CN1067230A - Nitrogen fertilizer plant's ammonia-containing water and contain ammonia circulating water treatment technology - Google Patents

Abstract

The present invention relates to a kind of nitrogen fertilizer plant ammonia-containing water and contain ammonia circulating water treatment technology, the deposed ammonia that it is characterized in that nitrogen fertilizer plant is not had a recovery value is directly as the make up water of circulating cooling system; Use not phosphorated humic acids series HAS water quality stabilizer conduct to contain the water quality stabilizer of ammonia recirculating cooling water system.The present invention is first for the ammonia-containing water of nitrogen fertilizer plant with contain the ammonia circulating water treatment a kind of reliable method is provided, and overcome not contain ammonia in the long-standing recirculating cooling water system or contain ammonia less and use water quality stabilizer to be not suitable for handling the prejudice of pH value greater than 9.5 industrial circulating water.

Description

Nitrogen fertilizer plant's ammonia-containing water and contain ammonia circulating water treatment technology

The present invention relates to a kind of Treatment of Industrial Water technology, specifically a kind of ammonia-containing water is made the technology of recycle system make up water.Mainly be adapted to nitrogen fertilizer production enterprise nitrogenous effluent and contain the processing of ammonia recirculated water.

Nitrogen fertilizer production is in China's history of existing decades.But, because in the past in nitrogen fertilizer production, ignore making full use of of environmental pollution and water, and exist following two problems: the ammonia-containing water in the first production process directly discharges, serious environment pollution always.The 2nd, the ammonia-containing water in the production process leaks to the fouling of aggravation equipment pipe, corrosion and long bacterium algae in the water coolant, the gently then underproduction, and heavy then stop production to overhaul is handled.The treatment process of nitrogen fertilizer plant's deposed ammonia recovery ammonia and deposed ammonia mainly contains following four kinds at present:

1, handles ammonia nitrogen waste water with the selectivity ion exchange method.

This method is to adopt ZC-1 ammonia nitrogen waste water scavenging agent, according to it to NH ⁺ ₄-N has good selectivity ion exchange to be handled, and the water after the processing can reach the provisional emission standard of ammonia nitrogen waste water.Make manipulation of regeneration with salt solution, can use repeatedly, contain NH ⁺ ₄The salt solution of-N.With blow-off method desorb ammonia, absorb ammonia with dilute sulphuric acid again, obtain (NH ₄) ₂SO ₄Can make fertilizer.Its problem is that investment is big, handles trouble, and the deposed ammonia that fluctuations in discharge is big in incompatible the production is handled.

2, the AO method is handled the nitrogen-containing wastewater novel process.

Under oxygen supply condition, rely on the effect of nitrobacteria that organonitrogen in the water and ammonia nitrogen are oxidized to NO ^- ₃, and then the effect that utilizes denitrifying bacterium under anoxia condition is with NO ^- ₃Be reduced to N ₂, it is finally returned in the atmosphere, the problem of its existence is that investment is many, the technology height, difficulty is big, is not suitable for manufacturer and uses.

3, administer the new method of weak ammonia of small nitrogenous fertilizer plant

Adopt weak ammonia enrichment recovery method recovery ammonia step by step.Full factory multiple spot is added soft water reclaim ammonia, the flow process of washing ammonia changes into and a bit adds soft water, promptly adds soft water in carbonization cleaning section (tower), and weak ammonia is delivered to refining again, equipressure reclaims enrichment step by step, uses for the composting material after making weak ammonia improve concentration.This method is the Ministry of Chemical Industry's promotion method, and has held study class in December, 1989 in the Jianyang, Sichuan, and this is one of optimization technology in the ammonia reclaiming process.But deposed ammonia still also has discharging inevitably.

4, technology waste dilute ammonia system carbonization mother liquor.

This method is to adopt the steam treatment weak ammonia in ammonia still, and then makes carbonization mother liquor.Its problem is that investment is big, the steam consumption height, and general nitrogen fertilizer plant can not be so many energy consumptions aspect the recovery deposed ammonia, so be difficult to apply.

In addition, also have methods such as gas formulation, weak ammonia refrigeration.Though but since these ways can be theoretically, the handling problem that solved deposed ammonia substantially of testing laboratory, small-scale production scene and utmost point discrete factory, can be owing to all there being a series of problems such as energy consumption height, investment are big in large-scale factory, and fail generally to apply.

The harm of deposed ammonia mainly contains two aspects:

1, the direct exhaust emission water body of ammonia-containing water makes environmental degradation.In little nitrogen fertilizer production, because the problem in equipment leakage and the technological operation, all containing inevitably in the water coolant and containing ammonia in ammonia, especially the carbonization system water coolant is frequent thing.Carbonization workshop section cleaning section (tower) though technology weak ammonia brainstrust adopted the whole bag of tricks to reclaim ammonia, but still also have weak ammonia discharging in various degree.Ammonia easily is oxidized to the nitrous ammonium in the presence of oxygen, nitrite is a kind of carcinogenic substance, and the chemical oxygen demand cod in the water is increased, and makes water eutrophication.So emission standard by environment protection: NH ₃-N discharging is 25～40mg/L, and COD is 150mg/L.So ammonia-containing water can not directly discharge.And the ammonia recovery value in the ammonia-containing water of present lower concentration is too little, and therefore, nitrogen fertilizer production enterprise all produces in order to guarantee now, and the direct exhaust emission water body of ammonia-containing water is had to pay the effluent charge that exceed standard.

2, the fouling, corrosion and the long bacterium algae that contain ammonia aggravation equipment pipe in the water coolant.

Ammonia is a kind of very easily water-soluble, the material that the solubleness in water is very big, and carbonic acid gas is very difficult water-soluble, the dissociation degree in water is very little.Therefore, make following equation in the water coolant:

Balance move right, the aggravation incrustation scale formation.

Ammonia is dissolved in or ammoniacal liquor enter be easy in the water coolant with water in carbon dioxide reaction generate ammonium salt, as following reaction formula:

Since the formation mass consumption of ammonium salt the CO in the water ₂Make

Balance moves right rapidly, and it is fast to make incrustation scale form speed, and quantity is big, so the people of nitrogen fertilizer plant generally acknowledge: ammoniacal liquor enters water coolant, evil is just gone through in the equipment pipe fouling especially.Owing to contain ammonia fouling aggravation in the water coolant, and the dissolving of carbonate and fouling, accelerated the galvanic corrosion of equipment, owing to, have to use the mechanical means scale removal, cause equipment to strike and shovel into rough surface again in order to keep production, more perishable, that have in addition the perforation crack, pipeline since fouling seriously have to change by stages and in groups, especially the obstruction of sprinkling equipment usually causes accident and parking maintenance.

Because the ammonia in the water makes water eutrophication, impel the microorganisms producing breeding more vigorous again, more aggravated the biological corrosion and the biological fouling of equipment.Ammonia makes pH value be difficult to control in the recirculating cooling water system of dosing, consumes a large amount of acid and chlorine sometimes even cooling water circulation treatment technology is failed.

For above-mentioned reasons, ammonia is very big to the harm of cooling water system especially recirculating cooling water system, and people avoid ammonia to bleed by every possible means or enter cooling water system.The present little ammonia fertilizer overwhelming majority of manufacturing enterprise still adopts the once-through cooling water cooling, the employing that also has recirculated water and do not carry out dosing and handle, consequently water loss is big, equipment scaling, the long bacterium algae of burn into cause heat-transfer effect poor, make Roots's machine compressor inflate quantity reduce especially carbonization production system, hot season is bad because of conducting heat, cause vicious cycle, gently then decrement production, heavy then stop production; Equipment corrosion is fast, and maintenance is frequent, waste great deal of steel, aluminium, even, threaten the safe operation of producing because of heat-exchange equipment perforation leakage.Cause major causes such as cooling apparatus fouling, the long bacterium algae of burn into as follows:

1, water evaporates in process of cooling, makes that calcium magnesium acid carbonate concentration constantly increases in the recirculated water, and water and air full contact aeration make CO in the recirculated water ₂Concentration is significantly less than equilibrium concentration, adds the be heated intensification of water on interchanger, makes CO in the water ₂Overflow, thereby make:

Balance move right CaCO ₃, MgCO ₃Precipitation depends on equipment, pipe surface, forms the dirt layer.

