SA113340927B1 - Ammonium phosphate production arrangement and method therefore - Google Patents

Abstract

An arrangement (100) for production of fully soluble, pure and well defined mono- or di-ammonium phosphates, comprises an extraction section (10), a stripping section (20) and end treatment arrangements (90). The extraction section performs a liquid-liquid extraction of phosphate between a feed liquid (1) comprising phosphoric acid and being essentially free from nitrate ions, and a solvent (5) having a solubility in water of less than 2%. The stripping section performs a liquid-liquid extraction of phosphate between solvent loaded with phosphate and a strip solution (4). The solvent depleted in phosphate is recirculated to the extraction section for further extraction of phosphate. The strip solution is an aqueous ammonium phosphate solution, wherein at least 80% of the ammonium phosphate is monoammonium phosphate and/or wherein the solvent is a water-immiscible alcohol. The end treatment arrangements comprise a source of ammonia (60), an adding arrangement (70), a cooling arrangement

Description

— \ — Ammonium phosphate production arrangement and method therefore Full description Background of the invention The present invention is generally related to the production of phosphates 81701001070 from solutions containing phosphorus, and in particular the production of ammonium phosphates From feed liquid containing phosphoric acid. All 36 water soluble salts of Fie soluble fertilizers are obtained from phosphoric acid. Phosphoric acid is produced commercially by a "wet" or thermal process. The process of digestion in the wet state of phosphate rock is the most common process. As for heat treatment; It is an energy consuming process and therefore expensive. for this reason; The amounts of acid produced thermally are smaller EG and are used mainly for the production of industrial 0 phosphate compounds. The production of phosphoric acid for fertilizer is based almost solely on the digestion of rock phosphate in the wet state. This process is based primarily on the dissolution of apatite using sulfuric acid. after the dissolution of the rock; Calcium sulfate (gypsum ) and phosphoric 8610 are separated by filtration. To produce commercial oe phosphoric acid Class 1 high acid concentrations are needed and water is evaporated. Calcium sulfate has a range of crystalline forms Different crystal forms according to the prevailing conditions Jie temperature “concentration of phosphorus in the slurry” and the level of free sulfate Calcium sulfate is deposited as di-hydrate (08504.21120) or hemi- hydrate hydrate (CaS04.1/2H20) idl phosphoric acid during this process is characterized by a relatively low purity 1. goty

To obtain ammonium phosphates, “phosphoric acid of the commercial category is neutralized; with an aly concentration of about 754 out of 0205; by ammonia _to form mono— (MAP) ammonium phosphate or (DAP) di-ammonium phosphate by controlling the molecular ratio of ammonia to phosphoric acid during the neutralization process. Ammonia © is used in liquid or gaseous form. Non-aqueous liquid ammonia is usually preferred since excess heat from other systems is necessary to vaporize liquid ammonia to Le .gaseous form. Neutralization of commercial grade phosphoric acid is usually performed by ammonia in several stages using several Joli bowls. The molecular ratio of ammonia 0 to phosphoric acid is usually kept in the primary reactor(s) at a level that gives maximum solubility of the slurry (between 014 and 0.48 for DAP production and is usually less than 1 To produce MAP to control the operation; the molecular ratio of ammonia to phosphoric acid is determined by controlling the pH of the slurry. Excess heat of reaction is removed from the primary neutralization unit(s) by Adding water to the reactor(s). Evaporating the water cools the slurry. Ve while the molecular ratio of ammonia to phosphoric acid is increased from ol 1 328 the unreacted escapes from the reactor and the gaseous vapors must be cleaned with an acid. The slurry SY) from the primary neutralization reactor(s); usually containing between 16 to 77 liters of water; usually fed to a treatment unit b 801010018 j - granulation to complete the addition of 328 of the desired product. Neutralization and further evaporation of the water yields solid particles of 0. It is necessary to recover the unreacted ammonia from the gaseous vapors by cleaning with acid. After dd The solid ammonium 5 compounds are usually dried in a separate reactor to reduce the moisture content. 38 Loss of desiccant is usually recovered by cleaning with an acid. Solid ammonium phosphates are usually cooled by passing air through a cooling reactor. goty

