CN1396126A - Process and gas-film air tower for treating hydrazine contained sewage generated in production of azodimethylamide - Google Patents

Abstract

A process for treating the hydrazine-contained sewage generated during production of azodimethylamide features use of a gas-film air tower, and includes such steps as deposition, introducing supernatant to a pre-treater, adding calcium carbide dregs or lime, blowing-oxidizing in the gas-film tower, defoaming tail gas, cyclone separation, heat exchange, adsorbing by sulfuric acid in an absorption tower, exhausting tail gas, press-filtering of oxidizing liquid from the said gas-film tower, biochemical homogenizing, mixing with city sewage, anaenbic biochemical treating, depositing, and aerobic biochemical treating. Its advantages are no environmental pollution, and low cost.

Description

Hydrazine-containing water processing method and air film void tower that Celogen Az production etc. produce

Technical field

The present invention relates to high salinity, high ammonia nitrogen, acidity, the treatment process that contains hydrazine organic wastewater and equipment thereof that a kind of Celogen Az (being called for short: AC or ADC) blowing agent production produces.

Background technology

The composite product of AC blowing agent and modification is the auxiliary agent for the various plastics such as PVC, PE, ABS, SBS and rubber foaming. Because its nontoxic, odorless, pollution-free all can use various soft and hard plastics, therefore, makes it to become the topmost blowing agent of current plastics and rubber. China produces the AC blowing agent and starts from the sixties, so far manufacturer has reached family more than 30, spreads all over the ground such as Jiangsu, Shanghai, Zhejiang, Fujian, Guangzhou and Yunnan, and the whole nation produced about about 60,000 tons of AC in 2000, be the country of output maximum in the world, account for 1/4th of Gross World Product. Along with the raising of common people to environmental quality requirement; the natural resources such as conserve forests has become each national conscious action, is inexorable trend to mould Dai Mu, and; concerning China; light industrial goods is as the strong industry after entering the GATT, and Plastic Rubber Products will be rapidly developed, and then drives the growth of AC product; according to the insiders prediction; China 10 years from now on, the AC product will be being not less than the development of 5% annual growth, and be developed as developing direction with scale, environmental protection, PP Pipe Compound.

The AC production method has ketone connection nitrogen method and urea method, the state such as America and Europe and Korea S adopts ketone connection nitrogen method mostly, though its three wastes lack than urea method, but still have certain pollution, therefore, the low third world countries that require shift external AC manufacturer from environment high request country to environment process units one after another, then, repurchase or import AC crude product carry out composite modifiedly, anti-market to former exported country or other the 3rd state again, reach to evade environmental pollution and earn again the enormous profits purpose.

Domestic AC production process route is single, backward in technique, except having a 8000t/a production line that is shifted to introduce by Korea S, Kunming, Yunnan Province adopts the ketone connection nitrogen method, all other adopts the urea method process route, the advantage of urea method is that raw material is easy to get, technique is simple, small investment, cost are low, and shortcoming is of low quality, serious three wastes. The operations such as urea method production AC mainly contains hydrazine preparation, biruea condensation and washing, biruea oxidation and washing, AC is centrifugal and dry, wherein, condensed mother liquor and high concentration washings (be collectively referred to as and contain hydrazine organic wastewater) in biruea condensation and washing procedure generation are acid, contain the pollutants such as a large amount of CODcr (chemical oxygen consumption (COC)), ammonia nitrogen, sulfate radical and hydrazine hydrate in the water, take Zhejiang company as example, the concentration of emission of each pollutant is respectively in this strand waste water: CODcr 753～5465mg/l, average 3366mg/l, ammonia nitrogen 10678～19516mg/l, average 13593mg/l, hydrazine hydrate 82～384mg/l, average 190mg/ l, sulfate radical 30112～56596mg/l, average 40099mg/l, total emission volumn account for whole AC production process: 98.62%, 98.42%, 99.93%. 100%, be main during AC produces also be one waste water of refractory reason, Beijing Chemical Research Institute, Zhejiang University etc. are with its qualitative awkward biochemical organic wastewater. Before this, domestic all feasible improvement technology and the recovery schemes of economic technology that there is no, the treatment technology of this waste water also becomes numerous AC manufacturer and realizes that scale in " control is two up to standard " and the enterprise opens up the road blocking tiger of development thus.