2, evaporation of water concentrates and constantly replenishes the moisturizing of calcic magnesium salts, makes the calcium magnesium salts cause accumulation to become the residue fouling, makes

Balance moves right, and precipitation is separated out, and forms incrustation scale.

3, nutritive substance is abundant in the recirculated water, the breeding of thermal adaptation microbial growth, and sufficient dissolved oxygen is arranged.Make the vitality of microorganism very strong, metabolism is vigorous, and ight soil of microorganism and corpse and algae depend on and be bonded in the equipment pipe surface.Form the biofouling layer.

4, dissolving of lime carbonate magnesium salts (erosion) and fouling have the galvanic corrosion effect to metal, also have oxide compound and H in the water ⁺Ion makes metal produce chemistry or electrochemistry pitting corrosion and uniform corrosion, and the accumulation of biological warty coagulum and thread iron bacteria makes metal produce dirt erosion and perforation etc.

For the fouling that solves heat-exchange equipment and pipeline, the problem of the long bacterium algae of burn into, some has adopted the recirculated cooling water technology at the whole nation more than 1,000 tame small nitrogenous fertilizer plants.In April nineteen ninety, little nitrogenous fertilizer two water (gas making sewage, water coolant) the closed cycle technology of chemical design institute, Fujian and the research of Tianjin chemical research institute has obtained the prize for the achveivement in science and technology of State Scientific and Technological Commission.In August nineteen ninety, State Scientific and Technological Commission, State Bureau of Environmental Protection, the Ministry of Chemical Industry unite the little nitrogenous fertilizer two water closed cycle technology of project of hereinafter popularizing scientific and technological achievements.The little nitrogenous fertilizer water coolant closed cycle technology that Tianjin chemical research institute works out, the water treatment agent TS series that recycles of Yan Zhi this particularly, be adapted to little nitrogenous fertilizer in cooling water circulation aluminium equipment and the water conditioning of meta-alkalescence, for the Treatment of Industrial Water in the whole nation has especially been made outstanding contribution to the water treatment of nitrogenous fertilizer industry.

The water stabilizer that uses in the closed cycle of present national small nitrogenous fertilizer plant water coolant all is that phosphorus line formulation and phosphorus are compound prescription basically.The phosphorus that the TS series water stabilizer of obtaining national prize for the achveivement in science and technology also belongs to improvement is compound prescription and all-organic formula one class.Discrete enterprise also uses prescriptions such as molybdenum system on a small scale.Now several water quality stabilizers that will generally use now are described below:

1, traditional phosphorus line formulation:

Poly-phosphate becomes cooling water treatment chemical already, and it has good inhibition, scale-inhibiting properties, and price is more cheap, therefore still is widely used for now in the industrial colling processing, and the TS series water stabilizer of Tianjin chemical research institute exploitation in 1974 is exactly this prescription.Traditional phosphorus line formulation also is used with zinc salt except that using poly-phosphate, and zinc salt is the well behaved inhibiter of generally acknowledging, cost of water treatment is low, manages properly, also can obtain satisfied effect.But do not have phosphonate and poly carboxylic acid dirt dispersion agent in this class prescription, when PH is higher, precipitation aggravation, zinc salt at PH greater than separating out Zn(OH at 8.3 o'clock easily) ₂Precipitation, when pH value was higher, the calcium phosphate that forms after the poly-phosphate hydrolysis easily formed the dirt that is difficult to handle, and therefore, pH value can only be controlled at 6.0～7.5.In view of circulating water PH value is lower, then the concentration of inhibiter needs is higher.The pH value of Control Circulation water still needs to regulate by adding the vitriol oil.Therefore requiring to add the acid operation must be accurately strict, adds the acid operation and causes error to make troubles to production run.It is comparatively simple that this class prescription is adapted to equipment, the production equipment that the recirculated water cycles of concentration is lower.Use more 50～sixties abroad, still using so far.

2, phosphorus is compound prescription

Along with introducing large nitrogen fertilizer plant, it is that the phosphorus of representative is that compound prescription (domestic general abbreviation phosphorus line formulation, the external phosphatizing prescription that enlarges of claiming) is the water treatment prescription of forming with poly-phosphate-phosphonate-poly carboxylic acid-heterogeneous ring compound with TS-1 that Tianjin chemical research institute developed in 1975.It has been widely used in the water treatment of domestic large, medium and small all kinds of enterprises, and along with continuous summing up experience is gradually improved, it is not only in the nitrogenous fertilizer system, and applies in industries such as oil refining, petrochemical complex, metallurgy, chemical fibres, and this is the important water technology that current China adopts.Compare with traditional phosphorus line formulation, this class formulating of recipe considers that as inhibiter, phosphonate is as Scale inhibitors with poly-phosphate comprehensively, and poly carboxylic acid is as dispersion agent, and heterogeneous ring compound is as copper material corrosion inhibitor and spot corrosion control agent.Owing to introduced phosphonate and poly carboxylic acid, alkaline and non-alkaline incrustation scale all can be controlled preferably, and cycles of concentration can be brought up to more than three times, and pH value also can be controlled in greater than under 7.5 conditions, and the raising of pH value has also reduced the consumption of inhibiter.The correct coupling of various medicaments is very important in this class prescription, and the orthophosphoric acid salt in the prescription after the poly-phosphate hydrolysis is the nutrition source of bacterium and microorganism, and therefore, strengthening the sterilization algae removal processing is that this prescription uses an important step successfully.The operation that adds acid adjusting pH value in addition still needs strict control and management.

3, phosphorus is the alkaline water treatment technology

Along with the novel dispersant TS-604 that the non-alkaline incrustation scale of calcium phosphate one class is had the good distribution performance, TS-609, TS-607, TS-608 etc. succeed in developing, at phosphorus constantly research and development on the basis of compound prescription, the exploitation of alkaline water Processing Technology has been carried out phosphorus and is in some unsuitable restriction that it is compound prescription that original phosphorus is broken in summing up experience since 1980, realized recirculated water alkaline operation of (general PH is 8.5～9.0) under Balance of nature PH condition.This class prescription has also been avoided the error that adds the acid operation and bring except that having the advantage that phosphorus is compound prescription.Be subjected to user's very big welcome.Since the eighties, this class prescription has been successfully used to each industrial circle.Poly-phosphate in the prescription is as inhibiter, and the orthophosphoric acid salt after its hydrolysis also is an inhibiter, alkaline operation in addition, and the corrodibility of water is little, and the inhibiter consumption is few, and when operational condition fluctuateed, corrosion control was still better.The water quality lower for hardness, that corrodibility is stronger, recycle ratio is little, the system that the medicament residence time is not oversize, this class prescription is fine.In recent years, appearance along with the multiple copolymer dispersion agent, resembling the non-alkaline incrustation scales of this class such as calcium phosphate, calcium sulfate, zinc hydroxide, ferric oxide can be well controlled, and phosphorus is that the alkaline water treatment technology can be allowed in application in higher cycles of concentration and the system than long residence time (greater than 50 hours) and used.