It is for many applications Jie fertigation; any; adding water soluble fertilizers to the irrigation water; And foliar fertilization, “ol spraying fertilizers on the leaves.” Completely soluble ammonium phosphates are needed to avoid clogging fertilizing irrigation devices with insoluble solids. Ale] phosphoric acid in the wet state contains a large amount of impurities © such as iron « iron » cadmium « magnesium ¢ calcium » etc. which form solids other than Ale soluble in water upon neutralization with ammonia Therefore, the ammonium phosphates from Fertilizer 438 are not completely soluble in water. Therefore, fully water soluble fertilizers for fertigation irrigation must be specially produced from ad) phosphoric acid, which means further processing. 0 The current technology for the purification of phosphoric acid is based on the extraction of impure phosphoric acid in a process that takes place in the wet state into an organic solvent (ketones 0 “alcohols” tri-alkyl phosphates « etc.) followed by reflux extraction with water to form pure phosphoric acid, but with a concentration (J), which is then concentrated by evaporating the water. After that, sll phosphoric acid is neutralized with ammonia, which leads to the formation of bd ammonium phosphates products 1 Completely soluble in water according to the procedure described above. There are several drawbacks to current state of the art techniques related to the production of ammonium phosphates. Phosphoric 8610 as produced from a gypsum filter in the A hydrate process is not suitable for manufacture. Direct action of ammonium phosphates Further concentration of the acid shall be made by evaporation of water to a suitable concentration of 8010 000580016 (usually Zot Ms Yo of 0205). Normally, phosphoric acid is concentrated in three stages. The acid is evaporated from Filter (YA) from 0205) to 740 by 205 in a single stage vacuum evaporator. The acid AY the precipitated solids is then liquified and the acid AY concentrated to 754 from 205 in two stages. The interstage concentration is about 7448 of 0205; And 754 of 5205 is used to produce ammonium phosphates according to the procedure described Yo above. goty

Concentrating the acids during evaporation is a very energy intensive process. The amount of steam required to concentrate Sale phosphoric acid varies between 5-7.5 tons of steam per ton of phosphorus, depending on production conditions. In the case of purifying phosphoric acid by solvent extraction, the required energy is about 1 ton of steam per ton of phosphoricacid. The energy required to concentrate phosphoric acid is a major production cost. Expensive equipment (Jie lanl distribution systems) evaporation units waste gas cleaning units; condensation systems; cooling water systems; wastewater treatment systems; Acid storage facilities are necessary for the production of commercial grade phosphoric 0. It takes about 56 tons of cooling water to condense one ton of steam. In the barometric condenser, the vapor, Hake, comes into contact with water, and as a result, the impurities 0 present in the vapor contaminate the cooling water, resulting in quantities of SS of contaminated waste materials. Furthermore it; There is additional equipment to neutralize phosphoric acid with 317110018 in multiple stages of drying, cooling and cleaning ammonia from gaseous fumes. Production of phosphates 2001100100 of technical quality requires additional processing steps as described above. US Patent No. 0844147 describes a process for obtaining ammonium phosphates 0 crystalline from 00050001068610_ for a process in the wet state and ammonia. The process consists of the following steps: 0 create a mixture of dus acetone; Sk phosphoric acid in which all ingredients are ALE to mix with water; (b) precipitation of the impurities by adding ammonia and separation of the precipitated impurities to form a purified mixture; (c) contact of the mixture Eel with AY ammonia crystals ammonium phosphates supernatant liquid and (d) separation of crystals separating 0 os ammonium phosphates supernatant liquid And distillation of the supernatant to separate the acetone for recycling. Disadvantages of this method include the distillation of large amounts of acetone; A limited stock of ammonium phosphates » and the production of large quantities of diluted aqueous ammonium phosphates. An additional primary limitation of this procedure is its insufficient selectivity. The water miscible solvents are close in properties

© water resulting in co-recovery of anionic cationic pollutants to a large extent.