For solving this burst high salinity, high ammonia nitrogen, acidity, containing hydrazine organic wastewater, domestic and international many scientific workers have carried out a large amount of research, have put into practice work, the whole bag of tricks constantly is suggested, part has been applied to actual production, now is listed below one by one: method one, bleaching powder (or bleaching powder seminal fluid) oxidizing process:

The bleaching powder Main Ingredients and Appearance is clorox, the Main Ingredients and Appearance of bleaching powder seminal fluid is calcium hypochlorite, clorox (calcium) is unstable in water, easily emit oxygen and the chlorine of nascent state, the oxygen of nascent state and chlorine have very strong oxidability, organic matter in the energy oxidize water, thus the CODcr value reduced. Its technical process is that waste water through precipitation, then with after other low pollutant effluents mixes send biochemical treatment again through the bleaching powder oxidation when containing. The method engineering test is the result show, the CODcr clearance can reach 78%, and ammonia nitrogen can remove 35%. Advantage is: treatment process is simple, reduced investment; Shortcoming is: in wastewater treatment process, because chlorine discharges, easily cause secondary pollution and equipment corrosion, in addition, not good to ammonia nitrogen and hydrazine hydrate treatment effect, make the carbon-nitrogen ratio of originally imbalance more serious, add that a large amount of sulfate radicals still stay in water, make the waste water can not qualified discharge, can not process again by biochemistry again. Method two, adsorbed gas formulation:

Its technological principle and process are, waste water is by the interior adsorption column that the modified function polymeric sorbent is housed, remove most of sulfate radical in the waste water through absorption, regulate water to strong basicity with sodium carbonate again, afterwards through air lift, the tail gas water absorbs weak aqua ammonia processed, and with this weak aqua ammonia adsorption column that washs, regenerates, simultaneously, pay the product ammonium sulfate liquor. The method is that Nanjing University develops, only carry out the simulated wastewater Processing Test, result of the test shows that ammonia nitrogen removal frank can reach 97%, and the problem of its existence is: do not carry out the test of actual AC waste water, to CODcr and diazanyl originally to no effect, it is higher to go out salinity water, must further process, in addition, need a large amount of consumption sodium carbonate and add ammoniacal liquor, so processing cost is high. Method three, crystallization one concentration method:

Owing to contain sodium sulphate, ammonium sulfate and a certain amount of sodium chloride, the ammonium chloride of high concentration in the hydrazine hydrate, not only directly biochemical treatment. And waste in a large number useful material. For this reason, produce the ammonium chloride principle with reference to the connection alkaline process, high-concentration waste water is adopted separate the recycling scheme, namely waste water is after just heavy flocculation, and supernatant is refrigerated to 0 ℃, and crystallize out sal glauberi, mother liquor are again through evaporation and concentration. Cool off freezing, respectively precipitated sodium chloride, ammonium chloride and ammonium sulfate, the residue mother liquor returns port system and joins urea. Its advantage is: closed cycle is without the three wastes. Shortcoming is: recovery technique is long, investment is large, energy consumption is high, and operating cost is high, and the recovery product is at a discount. Method four ion-exchanges---oxidizing process

This method is former DRP technology. Its method is: under stirring energetically, in pH5～10 and 70 ℃～90 ℃, process waste water with chlorine or clorox, before chlorination with the distillation or from from waste water, removing organic acid in exchange process, make its concentration＜0.1%, from ammonium salt, remove ammonia with alkali, derivatives concentration to 0.01～0.1% when the air lift volatile compound is with minimizing before chlorination. This method exists: water outlet is qualified discharge directly, and the problems such as the secondary pollution of chlorine and processing cost height are arranged. Method five photocatalytic oxidations

The Beijing Chemical Research Institute is subjected to Juhua Group Co. to entrust the research of doing this respect. Its method based semiconductor band theory namely under light source irradiation, is excited the semiconductor surface electronics and moves into light induced electron. The photohole that produces has the strong electronic capability that gets, can capture electricity that semiconductor surface adsorbing pollutant in making it oxidized, also can capture the electronics in the hydrone and generate organic matter in the great hydroxyl radical free radical of oxidability (OH) oxidized waste water. Its effect is: the CODcr degradation rate only was 38.2% in 6 hours, and the hydrazine degradation rate is 92.9%, and, substantially inoperative to salt and ammonia nitrogen. Method six By Electrocatalytic Oxidations (or claiming the diaphragm-free electrolysis method)