4, all-organic formula

It is the toxicity problem at mineral compound such as chromic salt, zinc salt, nitrite etc., and the hydrolysis of poly-phosphate and the water technology that forms, and this is the important development direction of domestic and international water technology.All-organic formula mainly is made up of phosphonate (or phosphine carboxylic acid) and poly carboxylic acid.Since nineteen eighty-two, China has developed the all-organic formula water technology in succession, TS-205 for example, and TS-206, TS-207, and the similar prescription that provides for many factories, with external S-112, S-113, N-8365 is similar all to be this class all-organic formula.Because the medicament phosphonate and the poly carboxylic acid chemical stability of compositing formula are good, thereby can allow that medicament has the very long residence time (more than 100 hours), the alkaline operation of Balance of nature pH value and high rigidity and move than high concentration multiple (more than 3 times).Phosphonate in this class prescription is not only as Scale inhibitors but also as inhibiter, and it by with the synergy of poly carboxylic acid and the Ca in the water ^{+ 2}, Mg ^{+ 2}Cooperate the corrosion mitigating effect that improves prescription Deng divalent ion.Just because of this, the corrosion mitigating effect of prescription and water hardness, basicity are relevant, and will note the selection and the correct matching problem of medicament.

5, molybdenum system prescription

More domestic units had carried out the research of molybdate (and tungstate, vanadate) as cooling water treatment agent in recent years, and used in small-sized water circle device, had obtained anticorrosion-antiscaling effect preferably.Use molybdate separately in water coolant, obtain corrosion mitigating effect preferably, dosing is too big, and the regular job expense is too high.Its compound prescription is compared with phosphorus line formulation, and the water treatment expense is still very high.Therefore, how reducing the cost of water treatment in the molybdenum system prescription, is that molybdenum is the key that water technology is achieved success.

6, humic acids series water stabilizer

Humic acids series water stabilizer report was once arranged in the water treatment field at home, but use face is very little, and its major ingredient is that humic acids adds other compositions and is adapted to acidity or basic treatment, adds amendment again.Once in the introducing equipment of Beijing Yan Hua company, used, also tried out to open grave fertilizer plant in Jiangxi.Be characterized in that the water treatment expense is low, scale inhibition, scale removal, etch-proof performance are good, are a kind of up-and-coming water conditioners.

Though present widely used water stabilizer all has good scale inhibition, dispersion, corrosion inhibition, also being adapted to of having used under the meta-alkalescence condition, what have also has good corrosion inhibition to copper material (non-synthesis ammonia plant), aluminium, and what also have is low-phosphorous and non-phosphorus medicament.But all there are some common problems:

The one, prescription is complicated, the necessary rational Match of various medicaments, and water quality analysis control is strict, otherwise can produce various side effects;

The 2nd, all must stop to the pickling descaling scrubbing of recycle to extinction system before the dosing, the acid consumption is big, troublesome poeration and dangerous, pickle solution exhaust emission water body;

The 3rd, must continue after the pickling to stop pre-film more than 40 hours, troublesome poeration, and the analytical work amount is big;

The 4th, the feeding operations complexity, medicament has solid, liquid, powdery, bulk all to need to measure respectively interim adapted, therefore, measuring instrument and chemicals feeder etc. must be set;

The 5th, water quality analysis will be joined technician's break tour, establishes ad hoc analysis post and analytical instrument, and analysis frequency control is strict, analyzes loaded down with trivial detailsly, and workload is big;

The 6th, must add the vitriol oil and regulate pH value, need consume a large amount of acid when the carbonization water tank leaks when ammonia content is high in ammoniacal liquor or the technological operation accident recirculated water, not even do not replace recirculated water.Need accurately control add the acid amount, in order to avoid the etching apparatus pipeline causes the accident, so analysis operation need very prudent, and the storing of acid, add dangerous;

The 7th, must add Biocidal algae-killing agent, in order to prevent to develop immunity to drugs, also must be used alternatingly multiple biocide.Liquid chlorine, Babysafe toxicity are big, complicated operation and dangerous, when especially containing ammonia in the recirculated water, can reduce the ability of killing livestock of chlorine, chlorine consumption is increased, because the hypochlorous acid that the water-soluble back of chlorine produces is strong oxidizer, and ammonia is reductive agent, chemical reaction takes place in them, and the form of its product then by the pH value decision, is reacted as follows:

The chlorine ammoniac compounds also is a sterilant, and the time of keeping drug effect but its sterilization speed is slow is longer, and requires sterilization rapid in recirculated cooling water, because water is when outgasing in cooling tower, the chlorine ammoniac compounds will all be overflowed and do not had sterilizing ability.

The 8th, cycles of concentration is all not too high, generally doubly at 2-4, this class formula technique moves under high concentration multiple and can produce phenomenons such as fouling and corrosion, therefore need periodic blow down to control cycles of concentration in indication range, the result of blowdown has not only wasted water resources and medicament, but also having polluted environment, manipulation strength is also big;

The 9th, it is bigger investment to be set, and maintenance is the other filter device of trouble, and other filter is the sewer contaminate environment when backwash and suitable washing.And 3%～5% the other filter circulation of water is arranged.Increased consumption;

The tenth, above all kinds of water treatment agent expense is compared all somewhat expensive with humic acids series water stabilizer expense, make cost of water treatment higher;

11 is that above all kinds of water treatment prescription generally only is suitable for pH value 6～8.3 scopes, even phosphorus is the condition of water quality that the alkaline water treatment formulations also only is adapted to pH value 8.5～9.0, comprise the condition of water quality of also stipulating to be adapted to pH value 8.5～9.5 in the humic acids series water stabilizer HAS explanation use book.All require not contain in the circulating water system ammonia or contain ammonia less, be difficult to avoid in little nitrogen fertilizer production and contain ammonia in the water coolant, the designing technique and the level of management of just present national little nitrogenous fertilizer, carbonization cleaning section (tower) the discharging deposed ammonia in various degree of most producers, especially the leakage of carbonization water tank, sometimes also very serious, the discharging deposed ammonia that work accident causes also still exists, therefore, cause the pH value of recirculated water to increase suddenly, pH value reaches 10 usefulness acid and also is difficult to regulate when ammonia content is 1000mg/L, and the chlorination of having in containing ammonia recirculated water is killed livestock.To add sour chlorination expense and guarantee the water quality control criterion in order to reduce, have to the recirculated water displacement and contaminate environment.

Purpose of the present invention is exactly the treatment process that a kind of processing of ammonia-containing water will be provided and contain ammonia recirculated water, can handle the ammonia-containing water of nitrogen fertilizer plant economically with this technology, and it is abundant to seek a kind of source, cheap, the water quality stabilizer of non-secondary pollution can be adapted to contain the ammonia recirculating cooling water system again.Use this water stabilizer, can solve fouling, inhibition, sterilization algae removal, the safety of circulating water system, the secondary pollution of no medicament itself effectively, easy and simple to handle, analysis and Control is easy, convenient management, and deposed ammonia does not discharge and problem of environment pollution caused.

To achieve these goals, the present invention has adopted following technical proposals:

1, the deposed ammonia that nitrogen fertilizer plant is not had a recovery value is directly as the make up water of circulating cooling system.

2, use not phosphorated humic acids series HAS water quality stabilizer conduct to contain the water quality stabilizer of ammonia recirculating cooling water system.

HAS is that Jiangxi Province Pingxiang City humic acids industrial in 1984 researchs and produces, and has passed through provincial-level appraisal.