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-- US Patents Nos. 99781978" and 777911; are similar to US Patent No. 38441467 and consist of forming a mixture of Wl phosphoric acid and acetone or methanol in which all components are ALE to mix with water followed by the addition of ammonia to precipitate impurities and thereafter ammonium phosphates The defects are similar to those reported for US Patent oo TAGE EY US Patent No. 937546 describes the process of AY solvent from a purified product by dissolution of an extract phosphoric acid The remaining solvent is removed from The purified product by dissolving by adding ammonium or jl cations jl ground alkali or alkaline earth metal in an atomic ratio to phosphorus acid ranging between 0 sel) Dies US Patent No. 5,711,181 describes a process for separating Silica Jie and organic impurities from an organic solvent by washing it with an alkali Jl orthophosphate solution sufficient to maintain the pH of the solvent - the aqueous mixture at a rate ranging from about 9.5 to about AY US Patent No. 5,178,156 describes a process for producing a solution Aqueous alkali phosphate by mixing the SL VO phase containing an alkali compound with an organic phase containing A phosphoric acid by volume greater than Vi) and then separating the resulting aqueous phosphate solution from the organic phase. US Patent No. 5,751,077 describes a process for alkaline stripping for the process of forming phosphoric acid in a wet state from an organic solvent that is immiscible with water to produce a sodium phosphate solution 0 . In the international patent application published SAVOY [Yeu A] a method and arrangement for extracting 05 . & 1005 phosphorus extraction from solutions by adsorption of phosphorus ions in a scavenging agent and by releasing phosphorus ions to an effluent during scavenging agent regeneration. Renewal is performed by 801010018 J . goty anions are precipitated

—y— Introducing excess amounts of de triammonium phosphate in the form of triammonium phosphate remaining in the solution after precipitation of ammonia (using sale) unstable ammonia triammonium phosphate to replenish the scavenging agent. due to bad luck"; phosphate at ambient temperature and atmospheric pressure, which leads to the dissolution of the crystal accompanied by the release of . ammonium phosphate which requires further processing into stable forms of ammonia©. Not suitable for direct use in agriculture. triammonium phosphate 25 diammonium British Patent No. 116,075 discloses improvements in production processes in a solution of monoammonium phosphate. Enter crystals. Anhydrous phosphate lie in a reactor and is fed with ammonia other than diammonium phosphate at the bottom of the chamber. diammonium phosphate in the reactor. Ammonia 0 ammonium crystals are assembled in US Patent No. 5159,199,;_a process for manufacturing water-soluble by means of ammonium phosphates is disclosed. 5 significantly; It is derived from the reaction of iron-free iron phosphoric acid extraction into “strong mineral acid” and “strong mineral acid” 0861177 crude phosphate containing aqueous shall of phosphoric acid and separation of loaded extract b coldly miscible Vo phosphoric acid terminated and contact of remaining calcium loaded extract; and remove impurities

AMMONIUM AND 0°C; And 71 separated about Led with non-aqueous ammonia at ammonium temperature of water solubility from the extract. It is recommended to wash ALE solid low-grade hydrocarbon solvents with boiling phosphates to remove the organic extract attached to them. The process according to this list is characterized by several defects: 0 In the experiments that were carried out by the applicant; It is concluded that it is very difficult to produce ammonia according to current ideas even by using a large surplus of diammonium phosphate. Precipitated and this loss in the solvent can be expensive, ammonium phosphates crystals. Not acceptable from an economic point of view. Elimination of solvent adhesion by distillation is a YO goty process

—A— degrees Celsius) exceeds (YAS) which is difficult because the boiling point of solvents such as tributyl phosphate is a residual point. The solvent washing procedure (Y 4+) monoammonium phosphate fusion proved incomplete; Substantial amounts of AT hydrocarbon solvent bound to a hydrocarbon solvent will remain substantial from the extract even after vigorous washing. Furthermore it; Separating the hydrocarbon extract and solvent becomes a complex and expensive task due to the need for distillation. © A process involving the addition of ammonia to 180 55/7000 IPP No. 55/7000 describes the precipitation of phosphoric acid compounds by Jesse Not miscible in water. Ble sh. Precipitated ammonium phosphates. Jue compounds. ammonium phosphates and the washed crystals are dried. 817071017100 phosphates saturated from Sle with the remaining Sl solution from the scavenging unit are separated from the crystals by phase separation from the scavenging unit and the solution 0 using the remaining from the separate scavenging unit (sale) and saturated ammonium phosphates are made from use it for further extraction. sale) is required phosphoric acid for further adsorption to re-use the washing liquid spent from the remainder of the scavenging unit to further wash the crystals. The disadvantage of this process is the need for three-phase separation. And nitrophosphate fertilizers US Patent No. 75,185,971 describes a process for producing fertilizer Vo rock digestion (I) process from <8. ammonium-nitrate 1 calcium-carbonate , calcium nitrate to produce a solution of nitric acid with phosphate rock from hitric and 8610 phosphoric acid b) extraction of nitricacid and phosphoric acid with nitric solution and 8610 phosphoric acid extraction sale c) alcohol washing solution with ammonium | Containing some mainly concentrated ammonium nitrate of Yo amounting to about (2,900) and evaporating the stripping solution to form a slurry N/P with a molar ratio of crystalline phosphates, e) crystal separation of @ammonium-nitrate ; ammonium phosphates from the solution, f) recycle at least part of the solution to be used in step c, g) treat the carbon dioxide to form a solution By ammonia 5 the solute-purified product from the precipitating step. calcium carbonate ; ammonium nitrate 00 good