The Beijing Chemical Research Institute is subjected to Juhua Group Co. to entrust the research of doing this respect. Its principle is based on containing chlorion in the waste water, under the effect of oxygen and electric field, nascent state chlorine and hydrogen peroxide that wastewater electrolytic produces have strong oxidizing property, can make the organic matter degradation of difficult for biological degradation in the waste water outside. The little test result of this technology shows that the CODcr degradation rate is 90%, and the ammonia nitrogen degradation rate is 90%. Its subject matter is: water outlet can't be directly up to standard, and substantially without effect, and the lab scale processing cost is up to ton water more than hundred yuan to salt in the water and sulfate radical. Method seven HSB (efficient decomposer) engineering bacteria biochemical process

Juhua Group Co. of blue star water treatment Co., Ltd entrusts the research of doing this respect. Its method is the HSB engineering bacteria that utilizes Taiwan company to provide, with respectively process anaerobism, the biochemical treatment of oxygen, aerobic three phases of holding concurrently of AC waste water of in advance process neutralization and certain proportion dilution. Its advantage is: technique is simple, can utilize existing biochemical process sewage treatment plant to process; Its shortcoming is: waste water requires extension rate too large, and cost of engineering bacteria is very high and need constantly additional.

With the immediate technology of the present invention: air air lift method (also claim neutralization carries ammonia process) East China University of Science's height loyaly loves and waits the people to study air air lift method nitrogenous effluent in the production of stripping AC blowing agent in sieve-plate tower. Its technique be with script pH be 12, the waste water (it is not quite clear specifically to originate) of nitrogenous 1000mg/l is when normal temperature and pressure and the gas liquid ratio 1200, through one-level sieve-plate tower stripping, the clearance of ammonia can reach 90%, by stripping tower gas sulfuric acid absorption out, reclaim sulfuric acid ammonium. But its report points out simultaneously that also ammonia concentration increases to more than the 1600mg/l in the former water, and clearance descends on the contrary, improve clearance and must further improve gas liquid ratio. The problem that the method exists: 1, gas liquid ratio is very high, and not only energy consumption is large, processing cost is high, and the absorption of tail gas is brought difficulty, and from the ammonia nitrogen increase of exhaust emissions, total clearance descends; 2, water outlet is still below standard, does not point out further treatment measures in the literary composition; 3, point out in the literary composition that sieve-plate tower has enlarge-effect, return this, can predict, as adopt multistage sieve to pull tower, then its stripping effect can further reduce; 4, the actual waste water of its test water and AC production has greater difference, do not add research for hydrazine hydrate, sulfate radical and salt, process the AC nitrogenous effluent if utilize said method, then the ammonia nitrogen of water outlet is still up to more than the hundreds of milligrams per liter, CODcr does not reduce for how much, certainly will water outlet to be carried out after-treatment again, but because the existence of hydrazine and salt etc., biochemistry hardly may. 5, since one-level sieve-plate tower and multistage sieve-plate tower be very different aspect mass transfer, the heat transfer, for multistage wall panel, get over the sieve plate on upper strata, its gas phase contains ammonia concentration superelevation, and motive force is less, contain the raising of ammonia concentration along with waste water, cat head is given vent to anger and is contained ammonia concentration and also can rise, and must significantly increase gas liquid ratio, but owing to be subjected to the airspeed limitation of tower, air capacity can not significantly increase, and the result can cause the treatment effect severe exacerbation.