Fundamental component among the HAS is Sodium salts humic acids and Na ₂CO ₃, add various amendments and auxiliary agent again.Sodium salts humic acids extracts from peat, brown coal and weathered coal, is a kind of natural polymer aromatic hydroxy-carboxylic compound.Have very big molecular surface area, can be in conjunction with calcium magnesium.Ion Ji Ningchendian stops and dispersion calcium magnesium salts crystalline increases, and the calcium magnesium salts that humic acids forms is loose condensation product, not the adhering device pipe surface.More unlikely formation hard scale facts have proved, this product has high scale inhibition ability.Humic acids series water stabilizer can move under high concentration multiple.。Be generally more than 8, do not need blowdown.Because humic acids acts under alkaline condition, helps the passivation of metal, has slowed down the galvanic corrosion to equipment pipe, has good corrosion mitigating effect.But the introduction according to factory is the same with other water stabilizers, only suits to use in pH value 8.5～9.5 scopes.So professional in the art generally believes that existing all water stabilizers all require not contain ammonia and contain ammonia less in recirculating cooling water system.More dare not be the make up water of ammonia-containing water as recirculating cooling water system, in the Treatment of Industrial Water technical field, comprise HAS factory in Jiangxi the test in place to ore deposit fertilizer plant, so far not useful as yet water quality stabilizer is handled the precedent that pH value is higher than 9.5 industrial circulating water, and technology ammonia-containing water more of no use and equipment leakage ammonia-containing water are made the Technology of circulating cooling system make up water.

Water quality stabilizer HAS is nontoxic, without phosphorus, raw material is easily got, and is cheap, easy to manufacture, easy to use, simple to operate, non-secondary pollution in manufacturing and the use.Study repeatedly in practice, test through us, prove in containing ammonia recirculated water, to use to have following effect:

1, anti-scale descaling effect: the mechanism of action of humic acids basic treatment water quality stabilizer in recirculated water is chemical reaction and physical actions such as calcium, magnesium, carbonate, vitriol and ammonium salt generation copolymerization, complexing, the absorption in humic acids sodium salt and the recirculated water, generates the polymkeric substance of loose calcium humate magnesium salts and lime carbonate magnesium salts, ammonium salt etc.Since the complexing action of humate, CaCO ₃, MgCO ₃And CaSO ₄, MgSO ₄Can not freely precipitate with chloride salt and to be bonded on the equipment pipe, again because the absorption electrical function of humate, but etch has precipitated the carbonate that is bonded on the equipment pipe, vitriol etc., and its chemical reaction expressivity is as follows:

Humate is colloidal solution under alkaline condition, be the very big long-chain shape macromolecular compound of an internal surface area, and the calcium magnesium salts is had the absorption complexing action, makes the calcium magnesium salts crystal can not normal growth, makes that lattice is bent to be become, and reaches the purpose of scale inhibition.Because humic acids has infiltration and corrosion.Old dirty corrosion is come off, reach the purpose of scale removal.

2, corrosion inhibition: humic acids can make metal passivation under alkaline condition, and humic acid Si salt, molysite etc. form one deck inhibition protection film as thin as a wafer in the metallic surface, and the galvanic corrosion that can slow down metal all is suitable for carbon steel, cast iron, aluminium.

3, sterilization algae removal effect: because recirculated water is in alkaline condition, and medicament itself does not contain the nutritive substance phosphorus of microorganism, and ammonium salt is also sunk to anoxybiotic sediment hole by the humate complexation copolymerization, so, can suppress bacterium algae growth and breeding effectively, therefore, use in the circulating water system of humic acids strong basicity processing, do not need to add Biocidal algae-killing agents such as liquid chlorine, Babysafe.

The present invention handles and contains the ammonia circulating water treatment for the ammonia-containing water of nitrogen fertilizer plant first provides a kind of reliable method, and has overcome and do not contain ammonia in the long-standing recirculating cooling water system or contain ammonia less and use water quality stabilizer to be not suitable for handling the technology prejudice of pH value greater than 9.5 industrial circulating water.Research and tested various chemical reaction mechanisms in ammonia-containing water and HAS water stabilizer and the recirculated water and the basis of condition on, designed with the make up water of ammonia-containing water, used the technology of humic acids series HAS water stabilizer as the steady medicament of water of recirculating cooling water system as recirculating cooling water system.

Description of drawings:

Accompanying drawing 2: be existing circular water treating system running status synoptic diagram (is example with little nitrogenous fertilizer water coolant closed circuit circulatory system) before the present invention.

Accompanying drawing 1: be circulating water system operation of the present invention, view (is example with little nitrogenous fertilizer water coolant closed circuit circulatory system).

Accompanying drawing 3: be that existing small nitrogenous fertilizer plant is inhaled ammonia cold type water circulation system running status synoptic diagram before the present invention.

Accompanying drawing 4: be that the embodiments of the invention small nitrogenous fertilizer plant is inhaled ammonia cold type water circulation system running status synoptic diagram.

Embodiment:

Referring to accompanying drawing 2: existing circular water treating system technological process (is example with little nitrogenous fertilizer water coolant closed circuit circulatory system) before the present invention.

1, removes contamination: by circulating water pool (1), recycle pump (3), cooling tower (4), circulation line (37) compressor cold type (in the recirculating cooling water system of comprising compressor cylinder, circulator cylinder (5), carbonization water tank (7), inhale ammonia cold type (10), transformer coiled pipe (12), ice maker cold type (14), synthetic cold type (16), refining cold type (18), conversion cold type (20), steam turbine (23), total backwater ditch (28) being formed, clean with former water (26), remove mud scum, bacterium algae and foreign material.

2, pickling: after circulating water system is cleaned, be made into inhibiter with enough round-robin acid and add circulating water pool (1), ON cycle pump (3), through cooling tower (4), circulation line (37), divide again and be clipped to compressor cold type (5), carbonization water tank (7), inhale ammonia cold type (10), transformer coiled pipe (12), ice maker cold type (14), synthetic cold type (16) refining cold type (18), steam turbine (23), converge and flow into total backwater ditch (28), get back to circulating water pool (1) at last, so cycle pickling is about 24 hours, check the dirt of cooling apparatus, after the iron rust pickling is clean, again spent acid solution is drained into trench from wash water valve (2).

3, pre-film: after system carries out pickling, pre-immediately film.The Full System Capability prefilming agent is added circulating water pool (1), circulate as pickling process.Prefilming agent mainly is Sodium hexametaphosphate 99, sulphur phosphorus zinc etc.; its effect is to make the exposed metallic surface of equipment pipe form one deck compact protective film; need strict on-the site analysis; control various ionic concentration, temperature, time in the pre-film liquid; and the sulfuric acid in the concentrated sulfuric acid groove (34) injected add sour gauger (35) and add the pH value that circulating water pool (1) is regulated pre-film liquid; pre-film reached about 40 hours, formed layer protecting film until the metallic surface and could finish pre-film.Measure total content of inorganic phosphorus again, by wash water valve (2) blowdown, and make up water, controlling total inorganic phosphorus in indication range, just can put into operation.

4, raw water quality analysis: select different water conditioning agent prescriptions according to analytical results by different water quality, generally all need the technical skill service of water treatment research department, calculate and add dose first.

5, Jia Yuanshui: former water is added circulating water pool (1), and start water circulating pump (3) beginning circular flow.

6, add water stabilizer: the dose that adds first that will measure dissolves, mixes in the recirculated water of back adding circulating water pool (1) by chemicals feeder (31), makes it normal circulation.

7, add make up water: system is in the circulation process of cooling, and vaporize water, sewer are arranged, the seepage of splashing etc. lost water, for this reason, adds former water by make up water pipeline (26) in circulating water pool (1) and makes make up water.

