SK3392A3 - Method of water solution purification, polluted by nitrat ions - Google Patents

Abstract

Process for the purification of aqueous solutions contaminated with nitrate ions. This process is characterised in that it consists in precipitating double or mixed hydrated calcium nitroaluminates, such as especially calcium mononitroaluminate hydrate, by addition of at least one agent introducing the element aluminium and at least one agent introducing the element calcium into the solutions to be treated, the overall molar ratio of the element aluminium to nitrate, Al/NO3, being higher than 1, the overall molar ratio of calcium to nitrate, Ca/NO3, being greater than 2, and in that the precipitation reaction is performed with stirring and at basic pH, preferably higher than 10.5. The process according to the invention is intended especially for the treatment of polluted waters such as domestic sewage and industrial effluents and for the treatment of liquid manure.

Description

- 1 -91 / 3i- <? Z * í '«J i tfpAaob C-i .:

• - '. • t M t * · »t K; (í

Oblavi Techniques V.ynalea »e tyka aodsobu diSUmi vodni roatckii, unocií: - 'tdnych auaíéaaiiovýiaa ions ·

The UVXor® recycled solids, vanicides in the production of various types of fertilizer, preferably fertilizer, and more suitable for use as a fertilizer.

In the prior art, the term " unldnd " is used once and for all. In the present invention, there is disclosed a process for the production of fertilizers for use in the manufacture of such fertilizers. v.yscUnu douin κ ic ic ic ky ky ky ky ky ky ky ky mnohé mnohé mnohé mnohé mnohé,,,,,,,,,, ye ye ye ye ye ye ye any any any any any any any any any any any any ičné ičné ičné ičné ičné ičné ičné ičné ičné ičné ičné oh salt is vi? vétlSSné pM-inxd & doprováaeno vanJketa toki.t? waste and oboh < m ďuaiónanovýhonu! · In the case of wastes and other violet forums, JCS does not. The nitrates are: avionic. the duo is available in Cocoa in cocoa and other nitrogen nitrogen. Jacm waste in KeisädolnKo-potrin'ináhekéw pniisyalu. t un č any any any í í í í í í í í 3 3 dní dní 3, af 3 af af af af af af af

[0020] The muco-nitric nitric acid and / or nitrogen are sucked into the mucosa. Liquid fat fertilizer providing one or more rich nutrients. Nitrogen: Approximately half of nitrogen in the tube of a livestock man. Fertilizer Is Ρ »κ & the organic in the diazoacid form & nts, from 2 to J, p < / RTI > / 1 / the same water also contains smaller amounts of nitrogen and nitrogen, which can be found in the cauliflower. -tou preiwdnun tm čuaidnany.

To achieve this, the chemical fertilizer is a liquid livestock manure to be inspected.Introduction, including natural contains poor bacteria. the dialo-loss occurs by degassing the ammonia, the soil will be alkalinized with many organic compounds and nitrification of KH, +. The resulting nitrates can be extracted by roatliums, and they must be dried or dehydrated in a drop depth below the POA absorbent zone, which is also a guarantee for dewclaws and dwells in the ground or reduce the time to subsoil. .

The nitrates are soluble in the aqueous solution in the large dose, so it does not matter for the drug or phthalate of origin, they for the chemical nature of the cathode. For example, rospuotnoot, calcium nitrate OeWO. kg per liter at 0 ° C per liter of sodium nitrate 0,9 «Μi is 0.921 kg per liter pi'i "‘ Λ.

It is known that nitrates are present in repeated repeated doses if they are taken up in repeated doses. potentially toxic, it was not possible to convert from nitrate to duel tons, which caused mothomoglobinonium · Nitrates can also be converted into nitroaines, which are thought to be carcinogenic. water free from water. non-nitration of nitrates and chemicals and industrial ouoatlôs, such as mineral waters or natural chemical fertilizers / rossatiating liquids /, in opaque and groundwater, abrasive ·

I < a result of their high solubility in water, so in some cases water becomes unsuitable for ingestion.

In France «general in fcvropská bpoleí. The concentration of nitrate in drinking water is about 90 g / l. In some major networks, the French; '! the density reaches up to 100 c / i in the drinking water content of the drinking water, which is due to the lack of corrective agents to remove nitrates. nowadays, the problem of dprovy drinking water for consumption by various ways to control the flow of effluent to and from, or even tones of nitrates, such as the liquid subtitle fertilizer, noexiotu-is no economically advantageous, práwywlovô usable proceo. The present invention relates to a process for the treatment of physical water by the physical chemical removal of nitrous butadiene sulfonium ionics.

This process requires the treated water to contain a non-solvent for one liter of the solids to be treated. In the opposite case, the water to be treated must be coarse and flushed and one or more flocculation and filtration and / or one is impregnated. However, more than one type of ion exchange process, the ionic ion exchange process has the same properties as sulfate, chlorine, and bicarbonate. One of the main drawbacks of this process is that it can not be used in the supernatant of sulphate content in chloride conductors, because their affinity for nitrate is much more common in sodium chloride and béheat water treatment occurs alone in chloride lontôm nitrate o 5 he you. bôolodkeia Is the increase in chloride content? In the case of the water treated, these methods are particularly useful in the process of using the eluate after the regeneration process. What to do about tcaito chlorates, nitrates, and often rich eluates As their mercury concentrations are too high, they flow into the most flowing stream. In other cases, they are diverted to the closest biological plant or stored.