Existing treatment technology comprehensively compares

Method	Action principle	Advantage	Existing problems
				The bleaching powder oxidizing process	Utilize bleaching powder or bleaching powder seminal fluid in water, to generate hypochlorous acid, emit again nascent oxygen and chlorine, make organic substance decomposing	1. the treatment of wastes with processes of wastes against one another, the low 2.CODcr of processing cost removes and can reach 78%	1. water outlet can't up to standard 2. easily causes the clearance reduction process such as perishable 4. ammonia nitrogens of secondary pollution 3. equipment, salt more difficult.
Absorb--the air lift method	Utilize modification high energy polymeric absorbent gentle formulation combined desulfurization acid group and ammonia	1. simulated test deamination rate can reach 97% 2. recyclable ammonium sulfate	1. to removing CODcr and diazanyl originally to no effect, water outlet still below standard 2. salts is higher, biochemical impossible 3. a large amount of sodium carbonate and ammoniacal liquor of consuming, and processing cost is high
				Crystallization--concentration method	The principle of utilizing the connection alkaline process to produce ammonium chloride reclaims the various inorganic salts in the hydrazine-containing water	1. the sodium sulphate in the recovery waste water, ammonium sulfate, closed circuit the following of sodium chloride 2. waste water	1. recovery technique is long, investment is large, energy consumption is high, and processing cost high 2. reclaims the products sales resistance

		Ring

	3. waste water goes back to system the impact of product quality be can not be ignored
		The diaphragm-free electrolysis method	Utilize the hypochlorous acid of electrolysis and electrolysis generation and the organic matter in the nascent state oxygen degrading waste water	1. equipment is simple, easy to operate 2. little test results, and CODcr and ammonia nitrogen degradation rate can reach 90%	1. water outlet can not qualified discharge, and it is expensive still to need further to process 2. disposal costs, and ton water is more than hundred yuan
Photocatalytic oxidation	The hole that utilizes near ultraviolet excitation to produce--organic matter reacts in duplet and the waste water, thereby reaches the purpose of degraded					1. more satisfactory 3. processing costs of the degradation effect of the simple 2. pairs of sides of body of technique are low	1. bad to the degradation effect of CODcr, ammonia nitrogen, salt, water outlet can't be up to standard, still needs 2. reaction time of after-treatment long, and equipment is once invested greatly
		HSB engineering bacteria biochemical process	Utilize the special engineering bacterium to remove ammonia nitrogen, hydrazine, CODcr etc.	1. technique is simple, and under easy to operate 2. certain concentration, clearance is higher	1. waste water requirement dilution times multiple cost of larger 2. engineering bacterias and higher 3. water outlets of supplementary cost are not up to standard
Air air lift method	Utilize the one-level sieve-plate tower that nitrogenous effluent is carried out stripping					The clearance of ammonia can reach 90%	1. can not up to standard 2. can not to adapt to high-concentration waste water 3. gas liquid ratios high in water outlet, and energy consumption is large

In sum, the problem of prior art existence mainly is: 1, treatment effect is single, and can not realize qualified discharge; 2, the technical finesse weak effect of simple, the reduced investment of technique, on the contrary treatment effect exists again complex process, investment high preferably. The problems such as processing cost height; 3, above-mentioned technology often only works to one or both pollutants, can not change the difficult biochemical character of waste water, can't utilize biochemical process to carry out after-treatment.

Summary of the invention

The present invention adopts preliminary treatment---biochemical process, wherein, preliminary treatment by the treatment of wastes with processes of wastes against one another, the materials harmful to biochemical process such as the hydrazine hydrate in the significant reduction waste water, ammonia nitrogen, sulfate radical, making waste water is can be biochemical by difficult biochemical conversion, by oxygen/aerobic device (various the Sewage Plant all possess) biochemistry of holding concurrently, finally realize qualified discharge again.

The hydrazine-containing water processing method of the generations such as Celogen Az production is: the AC hydrazine-containing water is sent into preprocessor through the precipitation supernatant, add carbide slag slurries or carbide slag or lime, transfer pH to 10～14 slurries air film stripping oxidizing tower of making a gift to someone, in temperature 50 C～98 ℃, gas liquid ratio 300～900, pressure 0.01～0.2MPa, under 0.5～3 hour time of staying condition, carry out the stripping oxidation, cat head stripping tail gas is through foam removal, cyclonic separation, enter the absorption tower behind the heat exchanger, sulfuric acid with 50%～80% absorbs, not solidifying exhaust emissions, stripping tower is discharged the press filtration of oxidation solution entrance pressure filter, filtrate is entered biochemical homogeneous pond, the preliminary treatment water outlet transfers to pH6～9 with acid or alkali in biochemical homogeneous pond, but and mix with other industry biochemical waste water or municipal sewage, or dilute with water, be adjusted to 600～1800mg/l, send into again the facultative anaerobic biochemical pond, at MLSS 3～9g/l, DO 0.2～0.4mg/l, 10～20 hours time of staying, carry out biochemistry, water outlet was advanced a heavy pond precipitation 4～10 hours, mud returns oxygen compatibility pool, supernatant enters aerobic biochemical pool, at MLSS 2～5g/l, DO 2～4mg/1,15～30 hours time of staying, carry out biochemistry, water outlet was advanced the second pond precipitation 4～10 hours, mud returns oxygen compatibility pool, the supernatant discharging.

