Described treatment system preferably also comprises sludge dewatering equipment; Preferably the sludge outlet of described preliminary sedimentation tank, the sludge outlet of medium sediment pool are connected with the entrances that are one or more and described sludge dewatering equipment in the sludge outlet of second pond.Described treatment system preferably also comprises gas blower; Preferably the inlet mouth of described equalizing tank is connected with the air outlet of described gas blower respectively with the inlet mouth of described contact-oxidation pool.
The present invention preferably by the sludge outlet of described primary sludge through described preliminary sedimentation tank, enters from the entrance of sludge dewatering equipment, after carrying out sludge dewatering, and the water obtaining dewatered sludge He deviate from; The treatment process of the present invention to described dewatered sludge is not particularly limited, and with treatment process well known to those skilled in the art, the present invention preferably transports outward professional treatment; The present invention to described deviate from the treatment process of water be not particularly limited, with treatment process well known to those skilled in the art, the present invention preferably to described deviate from water again together send into equalizing tank with described containing chromium process water, carry out subsequent step b) ~ d) process.The present invention is the effect and the efficiency that improve described sludge dewatering, preferably primary sludge is first passed into before carrying out sludge dewatering sludge concentrator and carry out sludge condensation, the technique of the present invention to described sludge condensation is not particularly limited, with sludge condensation technique well known to those skilled in the art; The treatment process of the present invention to the condensed water that described sludge condensation obtains is not particularly limited, with treatment process well known to those skilled in the art, the present invention preferably again together sends into equalizing tank containing chromium process water and carries out subsequent step b with described described condensed water, the water deviate from) ~ d) process.
The present invention preferably sinks mud through the sludge outlet of described medium sediment pool in described, enters from the entrance of sludge dewatering equipment, after carrying out sludge dewatering, and the water obtaining dewatered sludge He deviate from; The treatment process of the present invention to described dewatered sludge is not particularly limited, and with treatment process well known to those skilled in the art, the present invention preferably transports outward professional treatment; The present invention to described deviate from the treatment process of water be not particularly limited, with treatment process well known to those skilled in the art, the present invention preferably to described deviate from water again together send into equalizing tank with described containing chromium process water, carry out subsequent step b) ~ d) process.The present invention is the effect and the efficiency that improve described sludge dewatering, preferably by heavy mud before carrying out sludge dewatering, first pass into sludge concentrator carry out sludge condensation, the technique of the present invention to described sludge condensation is not particularly limited, with sludge condensation technique well known to those skilled in the art; The treatment process of the present invention to the condensed water that described sludge condensation obtains is not particularly limited, with treatment process well known to those skilled in the art, the present invention preferably again together sends into equalizing tank containing chromium process water and carries out subsequent step b with described described condensed water, the water deviate from) ~ d) process.The present invention preferably will heavy mud in a part, and namely, heavy returned sluge, returns after mixing with described combination treatment water in hydrolysis acidification pool, again carry out step c) ~ d) process.
The present invention preferably by the sludge outlet of described secondary sludge through described second pond, enters from the entrance of sludge dewatering equipment, after carrying out sludge dewatering, and the water obtaining dewatered sludge He deviate from; The treatment process of the present invention to described dewatered sludge is not particularly limited, and with treatment process well known to those skilled in the art, the present invention preferably transports outward professional treatment; The present invention to described deviate from the treatment process of water be not particularly limited, with treatment process well known to those skilled in the art, the present invention preferably to described deviate from water again together send into equalizing tank with described containing chromium process water, carry out subsequent step b) ~ d) process.The present invention is the effect and the efficiency that improve described sludge dewatering, preferably secondary sludge is first passed into before carrying out sludge dewatering sludge concentrator and carry out sludge condensation, the technique of the present invention to described sludge condensation is not particularly limited, with sludge condensation technique well known to those skilled in the art; The treatment process of the present invention to the condensed water that described sludge condensation obtains is not particularly limited, with treatment process well known to those skilled in the art, the present invention preferably again together sends into equalizing tank containing chromium process water and carries out subsequent step b with described described condensed water, the water deviate from) ~ d) process.The present invention is preferably by a part of secondary sludge, i.e. two heavy returned sluges, return in contact-oxidation pool and process with described middle rank after water mixes, again carry out steps d) process.