The iodine and biological processes for the removal of dual ion ions by the use of weighted bacteria capable of activating these ions. Usually, they emit bacteria that are heterotrophic with their carbon-containing substrate, yuko are ethonol or acetic acid. The bacterial uuot results in an excess of blomay or cola, although it can be disposed of with a sludge or opal enema. But a gaseous tube is converted. .this process takes place only at temperatures above B - 10 ° J ·

In addition, the temperature of the entire process must be stable, so that the control is complicated and consequently the process is expensive. SUMMARY OF THE INVENTION The object of the present invention is to propose a solution for aqueous solutions, anionic and ionic surfactants that are simple, efficient and inexpensive. The present invention is to recycle a camphor, which creates a process of deboning and incorporates dual phthalene lions. The present invention provides a process for the preparation of aqueous solutions, characterized by a diluent, characterized by the inclusion of hydrated double or precipitated calcium nitrates, such as hydrated sodium nitrates. Alumina is added to the clarified solution, added with aluminum, this reagent being referred to as " quartz " activating altos, and aleopone One agent, adds calcium, the total molar molar of the aluminum to the dondonds, ΑΙ / ΝΘ-j, is greater than 1, and the total talar of the calcium to dianates, G'a / ωO, it is higher than 2f This precipitation reaction oo performs a pM basic pH, preferably greater than 10, >, and, in my opinion, suitable, formed and calibrated, e.g. afterwards, there is one or more fixes and physical aeparations of α / u's filter supports.

Taking the rhododonthods of the compounds present in the first solution and thus substantially reacting with the hydrated calcium nitrate, the process of the present invention is entirely satisfactory for the process of the present invention. value of a large number of diatomaceous duols in the form of hydrated double or tumbled calcium aluminosilicate is eliminated by the number of non-unfolding knots in the form of a hexavalent, as well as nonionic anions, such as sulphates, carbonates and chlorides, which form an insoluble precipitate in the presence of calcium or form complex calcium aluminates *

According to the invention, it is advantageous at room temperature. The values are not below 20 ° C or 10 ° C to 40 ° C according to the season, the invention is preferably carried out at a temperature of about 0 ° C, the advantage being below 20 ° C because the starting point of the reaction is more potent , on the other hand, ntra-a5 is a better reoccupation. If appropriate, the eeparaef nitrate ion conducts chemical treatments to remove undesired elutrients contained in the particulate waste. In the case where the waste is coated with the suspended solids, one or more precipitations of these substances can be carried out with a flocculant, for example using ferric chloride and a base or aluminum sulphate or possibly using an organic flocculant such as napF. acrylic-AMLD. After this, one or more of the filtration and / or lashing and physical aepuration wotodes follow. If dioptic waste encodes undesirable aniorites or cocapoatons, forming insoluble calcium salts, the punching of these components is preferred. when the reagent is added, calcium is added. The phases of the stage are then cleared away before they are removed from the body. Preferably, this precipitation is carried out with calcium hydroxide. This is the process of Jo Concentration, Concentration of Sulfates, Phosphates, Carbonates, Fluorides, etc., which are in the forum. calcium salts only slightly soluble. The scavenging of these and others does not limit the formation of other alumina, accompanying hydrated calcium nitro-aluminates. Accordingly, the treated waste contains undesired cations or components forming a copper soluble noble-insoluble hydroxides, precipitating these components and, preferably, adding basic agents. Calcium hydroxide is preferred. In addition, this operation does not reduce the concentration of anions which are sparingly soluble in the phono-salts of calcium salts, such as those which are partially soluble in the hydroxide form, such as e.g. lead. After the removal of the high - sixth, the odatronous douna - nna emerge.

The present invention and various other sources of relief provide the ulcers that are applied individually or in cablabiolol. As an example, aluminates, alumina aluminates, calcium aluminates forming natural cements such as nitrates can be cited. (JA., OA, C, 0-7 and CA and calcium aluminaferites. In the above formulas and the following symbols, the following meanings are used: ΰ stands for CaO A stands for AlnO ^ H stands for HoO. Calcium aluminates obtained by alination processes exhibit better acetylene and reactivity in these works, and hydrated calcium aluminates can also lead to the formation of complex alumina by means of, for example, Aluminium cements and commercial names of FONDs, CAs. LiXk is the same as cubic ΐ, they are also suitable.The latter compound is a cubic calcium aluminate C ^igíig which is thermally decomposed at about J00 ° J to C ^ .- Αγ and Oa (OH).. a complex stoichiometric composition for the formation of complex aluminates, ie C / Aj, in the case of reaction with calcium salt. and / or Ο γγ and λ 60 á & itné itné itné itné nebo nebo nebo or in combination and other compounds.