8, circulating water quality analysis: in the circulation process of cooling, because the loss of recirculated water and the adding of make up water, variation has taken place in circulating water quality, for stabilizing water quality, must regularly analyze circulating water quality.Analysis project is as follows: pH value, C ^{+ 2}A, Mg ^{+ 2}, total hardness, total alkalinity, turbidity, orthophosphoric acid salt, total phosphate, polyacrylic acid, NH ⁺ ₄, carboxyl ethylidene bisphosphate, specific conductivity, chlorine residue, CO ₂, total molten solid, K ⁺, heterotrophic bacterium etc., its analysis frequency height is analyzed loaded down with trivial details.

9, replenish water stabilizer: according to the circulating water quality analytical results, calculate the additional amount of the various medicaments of per tour every day, the medicament that measures is dissolved by chemicals feeder (31), mix the back and add circulating water pool (1), so constantly circulate.

10, add acid and regulate pH value: according to analytical results, pH value is adjusted in the pH value subject range of water stabilizer, is generally 7.8～8.3, minority is 8.5～9.5.The injection of the vitriol oil in the vitriol oil storage tank (34) is added sour gauger (35), add circulating water pool (1) again.Special messenger's on-the site analysis, strict control pH value can not superelevation, make it to cause side effects such as fouling, more can not reduce, and make it to cause the corrosion of equipment pipe and cause the accident.

11, add Biocidal algae-killing agent: recirculated water is in operational process, because water temperature is suitable, phosphorus in phosphorus line formulation and the compound prescription thereof and the ammonia in the water are the nutriment of microorganism, and easily growth bacterium algae in the cooling apparatus of open type influences the normal operation of the heat-transfer effect and the recycle system.So will regularly add Biocidal algae-killing agent, in order to solve the problem of developing immunity to drugs, also must be used alternatingly various Biocidal algae-killing agents, generally with liquid chlorine, Babysafe, bromogeramine etc. are as biocide.Liquid chlorine in the chlorine cylinder (32) is injected rotor chlorinating machine (33), add circulating water pool (1) again.And need strict control chlorine dosage, add that to have lacked the effect of killing livestock bad, added, not only consume highly, the more important thing is etching apparatus.

12, blowdown: the CL in analysis cycle water and the make up water ^-Or K ⁺Ionic concn is calculated cycles of concentration, and calculation formula is as follows:

Concentration multiple K=(CL-in the recirculated water (or K+) concentration)/(CL-in the make up water (or K+) concentration)

Contain in prior art, the especially recirculated water under the situation of ammonia, general cycles of concentration is controlled at 2～3 times, reasonable being controlled at about 4 times, otherwise the high concentration multiple operation can cause equipment pipe fouling, corrosion.By wash water valve (2) periodic blow down, sewer contaminate environment.

13, other filter: recirculated water is in operational process, owing to concentrate, residue, foreign material, dirt and water stabilizer slag etc. make increases such as recirculated water turbidity, suspended substance, influence circulating water quality.Therefore, 3%～5% of recirculated water must be connect from the pump discharge pipeline and be back to circulating water pool (1) after an arm (38) filters by other filter (29).Regularly other filter (29) is carried out removing residue mud along washing backwash then, enter trench by wash water valve (30), the discharge water contaminate environment.

14, the processing of ammonia-containing water and contain the replacement proble of ammonia recirculated water:

Small nitrogenous fertilizer plant is because of the reason of processing unit, produce ammonia-containing water inevitably, oil extraction water and blowdown (6) carbonization cleaning section (tower) waste discharge ammoniacal liquor as compressor, the carbonization water tank leaks waste discharge ammoniacal liquor (8), inhale ammonia blowdown (11), each analyzer room's blowdown (13), ice maker blowdown (15), synthetic center boiler, rearmounted boiler and cold friendship, blowdowns such as ammonia cooler (17), transformation system blowdown (19), refining ammonia cold type dirt (21), generally contain ammonia at 50Mg/L～20000mg/L in total sewer (27) of steam turbine water of condensation blowdown (24) and desulfurization washing cooling tower sewer (25) etc., surpass the emission standard several times, COD content is up to 300～3000mg/L, surpass several times of national standards, even tens times, these sewers can not enter in the existing circulating water treatment technology system.Therefore these ammonia-containing waters have to directly discharge, even the discharging of dilution back also is not easy up to standard.

After the more deposed ammonia that bled in the circulating water system, the pH value of recirculated water is increased, the water quality control breakdown, hyper acid and add acid neutralization consumption, and consumption chlorine is also high, therefore has to add former water recirculated water is replaced, discharge water contaminate environment, and waste medicament and water resources.

The existing water technology that generally uses all must be through above-mentioned 14 processes at small nitrogenous fertilizer plant, because complicated operation, workload is big, and technical difficulty is big, controls loaded down with trivial details strictness, processing costs is higher, difficult management, especially relatively difficult to the pre-film of quantity-produced small nitrogenous fertilizer plant parking pickling, so, this technology popularization speed is slower, and is fast slightly in the water shortage in north china area.

The present invention has simplified technology greatly, has saved pickling, pre-film, other filter, chlorination, has added sour blowdown, and made analysis, dosing, management become simple and convenient, and do not needed ammonia-containing water is disposed to environment in addition.

Referring to accompanying drawing 1, circular water treating system technological process of the present invention (is example with little nitrogenous fertilizer water coolant closed circuit circulatory system).

1, remove contamination:

By circulating water pool (1) recycle pump (3), cooling tower (4), circulation line (29), the compressor cold type (comprises compressor cylinder, the circulator cylinder) (5), carbonization water tank (7), inhale ammonia cold type (10), transformer coiled pipe (12), each analyzes post pollution discharge pond (13), ice maker cold type (14), synthetic cold type (16), refining cold type (18), conversion cold type (20), steam turbine (23), total sewer (27) in desulfurization cooling cleaning tower sewer (25) and above each post, in the circulating water system that total backwater ditch (28) is formed, clean with former water (26), remove mud scum, bacterium algae and foreign material discharge by wash water valve (2).

2, raw water quality analysis: according to analytical results, grasp the water quality situation, and calculate and add dose first, calculation formula is as follows

Add dose (kg)=((5-A) * 80)/1000 M first

The former water total alkalinity of A-(mmol/L)

M-recirculated water total amount (t)

5-controls total alkalinity (mmol/L)

The equivalent value of 80-HAS

1000-exchangeable bases coefficient

3, Jia Yuanshui: wash water valve (2) cuts out and go up blind plate, former water is added circulating water pool (1) and starts water circulating pump (3), beginning circular flow.

4, add water stabilizer HAS: will calculate the good dose (kilogram) that adds first and measure volume, and directly tremble and spread in the adding circulating water pool (1) with a dosing wooden dipper (32).If winter, temperature was low excessively, add again in the circulating water pool (1) after preferably in bucket, HAS being dissolved earlier with hot water.

5, add make up water: with the sewer of each workshop section, sewer when mainly being carbonization cleaning section (tower) carbonization water tank leakage ammonia comes together in total backwater ditch (28) by total blowdown ditch (27), water is mended in the circulating water pool (1) as a supplement then, if the water yield is not enough, add a part of former water to circulating water pool (1) by raw water tubes road (26) again.

6, circulating water quality analysis: analysis project is as follows: a week is analyzed once, pH value, total alkalinity, total hardness, Ca ^{+ 2}, M ^{+ 2}G, CL ^-, NH ⁺ ₄, turbidity, total molten solid, specific conductivity.Irregularly to former water with make CL in the ammonia-containing water of make up water ^-Analyze, calculate cycles of concentration, stockpile.