The present invention is the function improving water treatment purity further and realize process synchronous detection, preferably before middle rank process water carries out biological contact oxidization treatment, first carries out Ecological Disposal through ecological pool; Thus can in a small amount of waste water of filtering be difficult to decompose macromolecular compound and partial organic substances while, the Real-Time Monitoring of previous processed process water can also be realized; Described ecological pool has preferably put limnobios in a suitable place to breed, and the present invention is not particularly limited described limnobios, with limnobios well known to those skilled in the art, the present invention be preferably in fresh-water fishes, shrimp, freshwater snails and pasture and water one or more.The present invention be improve further water treatment purity and realize process after chromate waste water discharge synchronous detection function, preferably after treatment chromate waste water discharge before, first carry out Ecological Disposal through ecological pool and discharge again; Thus while reduce further COD content and realizing biological ammonia nitrogen removal effect, can also realize the Real-Time Monitoring of the chromate waste water after previous processed; Described ecological pool has preferably put limnobios in a suitable place to breed, the present invention is not particularly limited described limnobios, with limnobios well known to those skilled in the art, the present invention be preferably in fresh-water fishes, shrimp, freshwater snails and pasture and water one or more, be more preferably fresh-water fishes or shrimp, most preferably be fresh-water fishes.
The present invention adopts specific graticule mesh district Pyatyi filter type, treatment condition and treatment step are by the process of chromate waste water advanced row order segmentation, carry out comprehensive treating process again, effectively avoid the impact of plurality of impurities, decrease the cost of wastewater treatment, add effect and the efficiency of wastewater treatment, in hydrolytic tank acidication microbiological treatment effectively eliminate in waste water be difficult to decompose macromolecular compound and partial organic substances, in contact-oxidation pool, biological contact oxidization treatment can effectively go reduce COD content and realize biological ammonia nitrogen removal effect, the present invention is also provided with ecological pool, thus improve the function of water treatment purity and realization process synchronous detection further.
Leather waste water chromate waste water after above-mentioned treatment system process detects by the present invention, experimental result shows, through the above-mentioned treatment system of the present invention, the chromate waste water of process, wherein COD content is less than or equal to 60mg/L, BOD content is less than or equal to 20mg/L, suspended solid is less than or equal to 20mg/L, total chrome content is less than or equal to 0.05mg/L, ammonia-nitrogen content is less than or equal to 8mg/L, sulfide is less than or equal to 0.5mg/L, pH value is 6.5 ~ 8, secondary standard in " People's Republic of China's integrated wastewater discharge standard " (GB8978-1996) can be met, and it is basic close to primary standard.
In order to understand the present invention further, be described in detail to the treatment process of chromate waste water in leather waste water provided by the invention and treatment system below in conjunction with embodiment, protection scope of the present invention is not limited by the following examples.
Embodiment 1
First by the chromate waste water in leather waste water first through graticule mesh district filtering foreign material, then enter water collecting basin to carry out homogeneous and all measure process, enter reaction tank again, add after ferrous sulfate, sulfuric acid and inorganic polymer flocculant react, finally enter settling tank and carry out precipitation process, obtain containing chromium process water;
Then above-mentioned steps is obtained containing chromium process water, pass into equalizing tank and carry out homogeneous and all measure process, and use gas blower to carry out Air Exposure, and after adding manganous sulfate reaction, pass into preliminary sedimentation tank again, add after flocculation agent carries out flocculation sediment process, obtain combination treatment water and primary sludge;
Combination treatment water above-mentioned steps obtained again first passes into hydrolysis acidification pool and to be hydrolyzed acidification, then enters after medium sediment pool carries out intermediate precipitation process, obtain middle rank process water and in heavy mud;
The middle rank process water finally above-mentioned steps obtained first passes into after contact-oxidation pool carries out biological contact oxidization treatment, then enters after second pond carries out two-stage precipitation process, obtains the chromate waste water after processing and secondary sludge.