It reacts gently to reactivity and yields yields in less time when 1 to ': > hours. The yield can be further increased by the use of C a AA and IOO. The best yield and reactivity were achieved by the pM use of the OHn reagent, which corresponds to the CyA n depositing product with excess alumina ·

Initially, it is advantageous to use a stoichiometric strain which corresponds to the C / A-4 primer and O / k-j for the calcium salt solution. the calcium-supplying agent is calcium hydroxide or calcium-aluminate, optionally supplementing with additional calcium dodose agent such as calcium hydroxide. Preferably, the reaction may be initiated by the addition of hydrated double or mixed calcium nitrite. It adds calcium-nitrated calcium nitrate in an amount corresponding to 10 to 10% by weight of the total amount of calcium aluminate to be reacted.

Under these conditions, it has been found to accelerate the formation of hydrated double or lime calcium nitrate and to increase the nitrate precipitated yield. Hydrated double or aluminated calcium nitrate, which is predominantly produced in the reaction, is advantageously used to inoculate porous centers.

According to the invention, standing in the same way as the above-mentioned variants, the particular advantageous applications for water treatment and nitrate content are found. and other inorganic compounds such as liquid wastes and municipal sewage, or as a solution! and a material containing omonlakal nitrogen which can be converted to nitrates such as liquid rot. If the treated solution is diluted to aoonic or nitrogen in organic form, then the method of the invention makes it possible to reduce the level of contamination and to reduce or eliminate contamination. This applies extraordinarily to natural materials! as is a liquid slurry from which nitrification solutions are formed by nitrification.

Liquid dung or nursery still free from burr or spreading, in raw state. The high dissolved nitrogen content, especially in the ammoniacal form, causes the risk of considerable contamination, especially if the time of year does not assimilate the plants! large amounts of nitrate! needed for Their rdst. By simply thinning the liquid slurry from the present invention prior to spreading, the fertilizer quality is maintained and the pollutant is reduced.

A first preferred embodiment of the invention which relates to a particular solution solution! or nitrogen-containing auapenes in atao-nickel-like resembles, such as liquid slurry, from these steps: 1) ammoniacal nitrogen, contained in the solution reader, and nitrate nitrate biochemical oxygen uptake.

For this purpose, the accusation procedure can be used; a solution rich in ammonia nitrogen, such as a liquid manure or slurry component, is aerated and, if necessary, a B-solution and inoculated with a bacterial or other microorganism. 2) when most of the ammonia nitrogen is converted to nitrates, one or more calcium aluminates are added to the purified solution so that the total molar ratio of alumina to alumina is greater than 1 and the total molar ratio of calcium to nitrates is the stiffeners considered to be an anion was greater than 2. It is added if necessary, h; calcium hydroxide and / or other basic reagent for pH adjustment, preferably greater than about 10, and in the case of a precipitation reaction, and a pH of about room temperature. J) a thick suspension or solid precipitate is formed after separation, for example by filtration or filtration, the lacquer product preferably being useful as an additive for the enrichment or fertilization of agricultural pAds. 4) the liquid effluent that is generated at the end of the process is free of nitrite and the bulk of the contaminants compared to the liquid inlet process. It can be released into the wild without risk.

If the method of the invention is used to purify liquid effluents, such as slurry, then, unlike the prior art, not only is the large nitrate ion exchange removed, but also the insoluble hydroxide-forming ions of insoluble calcium salts. Another advantage is that the drain is clean, colorless and odorless. Liquid wastes contain bile organ organic substances that produce saturated color, moving from yellow to brown, and which are only biodegradable. It can be assumed that these colored organic compounds are bound in the precipitate of hydrated calcium mononitrile and / or in other precipitates, which accompany the formation of this precipitate, especially precipitates of insoluble hydroxides and insoluble calcium salts. The alkalinity of the supernatants or solids obtained at the end of step (3) makes it possible to balance the acidity of the falls. In addition, the content of low soluble nitrates makes it possible to supply nitrate fertilizer in - 9 - an amount that corresponds to the rate of consumption of roots and thereby eliminate the source of groundwater pollution and surface flows.

Nitrification according to step (1) involves the conversion of ammoniacal nitrogen to nitrates by the biochemical route in the presence of titrating bacteria and oxygen, exclusively supplied by aeration. It turns into normal conditions.

General ongoing help of autotrophic microorganisms in two phases; oxidation of the ammoniacal nitrogen by means of a suitable microorganism. an example is the genus Nltrosomonas. - followed by oxidation of nitrite to nitrates by a suitable micro-organism. An example is the genus Nitrobacter.

Nitrifying microorganisms can be found in the sludge of sewage treatment plants or, if appropriate, in a readily or completely nitrified liquid manure or slurry.