Air film stripping oxidizing tower has body of the tower, body of the tower has the tower end socket, be provided with successively gripper shoe, band microcellular rubber film, hold-down ring in the body of the tower, pad, body of the tower is provided with heat exchanger, and heat exchanger is provided with water inlet, delivery port, exhaust gas inlet and waste gas outlet, and the body of the tower bottom is provided with air inlet, the top is provided with the gas outlet, is provided with qi-emitting hole in gripper shoe.

Reach effect of the present invention, must possess following necessary condition: 1, main treating agent adopts the masters such as carbide slag, lime to contain the alkaline materials such as calcium hydroxide (or calcium oxide). 2, process under the conditions such as pH10～14, temperature 50 C～98 ℃, gas liquid ratio (volume ratio) 300～900, pressure 0.01～0.2MPa, 0.5～3 hour time of staying and 50%～80% sulfuric acid and carry out. 3, the stripping oxidation is carried out in the air film void tower that this patent proposes, and effectively liquid level is 1.5 meters～3.5 meters, and take air as the air lift carrier. 4, the Separation of Solid and Liquid of slurries should be substantially thorough, reduces gypsum and enter biochemical system. 5, the preliminary treatment water outlet is after soda acid is adjusted, and must can biochemical water (or town sewage) mix or 1～5 times of dilute with water with other, is no more than permissible value to guarantee biochemical influent concentration. 6, should take full advantage of the existing biochemical sewage treatment device of municipal sewage plant or enterprise, and require routinely biochemical sludge is cultivated and tamed.

Advantage of the present invention is:

1) under process conditions of the present invention, the hydrazine hydrate in the waste water can be oxidised with air to harmless nitrogen G﹠W;

2) utilize in the alkalescence of carbide slag (or lime) and the acidity of waste water, and make the formation strong basicity, the ammonium root all is converted into free ammonia, is removed by stripping again, reduces biological denitrificaion pressure;

3) by SO a large amount of in the Ca in the carbide slag and the waste water₄ ^2-Generate calcium sulfate precipitation, reduce and suppress bioactive Toxic SO₄ ^2-Concentration;

4) removal of above three kinds of pollutions can be carried out simultaneously synchronously, and the factor of impact biochemistry in the waste water is eliminated;

5) the air film void tower that proposes of the present invention can be avoided stifled tower, carry the problem such as liquid foam secretly, makes that gas-liquid contact is abundant, cost is low;

6) treatment of wastes with processes of wastes against one another, small investment, processing cost are low.

Description of drawings

Fig. 1 is process chart of the present invention;

Fig. 2 is air film void tower structural representation;

Fig. 3 is air film void tower internal structure schematic diagram.