Chromate waste water after above-mentioned treatment step process is detected, experimental result shows, through the chromate waste water of the present embodiment process, wherein COD content is 50mg/L, BOD content is 18mg/L, suspended solid is 20mg/L, total chrome content is 0.05mg/L, and ammonia-nitrogen content is 8mg/L, and sulfide equals 0.5mg/L, pH value is 8, meets secondary standard in " People's Republic of China's integrated wastewater discharge standard " (GB8978-1996).
Embodiment 2
First by the chromate waste water in leather waste water first through graticule mesh district filtering foreign material, then enter water collecting basin to carry out homogeneous and all measure process, enter reaction tank again, add after ferrous sulfate, sulfuric acid and inorganic polymer flocculant react, finally enter settling tank and carry out precipitation process, obtain containing chromium process water;
What then above-mentioned steps obtained passes into equalizing tank containing chromium process water and carries out homogeneous and all measure process, and use gas blower to carry out Air Exposure, and after adding manganous sulfate reaction, then pass into preliminary sedimentation tank, add after flocculation agent carries out flocculation sediment process, obtain combination treatment water and primary sludge;
Combination treatment water above-mentioned steps obtained again first passes into hydrolysis acidification pool and to be hydrolyzed acidification, then passes into ecological pool biochemical treatment, then enters after medium sediment pool carries out intermediate precipitation process, obtain middle rank process water and in heavy mud;
The middle rank process water finally above-mentioned steps obtained first passes into after contact-oxidation pool carries out biological contact oxidization treatment, then enter after second pond carries out two-stage precipitation process, after carrying out biochemical treatment by ecological pool again, obtain the chromate waste water after processing and secondary sludge.
Simultaneously, by the mud of medium sediment pool and the mud of second pond, wherein the reflux ratio of the returned sluge of medium sediment pool is 70%, the reflux ratio of the returned sluge of second pond is 80%, feeding hydrolysis acidification pool and contact-oxidation pool carry out circular treatment respectively, then by the mud of preliminary sedimentation tank, medium sediment pool non-reflow mud, second pond non-reflow mud sends into sludge dewatering equipment processed through sludge concentrator, and water processed obtained sends into equalizing tank circular treatment.
Chromate waste water after above-mentioned treatment step process is detected, experimental result shows, through the chromate waste water of the present embodiment process, wherein COD content is 30mg/L, BOD content is 10mg/L, suspended solid is 18mg/L, total chrome content is 0.04mg/L, and ammonia-nitrogen content is 5mg/L, and sulfide equals 0.3mg/L, pH value is 7, meets secondary standard in " People's Republic of China's integrated wastewater discharge standard " (GB8978-1996).
The explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection domain of the claims in the present invention.
To the above-mentioned explanation of the disclosed embodiments, professional and technical personnel in the field are realized or uses the present invention.To be apparent for those skilled in the art to the multiple amendment of these embodiments, General Principle as defined herein can without departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention can not be restricted to these embodiments shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (10)
1. the treatment process of chromate waste water in leather waste water, comprises the following steps:
A) by first for the chromate waste water in leather waste water filtering foreign material, then carry out homogeneous and all measure process, then after reacting with highly basic, finally carry out precipitation process, obtain containing chromium process water and chromium mud;
B) above-mentioned steps is obtained containing chromium process water, carry out homogeneous and all measure process and Air Exposure, and after reacting with manganous sulfate, then add after flocculation agent carries out flocculation sediment process, obtain combination treatment water and primary sludge;
C) combination treatment water above-mentioned steps obtained first carries out acidication process, then after carrying out intermediate precipitation process, obtain middle rank process water and in heavy mud;
D), after middle rank process water above-mentioned steps obtained first carries out biological contact oxidization treatment, then after carrying out two-stage precipitation process, the chromate waste water after processing and secondary sludge is obtained.