The rate of nitrification depends in particular on the temperature, the pH being maintained between 7.3 and 0 and the amount of oxygen utilized by the microorganisms. It is also important to ensure that the nitrification medium does not contain organic and inorganic compounds capable of modifying or even inhibiting the growth of micro-organisms. details of the conditions necessary for nitri-ficacl can be found in the " Mémento technicjue de l * eau " (Technical handbook on water), 9th edition, vol. lf atr. 900-901, DEGHEMONT. Preferably, adjusting the pH to that required by the pre-sterilization reaction in step (2) is carried out with potassium hydroxide, thereby obtaining residual potassium-rich sludge that increases their fertilizer value. It is preferred to pre-precipitate the hydrated double or mixed calcium nitrate (step (2) of the first embodiment), either before or after the nitrifying step (1), the insoluble fraction contained in the liquid material (s) to be separated, at least partially, or complete flocculation followed by filtration and / or deposition and separation. Solid-material οροίβδηδ is separated into protein-rich components, phosphates and nitrogen compounds, which are sparingly soluble in water. Advantageously, the solids are removed from the solids either solid in liquid liquid or otherwise similar to the material being processed before the nitrifying agent and the clay. If this is not the case, solid constituents that have some biological oxygen demand (BiCl) compete with the nitrification reagent, which is naturally disadvantageous.

If the filtrate is treated with purified liquid slurry or a similar waste solution, it is then subjected to: - nitrification according to (1), unless it has been carried out before, and then subjected to a stepwise process, leading to nitrate removal, according to the invention. ) and O).

The most abundant yield of the ritrate was under these conditions.

If appropriate, the solid materials are separated from the obtained pinch at the end of step O), for example by flocculation followed by filtration and / or settling by separation. On the one hand, the nitrate-free filtrate has a clean and practically odorless solution, which is capable of disintegrating into the nature or usable for irrigation, and on the other hand a solid material encompassing hydrated double or ammonium calcium nitrate aluminates which are used as fertilizers . With the aid of agricultural experiments, it has been shown that in a solid material containing hydrated double or mixed nitro-calcium nitrate, the dianic ions are often bound, but they overcome the accessible plant and assimilate a longer period of time.

The practical application of the liquid slurry processing process of the present invention can be explained by the following example of a plant installed on a pig farm.

Provided for performing the present invention in detail

The bedding comes from the repair and addition of an existing installed liquid slurry collection tank with a separating device.

After modification and modification, the new system consists of an input section formed by a nitrlflection tank N.

The nitrification vessel N is provided with an aeration system forming a microbubble to assist in the blowing of air and diffusion.

This sova t and va also includes a nitrate reaction reactor in the process of the invention and a device for the separation of descending aols.

The system can be supplemented with an overpriced stage, which, prior to the nitrification, adjusts the liquid slurry by separating the solid portions in a flashy manner such as by settling, by sieving the sieve, or by a BLK reducing step and aiding the oxygen uptake of the processed material. Flocculation can be accomplished using a weak cationic polyacrylamide.

A further section of the existing collection tank is the tank B used to store the effluent obtained after the nitrate ionization is separated.

Procedure 3

Liquid slurry daily flow into the system in m Depends on the number of pigs reared.

It produces an overpriced stage before nitrification; - organic sludge containing a high percentage of product. This sludge contains organic nitrogen and apparently all phosphorus. Can be used as fertilizer for enrichment! humus in the same earthquake company. a liquid slurry which is processed to contain a small amount of solid particles in suspension.

Nitrifi kače

The liquid slurry depleted of organic talc is fed to the nitrification tank N.

The residence time is adapted to the rate at which nitrification takes place.

processing

The processing procedures are as follows: curing

Procedures, in particular, useful for processing capillary liquor slurry, which is baking: At regular intervals, 3e withdraws a certain volume from tank N and transports the reactor. At the same time, a certain volume of nitrate free of the final effluent can be transferred from the effluent collecting tank d to the nitrification tank 11 to maintain a constant volume in the reservoir N in the next processing step. It removes the early objects and adjusts them and calculates them to maintain not only a constant level but also constant concentrations of NO 4 in the tank f. It is made possible by the fact that the dunnanand quantity, equivalent to the one produced in the process of speech, has to be relieved from the tank. The liquid slurry processed in the reactor is admixed with a suitable amount of alumina (and if necessary aluminum hydroxide). In mixing, no reaction continues. The reaction is completed and the nitrate salt is removed by suction through a sieve filter to remove salt. It is also possible to separate sdl by simple uauzenna and physical separation. ϋΛΙ is stored until it can be used as fertilizer. The effluent, which is free of nitrate (generally no more than 0, J to 0, 3 g / l NO / j) and an apparent potassium content, is present in the slurry inlet and is collected in the tank S. It is used. as a fertilizer, for example spray

According to a second embodiment of the invention, which is directed to the treatment of aqueous solutions containing many nitrate and small amounts of organic matter, such as wastewater or municipal wastewater or regeneration solutions for ion exchangers used in various transports, and variants of the invention are preferred. represented by the following steps: 1) at least one calcium aluminate and, if it is a calcium hydroxide or other alkaline pH-enhancing agent, is brought into the solution to be treated. teplotč. 3) upon completion of the reaction, the resulting suspension is subjected to settling and mechanical separation and / or filtration, after addition of a flocculating agent if necessary. 4) the filtrate obtained is then neutralized if necessary, which results in the alumina being precipitated out of the solution, in the form of an insoluble hydrooxide. 5) finally, the new suspension obtained by the previous process is subjected to a mechanical separation operation and / or to a filtering agent, whereby a clear water is obtained which can be introduced into the natural environment without any risk.

