CN1006223B

CN1006223B - Intensified biochemical treament of wastewater containing phenol and cyanide

Info

Publication number: CN1006223B
Application number: CN87100532.8A
Authority: CN
Inventors: 曾锦之
Original assignee: ANSHAN COKING REFRACTORY MATER
Current assignee: ANSHAN COKING REFRACTORY MATER
Priority date: 1987-01-26
Filing date: 1987-01-26
Publication date: 1989-12-27
Also published as: CN87100532A

Abstract

The present invention relates to a method for treating industrial waste water containing phenol and cyanide, particularly to for treating coking industrial waste water containing phenol and cyanide. The present invention relates to a method for strengthening biochemical treatment phenol and cyanide waste water by adding glucose growth hormone, and simultaneously, and an additive which is similar to a brown iron oxide is added. The present invention not only guarantees the advantage that phenol, cyanide and thiocyanide in the waste water are removed effectively by adding the growth hormone. The problems of sludge bulking, upward floating and running away are solved by adding the additive, and the removing rate of COD and sulfide is improved. The method is a phenol and cyanide waste water treatment method with simple technology, convenient operation and low cost.

Description

Strengthen the method for biochemical treatment wastewater containing phenol and cyanide

The invention belongs to method of wastewater treatment, be used to contain phenol cyanogen trade effluent.

The industrial wastewater containing phenol and cyanide that contains, particularly coking contains that wastewater containing phenol and cyanide is mainly derived from remained ammonia (discharging) after ammonia still process, crude benzol workshop section divides dried up, that tar and crude benzene refining divide is dried up, gas final cold sewer etc., just directly do not efflux as treated, water body outside the meeting severe contamination factory, the harm people ' s health.

At present, industrial processing contains wastewater containing phenol and cyanide, the employing biochemical processing method is more, the domestic biochemical device of China adopts biosorption process mostly, short in view of aeration time, volumetric loading big, the pre-treatment imperfection, add the reason of the aspects such as back operational administrative of going into operation, cause the waste water after the biochemical treatment, do not reach the standard that effluxes of national regulation.

According to Britain's " research of Water Rcsearch(water) " 1972.P1459-74,1973.P1137-53 " adding the method for growth hormone in waste water " that people such as J.P.Cooper of British Coke Research Association that puts down in writing on the magazine and R.L.Catchpole propose handles wastewater containing phenol and cyanide, begin to propose to add the pyruvic acid of some amount, with the composition of enzyme in the additional bacterium, thereby improve treatment effect.But because pyruvic acid is more valuable industrial chemicals, improving the biochemical treatment effect with it, is irrational economically.So people such as J.R.Cooper had proposed again to replace pyruvic acid with cheap glucose afterwards, because glucose growth hormone all at first changes into pyruvic acid no matter under aerobic or anaerobic condition.Pyruvic acid has perfected enzyme system in the bacterium, has improved the biochemical treatment effect, effectively the phenol in the degradation of sewage, prussiate, thiocyanide.But add that growth hormone can not increase sludge concentration (MLSS) but strengthen the volume index (SVI) of mud, make the active sludge come-up that lightens, very easily expand and run off, though in addition the clearance of COD is had certain effect, but very not obvious, also very low to the clearance of sulfide.

In view of the foregoing, the objective of the invention is to seek both to keep the saving grace that adds growth hormone, the materials such as phenol, prussiate, thiocyanide of promptly degrading effectively solve sludge bulking and this big disadvantage and improve a kind of method of strengthening the biochemical treatment wastewater containing phenol and cyanide of COD, sulfide clearance of running off again.

For realizing this purpose, take the measure of " when adding growth hormone-glucose, also dropping into a certain amount of brown iron oxide ", thereby solved the problem of mud come-up, reduced sludge index (SVI) and made sulfide and the clearance of COD obviously improves.So that " add growth hormone strengthen biochemical processing method " small-scale test that the people did such as the J.R.Cooper of British Coke Research Association is able to broadened application on technical scale.

The invention has the advantages that to increase any structures, and the price of employed glucose growth hormone and brown iron oxide is very cheap, 1 meter of the every processing in aeration tank ³Waste water only need be spent more 2～3 fens; And treatment effect is good again, so be the method for a kind of technology processing wastewater containing phenol and cyanide simple, easy to operate, with low cost.