Jay US SE HALL 7,217,091 main purpose is to use a liquid-liquid extraction to separate Ya calcium nitrate from calcium nitrate separation by low temperature precipitation which is a common application in the nitrophosphate process. There are a number of disadvantages related to this method. The final product is generally a mixture of ammonium phosphates, diammonium § monoammonium phosphate ;, ammonium nitrate ; © phosphate unspecified Jaa In addition to the above, nitric acid J co-extraction results in precipitation of calcium phosphates which makes liquid-liquid extraction impractical. Which limits the yield of phosphoric acid extracted product. In addition to the above; It takes a concentration of Je in the ammonium-nitrate solution used to remove the volatile components 0 A to reduce the amount of Al ammonium phosphates remaining dissolved in the ammonium-16 solution. like that; The method requires ammonium nitrate to be processed into a final product by evaporating water. In addition to the above, the phosphate product contains ammonium nitrate via the main solution attached to the sediment. In addition to Go crystallization is obtained by exceeding the solubility of dissolved salts by evaporation of water which requires equipment such as evaporation units, vapor distribution systems, Vo etc., as well as, a power source. in the end; Amyl alcohol and other solvents suitable for this process have a high solubility in water, which makes the process complex since the solvent has to be extracted

from water streams by extraction and distillation. British Patent No. 177174 describes a process for producing ammonium phosphates by digesting phosphate rock with nitric acid. The process consists of a) treating the leaching solution 0 with a solvent consisting of aliphatic alcohols containing ; - 1 carbon atoms to extract nitric acid phosphoric acid, b) purify the organic extract by contacting the extract with a solution consisting primarily of ammonium nitrate, c) treat the purified extract with ammonia to form an ammonium phosphates precipitate, and a light phase Contains the solvent, and a heavy aqueous phase containing ammonium nitrate and ammonium phosphates d) light phase separation YO by decanting and recycling of the light phase exposed to decanting to the extraction step e) sediment separation

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“yam ammonium phosphates Jue from the heavy aqueous phase, f) ammonium phosphates and part of the ammonium phosphates Jue phase (sale water) separated with water, g) is carried out to the step of ammonium phosphates and ammonium nitrate Heavy aqueous contains the purified extract, h) the aqueous solution is recycled from the purification step to the extraction step, heavy aqueous contains Sl i) the purified product is treated by solubilization from the extraction step and part of the © phase by distillation to extract the solvent from ammonium phosphates and ammonium nitrate on carbon dioxide to form aqueous phase ammonia, and j) treat the distilled aqueous phase with precipitated calcium carbonate 5 ammonium-—nitrate solution A number of related defects By this method according to patent lia, FOVALYY US Patent No. calcium precipitation of nitric acid results from the co-extraction of 07174 07 BR No. 0 extracted from a leaching solution. phosphoric acid reduces the yield of Le phosphates during the equation with ammonium nitrate, in addition to the above, it requires a high concentration of, which remains dissolved in a solution and for ammonium phosphates to reduce the amount of ammonia to an ammonium nitrate product as well; The method requires processing. ammonium-nitrate deposited on final ammonium phosphates by evaporation of water. In addition to the above, Veo