If the nitrate content of this clarified water is less than 50 mg per liter, and if it does not contain other ingredients or compounds in excess of the maturity permitted by the mandatory regulations, this water can be introduced into the drinking water distribution network.

If the contaminated water treatment solution, such as water that is disposed of or has contamination in the soil or fish farm, or such as municipal wastewater containing ammoniacal nitrogen, is preferably added to the type of process that has been mentioned is a nitrification step, or the process is preferably adjusted such that the nitric acid solution is. Sodium hydroxide, potassium hydroxide and / or calcium hydroxide can be used as the basic agent in the step (1) step. The basic agent is preferably added prior to the addition of the calcium aluminate. This will reduce the concentration of cations which are only sparingly soluble as insoluble hydroxides. Preferably, prior to addition of the calcium aluminate, a lime-adding element is added. This agent, which is different from calcium aluminate, is added to the solution to be treated. This is due to the reduction of the anion concentration, which is limited soluble in the form of calcium salts, such as sulfur, phosphate, carbonate, fluoride and the like. It is also preferred that the process is carried out such that the calcium hydroxide is an alkaline agent and a calcium delivery agent, and is added to the solution to be treated prior to calcium aluminate.

Thus, the solution undergoes the treatment by which the nitrate is removed. , by precipitation, after the decanting phases disposed of in the preceding stage, the process. These variants of the uoatup make it possible to create other complex aluminum alloys that lead inonanitroholinite to impregnate. A naturally occurring flocculating agent such as alginates or xanthan soluble resins is preferably used in the precipitation step. Salts such as ferric chloride or aluminum sulphate are also useful, but as polymers, for example polyacrylamides. The pH-adjusting pH of this variant of the process of the invention at the end of step (3), when rich in calcium nitro-aluminates, can and advantageously be used as an enrichment additive and fertilizer for soil soil. It is important that they contain limited soluble nitrates, allowing the nitrate nitrate fertilizer components to be gradual, dairy plant consumption, and eliminates the significant hazardous source of contamination of both surface streams and groundwater. It should be noted that the alkalinity of these slurries makes it possible to fed the kyaelos of the soil, which may be caused by the introduction of acidic substances into the air at the time. In this case, the filtrate assumes that it uses drinking water for the purposes of the drinking water treatment, or that the filtrate is intended to be discharged into the environment and is preferably used. neutralize the filtrate (step 4) by treatment with 00 to precipitate the carbonate. present foamy and hydroxide hydroxide. Also, in accordance with the process of the invention, such a process is also provided wherein the nitrate salt precipitating agent or reagent present in the solution may be solid; which, due to their properties, influence the kinetics of the formation of the corresponding nitroaluminates, both double and mixed, or even in the combination. Other features and advantages of the process of the invention and the particular embodiments thereof are exemplified by the following non-limiting examples, which are not to be construed as limiting the scope of the present invention.

Example 1 to 3

The aqueous solution containing calcium nitrate (CaNO3) is fed into a chemical reaction vessel equipped with a magnetic stirrer, the inlet concentration being 500 mg per liter or 125 mg per liter. In this example, calcium aluminate (referred to in the table below as CA) is used as the nitrate active ingredient, which is in the form of an aqueous solution. An additional amount of calcium is supplied in the calcium hydroxide Ca (OH) 9.

The actual process is performed by adding CA and Ca (OH) 0 while mixing the mixture. Further processing is carried out by stirring. The suspension obtained is filtered or treated with a flocculating agent and subjected to a settling and separating process. Afterwards, the determination of the nitrate ion is carried out using a specific electrode after the addition of buffer and adjusting the pH to 5.5.

Other conditions and results obtained in the Exemplification Example no. 1 to 3 are shown in Table I.

Table 1

EXAMPLE 1 EXAMPLE 2 Example J Initial Concentration of NO4 (rh / l) 500 125 125 of Ca in water solution (m < 2 > / l) 711 355 Ca (OH) -. if: · r Al / NO 4 · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · \ t ) 123 81 96 Yield (¾) 75 35 23

Examples 4 to Ú

The working conditions in these examples are the same as those in Examples 1 to 5, and with the addition of aluminum. The next working cloth, as a result, is shown in Table II

table

Example 4 Example 5 Example 6

Initial concentration of NO j (tug / 1) iCount O ^ A (uijf? / L) > 00 250 5 000 5 000 5 000 - 17 - Continuing Table II Example 4 Example 5 Example 6 Amount of Ca (0H) o C '0 0 0 Total Col. ai / no3 4752 9.19 1.0 Total molar pores Ca / NO ^ 7.25 14.28 7.0 Processing time (min) 950 (220) 160 1,100 Residual NO 2 concentration (mg / 1) 86 (96) 98 480 Yield (%) 83.4 (80.8) 60.8 79.1

Examples 7 to 9

The working conditions in these examples were identical to those in Examples 1 to 3, with the exception of the aluminum-providing agent. This diet was SECAK 71, an industrial cement supplied by LAPAHGE FUND INTEHNATIQNAL. SECAR 71 has a composition of about 70%, and about 29% of GaO and other oxidants. Other working sub-bases and the results of these examples are shown in table ill.