7, replenish water stabilizer: the empirical Calculation formula of adding dose is as follows:

Add dose (kg)=(P △ T α)/1000

P-is quantity of circulating water (t) per hour

△ T-dosing pitch time (h)

α-tonic experience factor generally gets 0.3～0.7

1000-unit conversion coefficient

8, scarfing cinder: annual overhaul is stopped, the blind plate of the wash water valve of dismantling (2), with the water discharging of circulating water pool (1), with manually go out clearly sediment hole, bottom, pond (33), (34), residue make fertilizer.Contain ammonia and COD contaminate environment in the discharge water.

And then get back to step 4, so constantly circular flow.

Referring to accompanying drawing 3: existing little nitrogenous fertilizer was inhaled ammonia cold type water circulation system technological process and is before the present invention finished:

1, remove contamination:

In the recycle system of forming by circulating water pool (1), recycle pump (4), circulation line (13), cooling tower (5), cooling coil (6), clean, remove mud scum, bacterium algae and foreign material etc. with former water.Rinse water is discharged from wash water valve (21).

2, pickling: after the recycle system is cleaned, be made into orchid-5 inhibiter etc. or clean-out system adds circulating water pool (1) with enough acid, ON cycle pump (4) is through circulation line (13) and cooling tower (5), arrive cooling coil (6) again, get back to circulating water pool (1) at last.So cycle pickling checked that dirt, iron rust discharge acid solution after cleaning up again from wash water valve (21) about 24 hours.

3, pre-film: after system carried out pickling, pre-immediately film added circulating water pool (1) with enough round-robin prefilming agents, ON cycle pump (4) circulation.Prefilming agent mainly is Sodium hexametaphosphate 99, zinc sulfate etc.Its effect is to make the bare metallic surface of equipment pipe form one deck compact protective film.Need strict on-the site analysis, control various ionic concentration and temperature in the pre-film liquid, time.And the vitriol oil in the concentrated sulfuric acid groove (12) injected add sour gauger (14), add the pH value of regulating pre-film liquid in the circulating water pool (1) again, pre-film reached about 40 hours, measured total content of inorganic phosphorus again, control total inorganic phosphorus in indication range by blowdown and moisturizing, just can put into operation.

4, raw water quality analysis: according to analytical results, handle the expert by different water quality clear water and design different water conditioning agent prescriptions, and calculate and add dose first.

5, Jia Yuanshui: former water is added circulatory pool (1), and start water circulating pump (4), beginning circular flow.

6, add water stabilizer: what will measure adds dose first by chemicals feeder (17) dissolving, and mixed evenly back adds in the circulating water pool (1), makes it normal circulation.

7, add make up water: system is in the circulation process of cooling, and vaporize water, sewer are arranged, the seepage of splashing etc. lost water.For this reason, in circulatory pool (1), add former water by make up water pipeline (3) and make make up water.

8, circulating water quality analysis: in the circulation process of cooling, with the adding of make up water, variation has taken place in circulating water quality.For stabilizing water quality, must regularly be analyzed as follows project: pH value, C to cycle water ^{+ 2}A, M ^{+ 2}G, total alkalinity, total hardness, turbidity, orthophosphoric acid salt, total phosphate, polyacrylic acid, NH ⁺ ₄, carboxyl ethylidene bisphosphate, specific conductivity, chlorine residue, CO ₂, total molten solid, K ⁺, heterotrophic bacterium or the like.

9, replenish water stabilizer: according to the circulating water quality analytical results, calculate the additional amount of every day, the various medicaments of per tour, the medicament that measures is dissolved by chemicals feeder (17), mixed evenly back adds circulating water pool (1).So circulation dosing.

10, add acid and regulate pH value: according to analytical results, pH value is adjusted in the pH value scope of application of water stabilizer, be generally 7.8～8.3, minority is 8.5～9.5, the injection of the vitriol oil in the vitriol oil storage tank (12) is added sour gauger (14), add circulating water pool (1) special messenger's on-the site analysis again, strict control pH value can not superelevation or low excessively.

11, add Biocidal algae-killing agent: recirculated water is in operational process, because water temperature is suitable, phosphorus in phosphorus line formulation and the compound prescription thereof is the nutriment of microorganism, the ammonia that bleeds or absorb the nutriment that airborne ammonia also is microorganism, the bacterium algae that very easily grows in the open type recycle system influences the heat-transfer effect of equipment and the normal operation of the recycle system.So will regularly add Biocidal algae-killing agent, in order to solve the resistance problem, also must be used alternatingly various biocides, generally with liquid chlorine, Babysafe, bromogeramine etc. are as biocide.Chlorine cylinder (15) is added liquid chlorine by rotor chlorinating machine (16) to circulating water pool (1).Strict control chlorine dosage, it is bad to have lacked the effect of killing livestock, and many can cause that corrosion consumes problems such as height.

12, blowdown: the CL in analysis cycle water and the make up water ^-Or K ⁺Ionic concn is calculated cycles of concentration, and calculation formula is as follows:

Concentration multiple K=(CL in the recirculated water ^-(or K ⁺) concentration)/(CL in the make up water ^-(or K ⁺) concentration)

Be generally 2～3, when cycles of concentration greater than 4 the time, must periodic blow down control, otherwise can cause the equipment pipe fouling corrosion, the sewer contaminate environment.

13, other filter: recirculated water in operational process owing to concentrate, residue, dirt, foreign material and water stabilizer slag etc. make increases such as recirculated water turbidity, suspended substance, influence water quality.Therefore, 3%～5% of recirculated water must be connect from pump discharge and be back to circulating water pool (1) after an arm (22) filters by other filter (12), regularly wash backwash flush away residue mud then, enter trench by blow-off pipe (19), (20), the discharge water contaminate environment other filter is suitable.

14, the processing of ammonia-containing water and the replacement proble that contains ammonia recirculated water: in the recycle system, break because of comb, perforation, wash out the more deposed ammonias that bled such as gasket, add that airborne ammonia is soluble in water, make that pH value increases in the water, water quality degenerates, it is too much uneconomical again to add acid, chlorination, have to former water is replaced a part of recirculated water, perhaps the ammonia recirculated water that contains in the system is all discharged, add former water, dosing circulation again.

The ammonia-containing water of carbonization system has to directly discharge.

And then get back to step 7, so continue circulation.

Accompanying drawing 4 has been described one embodiment of the present of invention, but is not limited to present embodiment.Present embodiment is the suction ammonia cold type closed water circulation system of small nitrogenous fertilizer plant:

The Ammonia Production scale of this small nitrogenous fertilizer plant is for producing 30000 tons of synthetic ammonia per year, and it is 500t/h that ammonia cold type quantity of circulating water is inhaled in design, and its technological process is as follows:

1, remove contamination: by circulating water pool (1) (this enforcement tank floor be provided with two square sediments holes (2), (3) its volume for long * wide * dark: 1m * 2m * 0.3 and 0.5m * 2m * 0.5m), in the recycle system that recycle pump (4), circulation line (13), cooling tower (5) and cooling coil (6) are formed, clean with former water, remove the Miao Zao of mud scum, foreign material and accumulation etc., with manually the thick incrustation scale that reaches 4～6mm on the comb having been knocked out some.Discharge by wash water valve (15).

2, raw water quality analysis: (the former water of this example is money rivers water)

Analytical data is as follows:

PH value 7.0

Suspended substance (mg/L) 100

Total solids (mg/L) 150

Turbidity (mg/L) 8.70

Total alkalinity (mmOl/L) 1.6

Total hardness (mmOl/L) 3.88

C ⁺²a（mg/L） 30.46

M ⁺²g（mg/L） 5.1

OL ^-（mg/L） 10.55

NH ₃-N（mg/L） 1.70

Dissolved oxygen (mg/L) 5.44

Specific conductivity (us/cm) 150

3, Jia Yuanshui: Jiang Yuanshui (14) puts into circulating water pool (1), and ON cycle water pump (4) circular flow.