The ultimate principle that adds the growth hormone method is: the degradation by bacteria dirt, and what play a major role is enzyme in the bacterium, and enzyme is a biological catalyst, does not have enzyme, and all metabolism all will stop, and if enzyme system is unsound, then degradation material is not thorough yet.

The purpose that adds growth hormone provides material conditions for perfecting enzyme system exactly, is not to satisfy the needs of bacterium to the carbon source and the energy, is harmful to because facts have proved to have thrown on the contrary more.

In the metabolism of bacterium to carbohydrate, pyruvic acid is the intermediate product of a key, and the glucose growth hormone that is added is because molecule is very little, can be without the lytic enzyme effect of bacterium, directly permeate through cell membranes enters in the cell, under the intracellular enzyme effect, change into pyruvic acid.

After the glucose that adds generates pyruvic acid, proceed decomposition reaction, generate the material of oxidized form (only proceeding to the decarboxylation stage) and non-oxide type two big classes, they are absorbed as synthetic plasmic raw material, because dosage seldom, no longer further decomposition enters the tricarboxylic acid cycle stage, thereby has perfected enzyme system.

Breakdown of glucose becomes the reaction skeleton symbol of pyruvic acid as follows:

C ₆H ₁₂O ₆+2NAD+2H ₃PO ₄+2ADP

2CH ₃COCOOH+2NADH ₂+2ATP

Wherein: C ₆H ₁₂O ₆-glucose

CH ₃The COCOOH-pyruvic acid

NAD-nadide (niacinamide usp, purine two nucleic acid) oxidized form

H ₃PO ₄-phosphoric acid

NADH ₂-nadide (niacinamide usp, purine two nucleic acid) reduced form

The ATP-adenosine triphyosphate

The ADP-adenosine diphosphate (ADP)

ATP

The ADP+ energy

Drop into croci, its main purpose has been a carrier function.Because its granularity is little, account for more than 50% less than 20 μ persons and (please see table 2), there is certain specific surface area (to reach 0.6m ²/ g), and the free bacteria that the attached suction of energy is run off easily, thus sludge concentration improved.Along with drainage water becomes subacidity, mud also is subacidity, and this makes croci (Fe ₂O ₃) have minimum part to dissociate, generate Fe ^{+ 3}Ion is with the S in the sulfide ^-2Ion combination generates Fe ₂S ₃Because of Fe ₂S ₃Be black, after sludge absorption, also make mud be black.Compound is discharged with mud, thereby has improved the clearance of sulfide.

According to Fig. 1 and embodiment the technical process of the inventive method is elaborated.

Fig. 1 is for strengthening the process flow sheet of biochemical treatment wastewater containing phenol and cyanide with adding glucose growth hormone and brown iron oxide.

(I) wastewater containing phenol and cyanide among the figure, (2) industrial fresh water, (3) equalizing tank, (4) aeration tank, (5) glucose growth hormone, (6) brown iron oxide, (7) settling tank, (8) efflux wastewater, (9) returned sluge, (10) send the mud of handling workshop section.

The trade effluent (1) that will contain phenol cyanogen, especially derive from remained ammonia (after ammonia still process, discharging) in the coking industry, crude benzol workshop section divides dried up, tar and crude benzene refining divide dried up, (wherein crude benzol workshop section divides dried up need through removing the benzene pre-treatment to the gas final cold sewer, tar and crude benzene refining divide dried up need through the oil removing pre-treatment) send into equalizing tank (3) with industrial fresh water (2) and regulate, for guaranteeing the optimum handling effect, make handled waste water, its pH value is 6.5～8.5,15～32 ℃ of water temperatures, COD import value＜800mg/L, send into aeration tank (4) again, the RS Regenerator Section in the aeration tank drops into the glucose growth hormone (5) of 3～4mg/L and the brown iron oxide (6) of mud gross weight 10%