Table III

Example 7 PH to ice 8 Example 9 NO 2 initial concentration (mg / 1) 175 500 500 SECA.hu 71 (mg / l) 655 7 620 .2 620 Amount of Ca (0H) o (mg / l) 1,000 4 000 2 970 Total moles of Al / WO ^ 4,4 6 4,46 4,46-18 - Continued Lli Example 7 Example 8 Example 9

Oa / NO-j 8.91 8, yi 7.19 Effect Time (min); > :).} 1,070 1,020 Residual Concentration no., (Mg / ι) 78 10? 169 yields (%) 07,6 79,6 66, l'H HM pros 10 u 11

The working subclasses in these examples were identical to those in Examples 1 to J, and the other aluminum additive added is a product which reacts with the aluminum. C ^ A, 60 hunt. O ^ Ay and 4 and masses. titumitu vópenetáho. This product is a dole in the examples of the marquee.

labulka IV

Example 10 Example 11

The concentration of MIX is counted. (mg / 1) 500 900 Breasts 2.i Uig / l) 4 990 4- 990 Amounts of OaCOHK (^ /]) J 965 Total Phold. Al / hO ratio ·. d / ir < · w > 7 4,45 Total molar ratio J, a / ttQ, 5,60 7,21 Residual concentration N (rng / 1) 18 j a:, 1 Time of payment í. ) 270 75 The yield (¾) 69, 8 89.6 - 19 - 3 was observed that an increase in the total Ca / NO 4 ruol ratio by the addition of calcium hydroxide results in a significant yield.

Examples 1? and 13

The operating conditions in these examples are identical to those in Examples 1 to 3, except for the Aluminum Delivery Agent, which is a 37% by weight product. C.jA, 95% by weight. and 8% by weight. titanáôútsópesójbóhatého.

This product will be referred to as the N symbol in the examples that follow, Other working conditions and results for these examples are shown in Table V.

Table V

Example 1? Example Initial MO concentration (ing / l) 500 500 Amount N (mg / 1) 4 390 4 3 ^ 0 Ca (Oll) .-, (mg / 1) 0 965 Total Al / NO ^ 4 molar ratio, 49 4.49 Total Ca / NO ratio 5.58 7.19 Time of action (min.) 540 100 Residual concentration of NO ^ (mg / l) 187 90 Yield ('P) 62.6 80.4

Hylo has been observed that by increasing the total Ca / NO 2 molar ratio of calcium hydroxide, the yields can be substantially improved. - 20 -

EXAMPLE 14 This invention does not provide processing liquids anymore.

The liquid liquid being tested is liquid manure liquid.

Nitrification and Conducting Slurry Aeration 7? hours by bubbling through the air in the microfluorophosphoric acid.

After nitration, the slurry contains 1000 cig / ml * nitrate, which is the initial concentrate. The suspended solids are removed by addition of aluminum sulphate in a 0.1 µg / liter slurry to be deposited by settling to produce an aqueous solution of the active alumina and calcium hydroxide, and CaCO 3 K, while maintaining the solution for 50 minutes. * The obtained suspension is clarified and the concentration of dextronate is determined after the addition of ionic buffer and a pH of 5.5 *.

Other worksheets and results obtained by the examples described are shown in Table VI.

Table VI

Example 14 Yearly Concentration Π0. ·, T:., 7/1) 000 000. Amount of αv OH Ca (OH) λg / 1) J 50? Total Al / Al 2 O 3 (molar) n Total ponier Oa / NQ ^ (polar) Time of melting tn in. Yo Residual Concentrate C Here r / 1) 600 Yield (%) 80

The initial secretion and the tip of the mutated au- tant, which bears the character of a protein, makes it possible to draw a good denitrire pencil. 21 -

Example 15

Into an aqueous solution containing calcium nitrate in the concentration corresponding to I 1! 0.70 g of calcium aluminate, characterized in the examples 12 and 19 by the symbol " N " and 1.91 g of Ca (OH) 2 per liter of solution, are added.

Under these conditions, the total Al / NO ratio is 2.25 molar and the total molar ratio of Ga / NO 4 is 9.6.

The pH and the nitrate concentration are varied as a function of the reaction time of the specific electrode being added to the buffer and adjusted to pH 5.5. The results of these measurements are recorded in the following Table VII. Table VII PMP 15 Gas (min.) NO ^ (mg / 1) pH 15 1 251 12.00 30 1 065 12.09 45 1 005 12.04 75 754 12.00 105 579 11.87 135 521 11 The yield of the precipitation reaction of dianate ions after 155 minutes is 75%.

Example 16

To an aqueous solution containing 1,608 mg of nitrate per liter is added 8.78 g per liter of calcium aluminate, characterized by the " N " and 1.93 g per liter of G ^ COHjg at the start of the reaction.