The AC hydrazine-containing water is sent into preprocessor through the precipitation supernatant, add carbide slag slurries (or carbide slag or lime), transfer pH to 10～14 slurries to send into stripping oxidation training (air film void tower), under the conditions such as temperature 50 C～98 ℃, gas liquid ratio 300～900, pressure 0.01～0.2MPa, 0.5～3 hour time of staying, carry out the stripping oxidation. Cat head stripping tail gas enters the absorption tower behind foam removal, cyclonic separation, heat exchanger, the sulfuric acid with 50%～80% absorbs, not solidifying exhaust emissions, and ammonium sulfate is sold or further done to the saturated ammonium sulfate mother liquor. Stripping tower is discharged the press filtration of oxidation solution entrance pressure filter, and filtrate is entered biochemical homogeneous pond, and filter cake goes landfill disposal. After pretreatment, hydrazine clearance 〉=95%, ammonia nitrogen removal frank 〉=96%, SO₄ ^2-Clearance 〉=97%, the BOD of preliminary treatment water outlet₅/ be promoted to more than 0.22 by 0.04 before processing, reaching can biochemical requirement. The preliminary treatment water outlet transfers to pH6～9 with a small amount of acid or alkali in biochemical homogeneous pond, but and mix with other industry biochemical waste water or municipal sewage, or dilute with water, be adjusted to 600～1800mg/l, send into again the facultative anaerobic biochemical pond, MLSS 3～9g/l, DO 0.2～0.4mg/l, the time of staying 10～20 hours, carry out biochemistry, water outlet was advanced a heavy pond precipitation 4～10 hours, and mud returns oxygen compatibility pool, supernatant enters aerobic biochemical pool, MLSS 2～5g/l, DO 2～4mg/l, the time of staying 15～30 hours, carry out biochemistry, water outlet was advanced the second pond precipitation 4～10 hours, mud returns oxygen compatibility pool, the supernatant discharging. Through bio-chemical effluent CODcr≤100mg/l, ammonia nitrogen≤15mg/l, hydrazine≤0.1mg/l, reach national grade one discharge standard.

Air film stripping oxidizing tower has body of the tower 2, body of the tower has tower end socket 6, be provided with successively gripper shoe 13, band microcellular rubber film 8, hold-down ring 12 in the body of the tower, pad 11, body of the tower is provided with heat exchanger 14, and heat exchanger is provided with water inlet 10, delivery port 5, exhaust gas inlet 9 and waste gas outlet 3, and the body of the tower bottom is provided with air inlet 7, the top is provided with gas outlet 1, is provided with qi-emitting hole 14 in gripper shoe 13.

The specific embodiment

Key technical feature of the present invention: 1) under strong alkaline condition, carry out simultaneously neutralization reaction, hydrazine oxidation reaction, air lift ammonia and calcium sulfate precipitation reaction in the stripping tower, in a step process, realize the removal of multiple pollutant; 2) adopt the unique air film void tower of design, both solved the difficult problems such as stifled tower, again the low purpose of implement device small investment and processing cost; 3) by the technique of preliminary treatment with biochemical combination, making AC waste water is can be biochemical by difficult biochemical conversion, namely control pretreatment deep, simultaneously, guaranteeing that waste water can realize qualified discharge 4 behind biochemistry) the employing carbide slag slurries is main treating agent, and the reclaim sulfuric acid ammonium, the dual purpose of the realization treatment of wastes with processes of wastes against one another and comprehensive utilization of resources.

Embodiment 1

The hydrazine-containing water processing method of the generations such as Celogen Az production: the AC hydrazine-containing water is sent into preprocessor through the precipitation supernatant, add carbide slag slurries, transfer pH to 10 slurries to send into air film stripping oxidizing tower, at temperature 50 C, gas liquid ratio 300, pressure 0.01MPa, under 0.5 hour time of staying condition, carry out the stripping oxidation, cat head stripping tail gas is through foam removal, cyclonic separation, enter the absorption tower behind the heat exchanger, sulfuric acid with 50% absorbs, not solidifying exhaust emissions, stripping tower is discharged the press filtration of oxidation solution entrance pressure filter, filtrate is entered biochemical homogeneous pond, the preliminary treatment water outlet transfers to pH6 with acid or alkali in biochemical homogeneous pond, but and mix with other industry biochemical waste water or municipal sewage, or dilute with water, be adjusted to 600mg/l, send into again the facultative anaerobic biochemical pond, at MLSS 3g/l, DO 0.2mg/l, 10 hours time of staying, carry out biochemistry, water outlet was advanced a heavy pond precipitation 4 hours, and mud returns oxygen compatibility pool, supernatant enters aerobic biochemical pool, at MLSS 2g/l, DO 2mg/l, 15 hours time of staying, carry out biochemistry, water outlet was advanced the second pond precipitation 4 hours, mud returns oxygen compatibility pool, the supernatant discharging.