Jue by means of the main solution attached to the sediment and consequently ammonium nitrate ammonium phosphates basic dissolve (WL) attached to ammonium-nitrate ammonium (to convert nitric acid B into precipitated sb sgla. This requires acidification and re-extraction ( phosphoric acid and ammonium nitrate 5 M) dissolved into the wash water which is costly. Finally, suitable solvents for this process are ge phosphoric acid Y. The process has a high solubility in water which makes the process complex as the solvent has to be extracted from Distillation aqueous stream from an organic solvent phosphoricacid US Patent No. 811,711 describes a process for stripping potassium J sodium so that it is, ammonia with a basic compound of solid organic solvent, dihydrogen phosphate moles, or with 1 0 aqueous salt, or with water in an amount up to Yo goty

— \ \ — To obtain a mixture of a liquid phase comprising an organic solvent phase substantially free of phosphoric acid and an Ak phase comprising dissolved phosphoric acid and dihydrogen phosphate dissolved from the base. A major disadvantage of this process is that the stripping process requires that the organic solvent be loaded with a solution of highly concentrated phosphoric acid © > 77050 wt. Thus, the process requires concentration of phosphoric acid by evaporation of water, equipment such as evaporation units, vapor distribution systems, etc., as well as a power source. A major drawback AT the process is that the product is an Ale solution that requires further processing. Russian Patent No. 474,849 describes a method for producing monoammonium phosphate using a solvent consisting of tributyl phosphate in a kerosene diluent 0. The method involves contact with a tributyl phosphate solvent, which is loaded with phosphoric acid, or with a solution of diammonium phosphate with an organic phase to Sle phase ratio of approximately JS! 1: Depleted solvent and 110008100000100 phosphate crystals ... in a solution of monoammonium phosphate. It should also be noted that the main solution can be separated and treated with ammonia to produce a recyclable diammonium phosphate solution. VO However, it has been shown, through many experiments conducted by the present presenter, that stripping a solvent consisting of tributyl phosphate in kerosene with a solution of 01800000010010 phosphate, according to the procedure described in Russian Patent No. 5744849, results in the formation of a sharp emulsion at Recontacting the stripped phosphoric acid solvent to extract more phosphate Emulsion formation makes the process inoperable in industrial applications A) where efficient recycling of the solvent is needed. GENERAL DESCRIPTION OF THE INVENTION The present invention relates to its general objectives; By producing OR 01-20000001000 phosphate mono or completely soluble, pure and well-defined avoids the problems of prior art. Another goal is to allow the production of solid ammonium phosphates without any dala for goty evaporation.

-117- About, source of water Sud using related equipment such as evaporators, steam distribution systems, etc., ammonium phosphates in enabling the production of AT compounds energy to produce heat. The objective of the solid is to use liquid-liquid recovery in a robust manner that enables efficient recycling of the process fluids. Other objectives in relation to the various embodiments presented will be discussed below. Preferred models are identified by dependent patent protections. In general terms, in the first aspect, an equipment for the production of pure ammonium phosphates comprising an extraction section, a cleaning section and end treatment arrangements. The bee extraction section is to perform a liquid-liquid phosphoricacid extraction comprising a feed liquid between an extraction of phosphate 0 and a solvent. The solvent has a water solubility of less than 77, preferably less than 71. It is liquid. nitrate ions essentially free of feed liquid

Wn feed liquid first extraction outlet JJ Yo

Jal second extraction outlet and at least a second phosphate extraction outlet in to perform a liquid-liquid extraction lee ad . phosphate The solvent loaded with phosphate between the liquid-liquid extraction of phosphate solvent for phosphate. strip solution and the second extraction solution The stripping section is a first stripping entrance, connected to a second extraction outlet amy Yo A second stripping entrance to provide the stripping solution, phosphate to provide the loaded solvent with, outlet _the entrance, a first stripping outlet to transfer the partially spent solvent At least in strip solution it is . 5010 solution Jail output and phosphate second extraction inlet First extraction inlet connected to goty