After half an hour of reaction, 5 g of calcium hydrated calcium nitrate-3GaO, Al2O4Ca (NO4) pnH2O3 containing 46% of the dry dry extract is added. In the reflections of this teat, the total molar ratio, Al / HO ^ equals% 8, and the total molar ratio Oa / ΚΌ ^ y is equal to 4.3. previous example. The results are listed in the following table Vili:

Table Vixi Example Oae (min.) B (aif / I) pH 13 h38 - 30 289 11, B2 43 l 41 n, cr 6ϋ 171 11.79 30 123 11.80 130 93 11.79

Example 17

This example does not relate to the processing of liquid manure. In the first step, measures are taken to remove them! solid components. For this purpose, the flocculating example of the Trade Name CO 084, which is polyacrylate at 73 tupl / l to precipitate proteinaceous material and phosphate, is added and the solids are removed after settling. The clarified solution is then nitrified above the β-line. The microfluidics and the inoculation of the liquid slurry processed by the liquid slurry from the previous filtration and by the increase of the nitrification microorganisms.

After nitrification, the slurry has an initial ni-nit concentration. equal to 2 737: ψ / 1 · these nitrates are precipitated as mononitroaluminates by the calcium aluminium calcium oxide, characterized in the examples 12 and 13 by the symbol “N ".

Another precipitating additive is added to the calcium hydroxide Ca (OH) 2. At regular intervals, during the reaction, the residue is filtered off and the residual dust, chlorine ions, phosphate ion, and SO2 SO4 are determined by ion chromatography.

In order to precipitate, 11,853 mg / l of calcium aluminate of the particular composition " N " as characterized in the preceding Examples 12 and 13 and 215 mg / l Ca (OH) 0.

In these conditions, after the addition of the compounds in the liquid liquid to be treated, the total polar fraction of Al / NO 2 is 2.25 and the total molar Ca / NO 2 moiety is equal in this treated solution to 3.6. The results of this test are listed in Table IX below:

Table IX 3as (min) Cl ~ (mg / 1) no3 ~ HPO / - S042 'Yield (%) 0 384 2 737 204 506 15 • 342 7 400 0 84 12 30 469 2 010 0 0 26 15 324 1 515 0 153 45 60 455 1 129 0 59 59 75 448 934 0 32 66 90 262 752 0 0 72 109 405 688 0 0 75 135 224 553 0 0 80 165 399 520 0 12 81 195 213 501 0 0 82 225 195 470 0 0 Chemical analysis slots Nitrified liquid slurry prior to precipitation and precipitation of nitrate are shown in Table X below:

Table X Results of chemical analysis (αιρ / Ι) filter 1 fused liquid The resulting effluent obtained slurry after postponement. nitrile precipitate rtl V »-1 • 11,7 • '' wd 4? .1, 6 191,6 i 611,6 760,8 na 148,4 110,8 Cu J 0,011 z n " \ t *? i nm N i 0, 1 0.01 P b 0.03 nm t 0.09 m and 0.06 nm From 0.06 nm NO, 2 717 470 Na, m m C1 184 195 ΡΆ, 89 nra «V 106 to pH 1.0 1 > 'i

Coagulation analysis (haiot.%) Αι, οί 18,00 CaO '19 71 71 Kn0 0,06 Na., 0 i κα NO-j 9,14 H 0 0 11,71 nm = impenetrable ranftärttv

It can be noted that the contents of Cu and Zn in the effluent are negligible. In this invention, the eagles are bound in the present invention as part of the effect and advantages of the present invention. The resulting nitrate-free effluent can be discharged into the wild without the risk of contamination. The nitrate-rich pellet is advantageous as a fertilizer and can be applied at times when the growth of plants requires nitrogen to be added.

Examples 16 and 19

An aqueous solution containing calcium nitrate Ca (NO 4) at a concentration of 125 rng / l nitrate ion is charged to a reaction vessel equipped with a magnetic stirrer. The aluminum-doped tin is the sodium aluminate NaAlCl 3 in aqueous solution. The calcium addition is carried out by adding calcium hydroxide CaOH to the reaction.

The treatment is carried out with simultaneous addition of NaAlOg and Ca (Oll) O. The PM of the process is mixed with the siues. The resulting suspension is filtered or treated with a flocculating agent and subjected to a settling process and the separation of the nitrate is carried out with a specific electrode. Further working conditions and reaction results are shown in the following Table d1.

Table IX et Example 18 Example 19 Initial NO concentration (mg / l) 125 125 NaA 10 0 concentration in solution (mg / l) 2 950 1 475 Ca (O 2) concentration, mg / 1 5 255 2 590 continuation of Table XI Example 18 pi 19 / molar ratio da / XO-j 35 17.5 diol Dotaer A1 / NO. ≫ 18 9 i > both processing t min) 13 16 Residual concentration tlOj (mg / l) 62 114 Yield (> j) 30 8

Examples of (1) to (11) aqueous solution containing 300 up / l nitrate, which corresponds to the deposition of the supernatant obtained after nitrification and precipitation of solids, have been described in Example 14, and the dianate removal agent can be used. you are able to produce hydrated nitroaluminate calcium.

After the reaction, the resulting suepension was filtered and the usual nitrate concentration was measured.