Embodiment 2

The hydrazine-containing water processing method of the generations such as Celogen Az production is: the AC hydrazine-containing water is sent into preprocessor through the precipitation supernatant, add lime, transfer pH to 14 slurries to send into air film stripping oxidizing tower, 98 ℃ of temperature, gas liquid ratio 900, pressure 0.2MPa, under 3 hours time of staying condition, carry out the stripping oxidation, cat head stripping tail gas is through foam removal, cyclonic separation, enter the absorption tower behind the heat exchanger, sulfuric acid with 80% absorbs, not solidifying exhaust emissions, stripping tower is discharged the press filtration of oxidation solution entrance pressure filter, filtrate is entered biochemical homogeneous pond, the preliminary treatment water outlet transfers to pH9 with acid or alkali in biochemical homogeneous pond, but and mix with other industry biochemical waste water or municipal sewage, or dilute with water, be adjusted to 1800mg/L, send into again the facultative anaerobic biochemical pond, at MLSS 9g/l, DO 0.4mg/1,20 hours time of staying, carry out biochemistry, water outlet was advanced a heavy pond precipitation 10 hours, and mud returns oxygen compatibility pool, supernatant enters aerobic biochemical pool, at MLSS 5g/l, DO 4mg/l, 30 hours time of staying, carry out biochemistry, water outlet was advanced the second pond precipitation 10 hours, mud returns oxygen compatibility pool, the supernatant discharging.

Comparative Examples: the hydrazine-containing water processing method influent concentration that the Celogen Az production of 3 Comparative Examples of lab scale and 3 Comparative Examples of pilot scale etc. produce is different, and process is identical with embodiment 1, embodiment 2. Influent concentration, essential condition and the results are shown in Table 1, table 2.

Table 1 pretreating effect

Application examples		CODcr			NH 3-N			Hydrazine			Essential condition
														Before the processing	After the processing	Clearance %	Before the processing	After the processing	Clearance %	Before the processing	After the processing	Clearance %	Gas liquid ratio	Temperature	pH
		Lab scale
	1		2520	1880	25.4	10022	158	98.4	-	-	-	-	70	11
															2	7732	3535	54.3	23.72	307	98.7	-	-	-	-	70	11
	3		1323	871	34.2	3914	450	88.5	-	-	-	-	50	11
		Pilot scale													1	-	-	-	12877	247	98.1	35.3	18.1	48.7	700	70	14
2	-		-	-	12877	187	98.5	35.3	22.0	37.6	800	70	14
														3	-	-	-	29312	230	99.2	99.0	58.0	41.8	800	70	14

The Biochemical Treatment of table 2 pretreated water

Application examples		CODcr			NH 3-N			Hydrazine			Essential condition
												Before the processing	After the processing	Clearance %	Before the processing	After the processing	Clearance %	Before the processing	After the processing	Clearance %	After pretreated water carries out suitable dilution, advance again the AOO biochemical device and carry out biochemical treatment.
		Lab scale	1	1369	54	96.0	107	11.5	89.2	48.7	0.05											99.9
2	3535											133	96.2	307	94	70.0	18.4	0.02	99.9
			3	1262	45	96.4	151	6.9	95.4	11.6	0.02									99.9
Pilot scale	1											980	55	94.0	100	23	77.0		0.01
		2	1282	42	97.0	126	20	84.0	3	0.02	99.0
	3											1580	47	97.0	151	20	87.7	3	0.03	99.0

In the AC waste water blowoff oxidation test stage of the present invention, a large amount of free ammonias and calcium sulfate suspended solid exist in the water behind the adding calcium hydroxide. If directly carry out the stripping oxidation, no matter be at packed tower, or in the test of sieve-plate tower, all occurred stifled tower, gas-liquid contact bad, carry the liquid foam secretly, process the problems such as load is limited. For this reason, preneutralization suspension is carried out again stripping of liquid-solid separation, though avoided the problems referred to above, deamination goes the hydrazine effect that larger improvement is arranged, but new problem occurred, i.e. during centrifugation, a large amount of ammonias escape, and not only operating environment worsens, and has also polluted environment; More seriously, parting liquid is with the carrying out of stripping, and its basicity progressively descends, and makes deamination not thorough. In addition, with testing with the void tower of dispersion plate, occur again that the gas liquid ratio requirement is high, distribution grid easily blocks. The problems such as deamination weak effect. After be subjected to the inspiration of aerobic biochemical aeration mode, through comparative measurements, the suspension of finding preneutralization is very similar to biochemical Aerobic Pond, and good air-distribution and the gas-liquid-solid three-phase mass transfer of biochemistry pool, can satisfy stripping oxidation needs fully, so we will be through the biochemical aeration film grafting after the structural change in the stripping oxidizing tower, thereby has solved the existing defective of above-mentioned each tower and deficiency.