4, dosing first: water stabilizer HAS is directly trembled in the recirculated water that spreads adding circulating water pool (1) according to the Total Water and the raw water quality analytical data that add in the circulating water pool (1).

It is as follows to add the dose calculation formula first:

Add dose (kg)=((5-A) 80)/1000 M first

The former water total alkalinity of A-(mmol/L) in the formula

M-adds circulatory pool Central Plains water inventory (t)

5-controls basicity (mmol/L)

1000-exchangeable bases coefficient

With the actual water capacity of A=1.6mmol/L M=130t(circulating water pool), the above formula of substitution calculates that to add dose first be 35.36kg.Every bag of 25 kilograms of dresses of HAS, actual adding one and half becomes Umber with the recirculated water color, and pH value reaches more than 8 and is as the criterion.

5, add make up water: system is in the circulation process of cooling, and vaporize water is arranged, the percolating water that splashes etc. lost (no sewer).For this reason, by water shoot (8) or (11) with carbonization cleaning section (7) (after adopting " a bit adding water; enrichment step by step " technology to reclaim, the deposed ammonia discharging that causes because of processing unit temperature operation etc. is still arranged) or the ammonia-containing water of carbonating tower water tank (9) (when the carbonization water tank leaks ammonia) directly enter circulating water pool (1), as the make up water of inhaling ammonia cold type water circulation system, use former water (14) to supply again when not enough.The present embodiment amount of makeup water is 1～3% of quantity of circulating water 500t/h, promptly per hour adds 5～15t make up water.

6, circulating water quality analysis: in the circulation process of cooling, because the coacervation of the loss of recirculated water and the adding of make up water (ammonia-containing water) and formation humate, make the composition of circulating water quality that variation take place, produce problems such as fouling corrosion in order to prevent water quality from degenerating, must periodic analysis.

The control water-quality guideline.Present embodiment gets following data do water quality analysis two days later in operation:

Total hardness (mmOl/L) 2.2

Total alkalinity (mmOl/L) 16.0

PH value 8.0

After one week of operation, get following data do water quality analysis

PH value 9.60

Total alkalinity (mmOl/L) 5.0

Total hardness (mmOl/L) 4.0

C ⁺²a（mg/L） 36.87

M ⁺²g（mg/L） 2.19

CL ^-（mg/L） 56.72

NH ₃-N（mg/L） 187.0

Total molten solid (mg/L) 456

Humic acids (PPM) color directly perceived

7, the steady medicament of make up water: the color according to water in above-mentioned circulating water quality analytical data and the recirculated water directly perceived determines to add dose.Good HAS elder generation weighing is good with calculating.Put into a dosing wooden dipper/(12), write down the shared volume of HAS, directly tremble then in the recirculated water that spreads pump inlet place that adds circulating water pool (I), so that borrow the abundant stirring and dissolving of power of pump rotation.

The dose of its additional dosing calculates by following experimental formula:

Operation replenishes and adds dose (kg)=(P, △ t α)/1000

P-quantity of circulating water (t/h) per hour in the formula

△ t-dosing pitch time (hour)

α-dose experience factor generally gets 0.3～0.7

1000-exchangeable bases coefficient

Present embodiment per hour quantity of circulating water is: 500t/h

Dosing pitch time is 24 hours, and is darker when the recirculated water color, is dense slightly dark brown, pH value desirable 0.3 more than 8, more shallow when the recirculated water color, is Sandy, and pH value is lower than at 8 o'clock desirable 0.7.

Calculate from above formula: to add water stabilizer HAS be 4～8kg every day during operation.

Note following item:

No matter be dosing first or additional dosing, when temperature is very low,, again HAS is trembled to spread with the dosing wooden dipper and add equably in the bucket with half barrel of about 40～50 ℃ of hot water of bucket splendid attire, stir with wooden stick or bamboo chip, make and pour that circulating water pool (1) is interior to get final product after the dissolving of HAS powder into.Under general temperature, HAS directly shed the pump inlet place in the pond with the dosing wooden dipper or directly tremble in the packing bag and spread the pump inlet pipe that adds circulatory pool (1) and get final product, pay special attention to not want disposable pouring into, it is insoluble to prevent that HAS from luming.Allow HAS behind recycle system thorough mixing, observation cycle water color, if being the dark brown pH value, the recirculated water color reached 8, then the dose that adds first that calculates of formula has reached requirement, if the recirculated water color is the Sandy pH value less than 8, then add again a bit, till recirculated water is dark brown, pH value＞8 in adding first on the dose of by formula calculating.Operation replenishes and adds dose except being as the criterion with the observation color, importantly control pH value greater than 8 and total alkalinity greater than total hardness, if total alkalinity is less than total hardness then must add dose on the dose in adding of by formula calculating, till total alkalinity is greater than total hardness.If the concentration of make up water ammonia-containing water is higher,, also must be as the criterion and replenishes HAS on time with color though pH value is very high.

8, scarfing cinder: the dismantle blind plate of wash water valve (15) of annual overhaul, with the water discharging of circulating water pool (1), with the residue that manually goes out two sediments holes, bottom, pond (2), (3) clearly, discharge cycle water contains ammonia and COD contaminate environment in the water.

And then get back to step 4, and so constantly circulation is carried out, and brings into operation the existing time more than 2 years so far on April 28th, 1989, and effect is obvious.

It is as follows that the present invention and the existing water technology that generally adopts contrast its good effect:

1, the steady medicament expense of water is reduced: the embodiment of the invention (take nineteen ninety degree as example) year medicament expense is as 4610 yuan, and traditional phosphorus to be compound prescription etc. use (water yield is identical running time) year medicament expense in the carbonization Water in Water Tank circulatory system be 19200 yuan. The embodiment of the invention year medicament expense for existing method for treating water year medicament expense use 1/4.

2, the processing before the dosing is simple: the present invention need not stop pickling and pre-film only need sweep the mud scum foreign material and get final product. And traditional phosphorus is needing to stop in compound prescription and the HAS description of product use book with the sour corrosion inhibiter of preparing or cleaning agent total system to be cleaned more than 24 hours, is mixed with the pre-film of prefilming agent more than 40 hours with two or more medicaments. Manipulation strength is large, and is dangerous, analyzes very complicated, and expense is many, and the impact that needs to stop is produced or only treated that annual overhaul could use, and the pickle emission of serious pollution of environment.

3, feeding operations is simple: the medicament that the present invention uses only is a kind of pulverulent medicament, directly add to get final product, and traditional water treatment agent that generally adopts now is 5～10 kinds of interim metering proportions such as solid, liquid, powdery, bulk, troublesome poeration.

4, environmental protection, security situation: nontoxic, without phosphorus, the not often blowdown of water treatment technology of the present invention and medicament, non-secondary pollution. Do not use the concentrated sulfuric acid and liquid chlorine etc., handling safety, medicine storing safe ready. If the recirculated water seepage also can in time be found from the change color of water. The concentrated sulfuric acid, liquid chlorine operation are dangerous, storing has specific (special) requirements and traditional technology of generally using now need add, and the contaminated environment such as phosphoric acid and COD are arranged in pickling and the periodical blowdown water, and the recirculated water seepage also is difficult for finding.

5, sterilization algae removal problem: the present invention need not add any Biocidal algae-killing agent. And traditional, existing technology must alternately add the Biocidal algae-killing agents such as liquid chlorine, Babysafe, bromogeramine, because phosphorus is the nutriment of microorganism, sterilization algae removal is frequent, and expense is high.