Other process conditions and results obtained by Jnou in Table XII *

Table XXI

Example? 0 Example 21

Amount of added net (mg / l) 3.5

ABOUT

Quantity added (ffl.g / 1)

Amount of O ^ ÍCjA.CaO added)

Total Thiol ϋ 0‘kc 1 *

Al / KO Λ A ((ag / 1) Continued Table XII Example 20 Example 21 Total molar ratio 3.3 4 Ca / NO., Bob treatment (udri) 180 90 Residual NO 2 concentration (mg / l) 572 410 Yield ( 81 86

Examples 22-24

The aqueous solution contaminated with nitrate ionics and ionic lime is purified by means of a reagent charcterised in Examples 10 and 11 designated " M ". In these Examples 22 to 24, a model aqueous solution is used for processing, which contains, prior to processing, as an aqueous solution. the main contaminant NQ ^ at a concentration of 3 g per liter.

The reading procedure is constant for all three, whose denote is that: - the total polar ooiner λΙ / IJO ^ 2 - the total molar ratio Ca / NO ^ = 4 In the following Table XIII, the results showing! and the possibility of their removal.

Table XIII

An example is the ion of Y

IWD Time Extraction Reaction Yield (NO deprivation) 22 chloride 1 o o 23 phosphate 1,000 24; sulphate 1000 120 min. 70% 52% 120 min. 78% 100% 120 min. 68% 99%

Claims (12)

dV 3 3-42 - 1. ϋ ľ 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. double-stranded calcium nitrates, such as calcium mononitrile, by the addition of a one-component, one-to-one aluminum-doping alumina, and one-to-one calcium supply, the total aluminum to dual ratio & and the total uterine calcium content to nitrate is greater than 2, and is carried out with a clotting rank and using a pH of about pH. 2. A process as claimed in claim 1, wherein the reaction is carried out at room temperature. j. 2. A process as claimed in claim 1 or 2, wherein the precipitating reuking is carried out at a pH above 10 .mu.m. 4. A process as claimed in claim 1, wherein the aluminum-supplying agent is selected from an alkali metal aluminate. · ». The claim according to one of claims 1 to 0, characterized in that the aluminum delivery agent is selected from calcium aluminate. 6. A process as claimed in claim 7, wherein the aluminum-supplying agent is provided with products that contain and / or perform and / or perform a compound or other compound. 7. Treatment of nitrogen-containing solutions and suspensions in an aionic form according to one of claims 1 to 6, characterized in that the following steps are carried out sequentially: 1) biochemical nitrogen in the presence of oxygen , present in the treated solution, to nitrates, 2) after the majority of the ammonia nitrogen is converted to the nitrates, at least one calcium aluminate is added to the treated solution so that the total aluminum to nitrate ratio of Al / NO is more than 1 and a total calcium / nitrate ratio of Ga / NO 4 is greater than 2, and if necessary calcium hydroxide and / or other basic agent is added, thereby adjusting the pH to a basic value, preferably above 10, 5 and the reaction is carried out with stirring at room temperature, 3) after separation, the dense or solid precipitate is stored and is preferably used to enrich the soil. lské falls and as a fertilizer, 4) a liquid effluent free of dusičnanft, is removed. Process according to claim 7, characterized in that the solution to be treated 3e alkalizes the additional potassium hydroxide. 9. Process according to claim 7 or 8, characterized in that prior to precipitation of the hydrated, especially mixed or double calcium nitro-nitrate, either before or after the nitrification step (1), the solids contained in the treated solution are separated off at least partially. any flocculation that is filtered and / or sedated and physically separated. 10. A process according to claim 9, wherein the separation of the solids is carried out before the nitrification step (1). IX. Process according to one of claims 1 to 6, characterized in that the solution is treated with nitrate-contaminated water, such as water or municipal waste water, and at least one calcium aluminate (o) is added to the solution to be treated. ) and, if necessary, calcium hydroxide and / or other basic agent, the pH is adjusted to a basic value, preferably above 10 ° C, in such quantities that the aluminum to nitrate molar ratio and µl / NO 3 is greater than 1 and the total molar ratio of calcium to duodenate & a / da ^ was greater than 2, 2) the reaction response and e & using other pM room temperatures, j) after quenching this reaction, the obtained paper is subjected to settling and physical separation operation and / or filtration, if necessary by adding flocculating agent, if necessary 4) then, if necessary, obtained (b) finally, the new obtained strip is subjected to settling and postponing by physical and / or filtration, and the purified water is recovered, which can be brought into the environment without risk of melting. 12. Process according to claim 11, characterized in that the solution to be treated is water, such as water from agricultural or municipal waste, comprising water-soluble alumina including ammoniacal nitrogen and the solution of the solution is removed prior to removal of the nitrate. * lď. A method according to claim 1 or 12, characterized in that prior to the addition of the calcium aluminate and the basic agent, there is no cationic additive which is poorly soluble in the form of hydroxide. 14. A process as claimed in any one of claims 11 to 13, characterized in that the calcium aluminate additive and the calcium-providing agent, which are little soluble in the calcium salt form, are present prior to calcium aluminate. 15. A process as claimed in claim 11, characterized in that the low-calcium 3-anion-soluble and low-water-hydroxide-soluble anions are precipitated by addition of calcium hydroxide. 16. A process according to one of claims 11 to 15, characterized in that the filtrate obtained at the end of step (4) is neutralized using carbon dioxide.