When air enters from the tower bottom (head), qi-emitting hole through gripper shoe, borrow air pressure with air film with differential of the arc shape jack-up, the micropore that evenly gathers on the air film becomes up big and down small infundibulate, and air namely forms microvesicle and enters in the tower, and rises with liquid level, constantly contact exchange with water, the ammonia of carrying under one's arms progressively becomes large, discharges to the broken bubble of liquid level. When air stops, air film springs back to rapidly the gripper shoe place, the micropore sealing, thus it is first-class to stop water and solid to pour lower seal into, and therefore, air film has become one-way membrane.

Claims (5)

1. the hydrazine-containing water processing method that produces such as Celogen Az production, it is characterized in that: the AC hydrazine-containing water is sent into preprocessor through the precipitation supernatant, add carbide slag slurries or carbide slag or lime, transfer pH to 10～14 slurries air film stripping oxidizing tower of making a gift to someone, in temperature 50 C～98 ℃, gas liquid ratio 300～900, pressure 0.01～0.2MPa, under 0.5～3 hour time of staying condition, carry out the stripping oxidation, cat head stripping tail gas is through foam removal, cyclonic separation, enter the absorption tower behind the heat exchanger, sulfuric acid with 50%～80% absorbs, not solidifying exhaust emissions, stripping tower is discharged the press filtration of oxidation solution entrance pressure filter, filtrate is entered biochemical homogeneous pond, the preliminary treatment water outlet transfers to pH6～9 with acid or alkali in biochemical homogeneous pond, but and mix with other industry biochemical waste water or municipal sewage, or dilute with water, be adjusted to 600～1800mg/l, send into again the facultative anaerobic biochemical pond, at MLSS 3～9g/l, DO 0.2～0.4mg/l, 10～20 hours time of staying, carry out biochemistry, water outlet was advanced a heavy pond precipitation 4～10 hours, mud returns oxygen compatibility pool, supernatant enters aerobic biochemical pool, at MLSS 2～5g/l, DO 2～4mg/l, 15～30 hours time of staying, carry out biochemistry, water outlet was advanced the second pond precipitation 4～10 hours, and mud returns oxygen compatibility pool, the supernatant discharging.

2. the hydrazine-containing water processing method that produces such as a kind of Celogen Az production according to claim 1 is characterized in that said carbide slag slurries or carbide slag or lime, is the main alkaline material that contains calcium hydroxide or calcium oxide.

3. the hydrazine-containing water processing method that produces such as a kind of Celogen Az production according to claim 1, it is characterized in that said air film stripping oxidizing tower has body of the tower [2], body of the tower has tower end socket [6], be provided with successively gripper shoe [13], band microcellular rubber film [8], hold-down ring [12] in the body of the tower, pad [11], body of the tower is provided with heat exchanger [4], heat exchanger is provided with water inlet [10], delivery port [5], exhaust gas inlet [9] and waste gas outlet [3], the body of the tower bottom is provided with air inlet [7], the top is provided with gas outlet [1], is provided with qi-emitting hole [14] in gripper shoe [13].

4. the hydrazine-containing water processing method that produces such as a kind of Celogen Az production according to claim 1 is characterized in that said stripping oxidation carries out in the air film void tower, effectively liquid level is 1.5 meters～3.5 meters, and take air as the air lift carrier.

5. air film stripping oxidizing tower, it is characterized in that said air film stripping oxidizing tower has body of the tower [2], body of the tower has tower end socket [6], be provided with successively gripper shoe [13], band microcellular rubber film [8], hold-down ring [12] in the body of the tower, pad [11], body of the tower is provided with heat exchanger [14], heat exchanger is provided with water inlet [10], delivery port [5], exhaust gas inlet [9] and waste gas outlet [3], the body of the tower bottom is provided with air inlet [7], the top is provided with gas outlet [1], is provided with qi-emitting hole [14] in gripper shoe [13].

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