6, regulate the pH value problem: the present invention does not need to add in addition the concentrated sulfuric acid and regulates pH value, and after especially ammonia-containing water added, pH value increased suddenly, does not need acid adding to regulate yet.

7, analysis and Control situation: the present invention only analyzes need do total hardness, total alkalinity, pH value analysis, first quarter moon or January are analyzed once, for stockpile, do a recirculated water complete analysis in first quarter moon or January, its analytical instrument is simple, need not be furnished with ad hoc analysis personnel and ad hoc analysis instrument and equipment. Drug concentration can be directly perceived, regulates easily. And traditional existing technology needs strict control to circulating water quality. Analysis frequency requires tight, and procedure of test is loaded down with trivial details. Analysis project is nearly 20 multinomial. And when the pre-film of pickling, in time do large component analysis, need to be equipped with the ad hoc analysis personnel and work in three shifts. Otherwise the concentration of various medicaments especially acid will not have side effects in the control indication range, even can have an accident.

If there is more ammonia to be bled into system, the adjusting of medicament is difficult to control, has to circulatory system water is replaced and discharged.

7, other filter device and periodical blowdown problem are set: the present invention need not arrange the other filter device of the large again pollution discharging thing of investment, does not need periodical blowdown yet, cleaning pond when only needing overhaul to stop, and traditional existing technology must be established other filter device and periodical blowdown.

8, the control of cycles of concentration: cycles of concentration of the present invention can be controlled to more than 9 times, does not need at ordinary times to control cycles of concentration and blowdown. And traditional existing technology cycles of concentration general control is at 2～4 times, and the problems such as fouling, the long bacterium algae of burn into can appear in the high concentration multiple operation.

9, packing, storing and packing material are processed problem: the water quality stabilizer HAS that the present invention uses is a kind of powdery solid only, stores and transports with bag weaved and polybag double casing. There is not specific (special) requirements, packaging bag is nontoxic, can do other packaging bags after washing, and the water stabilizer of traditional prior art, drug variety are many, store and transport pretty troublesome, especially the concentrated sulfuric acid, liquid chlorine and liquid preparation have specific (special) requirements, and dangerous, and pail pack, the seriously polluted inconvenience of packaging bag are processed.

10, adaptability problem: the present invention is adapted to various industrial cycle indirect cooling waters, and pH value is the same greater than its effect of water quality of 9.5. Especially can be adapted to little nitrogenous fertilizer, cooling water closed circuit circulatory system in the closed water circulation contains the situation of ammonia, contain NH with what the small nitrogenous fertilizer plant contaminated environment felt a delicacy about jointly, waste water is made the supplementing water of the circulatory system, solved the processing problem without the ammonia-containing water of recovery value, this is important crucial part of the present invention. And traditional prior art is not suitable for pH value greater than 9.5 situation, not only disposal cost is high but also because of the difficulty displacement of having to greatly when particularly having ammonia to be bled into system, more can not make circulatory system supplementing water with ammonia-containing water, without the ammonia-containing water of recovery value still exhaust emission environment.

Claims (6)

1, a kind of nitrogen fertilizer plant's nitrogenous effluent and contain ammonia circulating water treatment technology comprises and removes contamination, raw water quality analysis, Jia Yuanshui, adds the steady medicament of water, adds the circulation make up water, the circulating water quality analysis, replenishes operations such as adding the steady medicament of water; It is characterized in that:

A, with nitrogen fertilizer plant's ammonia-containing water directly as recycle system make up water;

B, use the series of phosphorated humic acids not HAS water quality stabilizer as the water quality stabilizer that contains the ammonia recirculating cooling water system.

2, nitrogen fertilizer plant's ammonia-containing water according to claim 1 and contain ammonia circulating water treatment technology is characterized in that its technological process is: A, remove contamination;

B, raw water quality analysis;

C, Jia Yuanshui;

D, add the steady medicament HAS of water;

E, add make up water;

F, circulating water quality analysis;

G, additional water stabilizer;

H, scarfing cinder;

And then get back to operation E, constantly circular flow.

3, nitrogen fertilizer plant's ammonia-containing water according to claim 1 and 2 and contain ammonia circulating water treatment technology, it is characterized in that removing contamination of its technological process is not need pickling, pre-film, other filter, chlorination, add under the situation of acid, blowdown in subsequent disposal, whole circulation system is cleaned with former water, remove mud scum, bacterium algae and foreign material etc.

4, according to one of claim 1 to 3 described nitrogen fertilizer plant ammonia-containing water and contain ammonia circulating water treatment technology, what it is characterized in that its technological process adds water stabilizer HAS, is by calculating good dosage, HAS directly being added in the circulating water pool (1).

5,, it is characterized in that the particular content of its technological process is according to one of claim 1～4 described nitrogen fertilizer plant ammonia-containing water and contain ammonia circulating water treatment technology:

A, remove contamination:

By circulating water pool (1), recycle pump (3), cooling tower (4, circulation line (29), the compressor cold type (comprises compressor cylinder, the circulator cylinder) (5), carbonization water tank (7), inhale ammonia cold type (10), transformer coiled pipe (12), each analyzes post pollution discharge pond (13), ice maker cold type (14), synthetic cold type (16), refining cold type (18), conversion cold type (20), steam turbine (23), total sewer (27) in desulfurization cooling cleaning tower sewer (25) and above each post, in the circulating water system that total backwater ditch (28) is formed, clean with former water (26), remove mud scum, bacterium algae and foreign material discharge by wash water valve (2);

B, raw water quality analysis: according to analytical results, grasp the water quality situation, and calculate and add dose first, calculation formula is as follows:

Add dose (kg)=((5-A) 80)/1000 M first

The former water total alkalinity of A-(mmOl/L)

M-recirculated water total amount (t)

5-controls total alkalinity (mmol/L)

The equivalent value of 80-HAS

1000-exchangeable bases coefficient

C, Jia Yuanshui: wash water valve (2) cuts out and go up blind plate, former water is added circulating water pool (1), and start water circulating pump (3), beginning circular flow;

D, add water stabilizer HAS: will calculate the good dose that adds first and measure volume with a dosing wooden dipper (32), directly trembling looses adds in the circulating water pool (1), if temperature was crossed and added in the circulating water pool (1) after low preferably elder generation dissolves HAS in bucket with hot water again winter;

E, add make up water: with the sewer of each workshop section, sewer when mainly being carbonization cleaning section (tower) carbonization water tank leakage ammonia comes together in total backwater ditch (28) by total blowdown ditch (27), water is mended in the circulating water pool (1) as a supplement then, if the water yield is added a part of former water to circulating water pool (1) by raw water tubes road (26) inadequately again;

F, cycle water analysis: analysis project is as follows: pH value, total alkalinity, total hardness, Ca ⁺⁺, Mg ⁺⁺, Cl ^-, NH + ₄, turbidity, total molten solid, specific conductivity; Irregularly to former water with make Cl in the ammonia-containing water of make up water ^-Analyze, calculate cycles of concentration, stockpile;

G, additional water stabilizer: the empirical Calculation formula of adding dose is as follows:

Add dose (Kg)=(P △ T α)/1000

P-is quantity of circulating water (t) per hour

△ T-dosing pitch time (h)

α-tonic experience factor generally gets 0.3～0.7

1000-unit conversion coefficient

H, scarfing cinder: the left alone without help car of annual overhaul, the blind plate of the wash water valve of dismantling (2) is with the water discharging of circulating water pool (1), with the residue that manually goes out (33) (34), sediment hole, bottom, pond clearly;

6,, it is characterized in that in circulating water pool (1), being provided with 1～2 sediment hole (33), (34) according to one of claim 1 to 5 described nitrogen fertilizer plant ammonia-containing water and contain ammonia circulating water treatment technology.

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