2. treatment process according to claim 1, is characterized in that, in described heavy mud in comprising heavy returned sluge and in heavy non-reflow mud; Described secondary sludge comprises two heavy returned sluges and two heavy non-reflow mud;
In described, the reflux ratio of heavy returned sluge is less than or equal to 70%; The reflux ratio of described two heavy returned sluges is less than or equal to 80%.
3. treatment process according to claim 2, is characterized in that, after heavy returned sluge mixes with described combination treatment water in described, then carries out step c) ~ d) process;
Described two heavy returned sluges and described middle rank process after water mixes, then carry out steps d) process.
4. treatment process according to claim 2, it is characterized in that, by described primary sludge, described in one or more in heavy non-reflow mud and described two heavy non-reflow mud, after carrying out sludge dewatering, then the water deviate from is carried out step b) ~ d) process.
5. treatment process according to claim 1, is characterized in that, after described chromium mud and sulfuric acid reaction, obtains the basic chromium sulfate produced for leather;
Described highly basic is sodium hydroxide and/or potassium hydroxide.
6. the treatment system of chromate waste water in leather waste water, comprises graticule mesh district, water collecting basin, reaction tank, settling tank, equalizing tank, preliminary sedimentation tank, hydrolysis acidification pool, medium sediment pool, contact-oxidation pool and second pond;
The outlet in described graticule mesh district is connected with the entrance of described water collecting basin, and the outlet of described water collecting basin is connected with the entrance of described reaction tank, and the outlet of described reaction tank is connected with the entrance of described settling tank;
The liquid exit of described settling tank is connected with the entrance of described equalizing tank, the outlet of described equalizing tank is connected with the entrance of described preliminary sedimentation tank, the liquid exit of described preliminary sedimentation tank is connected with the entrance of described hydrolysis acidification pool, the outlet of described hydrolysis acidification pool is connected with the entrance of described medium sediment pool, the liquid exit of described medium sediment pool is connected with the entrance of described contact-oxidation pool, and the outlet of described contact-oxidation pool is connected with the entrance of described second pond.
7. treatment system according to claim 6, is characterized in that, described treatment system also comprises sludge dewatering equipment; The sludge outlet of described preliminary sedimentation tank, the sludge outlet of medium sediment pool are connected with the entrances that are one or more and described sludge dewatering equipment in the sludge outlet of second pond.
8. treatment system according to claim 6, is characterized in that, described graticule mesh district comprise in cross grid, horizontal grid, longitudinal grid, the first gridding grille and the second gridding grille one or more.
9. treatment system according to claim 6, is characterized in that, described treatment system also comprises gas blower; The inlet mouth of described equalizing tank is connected with the air outlet of described gas blower respectively with the inlet mouth of described contact-oxidation pool.
10. treatment system according to claim 6, is characterized in that, is also provided with ecological pool between described medium sediment pool and described contact-oxidation pool; The liquid exit of described medium sediment pool is connected with the entrance of described ecological pool, and the outlet of described ecological pool is connected with the entrance of described contact-oxidation pool;
Fresh-water fishes have been put in a suitable place to breed in described ecological pool.
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| CN102503039A (en) * | 2011-11-14 | 2012-06-20 | 安徽银河皮革有限公司 | Nuisanceless leather wastewater treatment method |
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| CN101239769A (en) * | 2008-02-01 | 2008-08-13 | 浙江大学 | Leather-making waste water reusing treatment method |
| CN101353196A (en) * | 2008-09-21 | 2009-01-28 | 河北华斯实业集团有限公司 | Fur nitro dyeing wastewater treatment and cyclic utilization method |
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