(so that MLVSS/MLSS is as the criterion in 0.4～0.7 scope, wherein MLVSS is a volatile sludge concentration, and MLSS is a sludge concentration), the aeration time of aeration tank is 7～8 hours, the COD of aeration tank removes volumetric loading Fv=1.5～2.5kg COD/m ³.d, in the aeration tank, also to add an amount of phosphoric acid or phosphoric acid salt, to satisfy the metabolic needs of microorganism, waste water behind the aeration is sent into settling tank (7) again, efflux wastewater (8) is separated with mud, make the waste water after handling through aeration that enough dissolved oxygens (DO) be arranged, should guarantee to reach 2.5～3.5mg/L(and rely on that air blast realizes in the waste water).Reason is, if dissolved oxygen (DO) quantity not sufficient, the advantage performance of this method decyanation is not come out, but excessive when the DO amount, can occur containing ammoniacal substance again, produces nitrite anions in advance.Denitrification phenomenon except increasing the COD value, also may take place in the appearance of nitrite anions in settling tank, cause the mud come-up, make active sludge (9) return the aeration tank, be to guarantee the optimum handling effect, its reflux ratio is with 200～300% be advisable (through verification experimental verification).Purpose is to strengthen reflux ratio can make the sludge retention time in the settling tank can not be long, even a small amount of nitrite anions appears in the aeration tank, also can not cause denitrification phenomenon, just can not cause the mud come-up, excess sludge (10) will be delivered to sludge treatment workshop section and handle.

Table 1 shows the emission standard of China's Iron And Steel Industry coked waste water.

Table 2 shows the total analysis result of brown iron oxide.

Table 3 shows the annual index of handling the phenol-cyanogen sewage of Benxi coking subsidiary factory of North Platform Steel Plant with the inventive method, maximum monthly average index and maximum desired value.

Embodiment 1,

The phenol amount that contains when the phenol-cyanogen sewage of coking subsidiary factory of Benxi North Platform Steel Plant enters the aeration tank is 137mg/L, prussiate is that 20.2mg/L, COD are that 684mg/L, thiocyanide are 79.37mg/L, after present method processing, aeration tank outlet waste water contains phenol 0.08mg/L, and clearance is 99.94%; Contain prussiate 0.08mg/L, clearance 99.6% contains COD155mg/L, and clearance is 77.34%; Contain sulfohydrate 2.59mg/L, clearance is 96.74%.

Embodiment 2

Containing phenol when the phenol-cyanogen sewage of coking subsidiary factory of Benxi North Platform Steel Plant enters the aeration tank is that 250mg/L, prussiate are that 19.8mg/L, COD are 1205.08mg/L, thiocyanide 141.70mg/L, and after handling with present method, it is 0.145 that aeration tank outlet waste water contains phenol

Table 1. China Iron And Steel Industry coked waste water emission standard

（GB4911-4913～85）

A-newly founds the factory, and B-has factory now

The total analysis result of table 2. brown iron oxide

(physicochemical property analysis)

(sreen analysis)

Table 3, handle annual index, maximum monthly average index and the maximum desired value of the phenol-cyanogen sewage of Benxi coking subsidiary factory of North Platform Steel Plant with the inventive method.

Annotate 1: press criterion calculation shown in the table 1.

Mg/L, clearance are 99.94%; Containing prussiate is 0.12mg/L, and clearance is 99.39%; Containing COD is 273.4mg/L, and clearance is 77.27%; Containing thiocyanide is 4.3mg/L, and clearance is 96.97%.

Claims

1, a kind of usefulness adds the method that glucose growth hormone is strengthened the biochemical treatment wastewater containing phenol and cyanide, it is characterized in that:

A) dosage of glucose growth hormone is 3～4mg/L;

B) when adding glucose, also add croci, its granularity is for to account for more than 50% less than 20 μ persons, and dosage is 10% of a mud gross weight, is as the criterion in 0.4～0.7 scope with MLVSS/MLSS.

C) handled waste water with temperature be that 15～32 ℃, pH value are 6.5～8.5, to remove volumetric loading be 1.5～2.5kg COD/m for COD import value＜800mg/L, COD ³.d treatment effect the best the time;

D) in the biochemical treatment process, the reflux ratio of active sludge is advisable with 200%～300%.

2, method of wastewater treatment according to claim 1, it is characterized in that handled waste water is to derive from the industrial any wastewater containing phenol and cyanide that contains, the especially coking industry to need to divide dried up need to divide dried up, gas final cold sewer etc. to contain wastewater containing phenol and cyanide through the pretreated tar of oil removing and crude benzene refining through removing remained ammonia, crude benzol workshop section that benzene handles.

3, processing method for waste water according to claim 1, the waste water after the biochemical treatment that it is characterized in that coming out from settling tank should guarantee that dissolved oxygen (DO) is 2.5～3.5mg/L.