S1 The solvent that is at least partially depleted in phosphate to extract more phosphate . The strip solution is Euan, Sl ammonium phosphates at least 7860 of ammonium phosphates 4 The inserted strip solution is monoammonium phosphate and/or where the solvent is water-miscible alcohol immiscible alcohol © . The dalled end-treatment arrangements include a source of ammonia, an 800100 arrangement, a refrigeration setup, an aly precipitate remover and a sale circulation system. The addition outfit is connected to a source 58_shes for adding ammonia from an ammonia source in at least a partial stream of 0 strip solution. A cooling arrangement is configured to cool the heat generated by a chemical reaction when ammonia is added from an ammonia source in at least a partial stream of solution 5010 . The shee precipitate remover is used to separate crystals from the loaded strip solution. The recycling system is connected between the outlet of the precipitate remover Vo and the second discharge inlet of the discharge section. The recycling system is configured to reuse the strip solution from the precipitate remover as the inlet strip solution. In a second aspect, a method for the production of ammonium phosphates 48 comprising the extraction of phosphates from a feed liquid containing phosphoric acid by means of 0 liquid-liquid extraction in a solvent. The solvent has a water solubility of less than 77, preferably less than 711. The feed liquid is essentially free of 1005 nitrate. The solvent is removed from at least part of the phosphate by liquid-liquid extraction in the strip solution. The strip solution is an aqueous ammonium phosphate solution Yo. The strip solution loaded with stripped goty phosphate is separated

— ¢ \ — phosphate and the solvent at least partially depleted in the phosphate . sale) The at least partially depleted solvent in the phosphate is recycled to extract more 0800500816 ...in the extraction. The ratio of TAG to JN of ammonium phosphates in the introduced strip solution is monoammonium phosphate and/or the solvent is water—immiscible alcohol . .ammonia is added in at least a partial stream of the stripping solution. The heat generated when said 801010018 is added in the said partial current at least of the said solution is cooled down. The blues are removed from the loaded strip solution. The Bale strip solution is cycled after the crystallization step to be used as the output from the strip solution 0 in the decolourization process. One of the advantages of the present invention is that it is possible to produce fully soluble, pure and well-defined mono or diammonium phosphate 23 in an industrially applicable process in an efficient and economical manner. Lad additional features regarding the different models offered are discussed in detail below. VO BRIEF EXPLANATION OF THE DRAWINGS The invention may be best understood.” Together with its other goals and advantages. With reference to the following description with accompanying figures and tables; In which: Figure Jig 1 is a workflow diagram of the steps of an embodiment of a method for producing ammonium phosphates ; 0 shape? J A schematic diagram of a model of a monoammonium phosphate production plant ; the shape ? It represents a schematic diagram of one of the models of a facility for the production of diammonium phosphate ; goty

ac \ — fig; It represents a schematic diagram of one of the models of the equipment for the production of Monoammonium, Diammonium phosphate; phosphate ; Jig © Jal A schematic diagram of the AT model of a plant for the production of monoammonium, diammonium phosphate ; phosphate ; © Fig. + Jia outline of the AT model with diamond phosphate equipment » WY :

Figure Jia 1 shows a diagram of the AT model of a monoammonium phosphate production plant. phosphate.

3 Let's see 1 Description Ye Some of the terms used frequently in the present disclosure should be interpreted as follows: Typically organic; It is preferable to dissolve types of extractable solutes from (Bila) solvent-phase mathematical solution. Extract - typical organic ¢ active ingredient 3 of an extractable solvent.

Vo solvent extraction (liquid-liquid extraction)—Separation of one or more solutes from a mixture by mass transfer between immiscible phases in which at least one phase is typically an organic liquid. offset The solvent from 1005 or acids discarded from the process solution to prepare the solvent for reuse.

,. Diluent: A typical organic ¢ liquid in which an extract is dissolved to form a solvent Yo Dissolution-purified product: an aqueous phase from which a solute has been removed by extraction.

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The present disclosure is based on the extraction of phosphoric acid with a solvent that is immiscible with water, or at least to a large extent immiscible with water. References suggest many solvents that are not miscible with water as suitable for the extraction of phosphoric acid. The proposed solvents can generally be divided into the following groups: 0 ° tributyl phosphate jisalkyl phosphates , b) amines such as tri- isoamyl alcohol, n—-amyl alcohol, (ix alcohols (z , h—octylamine) cyclohexanol, methyl cyclohexanol, tertiary amyl alcohol, isobutanol, n- butanol, heptanol d) ketones such as methyl-isobutyl ketone, methyl propyl ketone, diethyl ketone, methyl ethyl ketone, methyl-n- butyl ketone +( butyl acetamide Ji. amides 01 , and esters (5 , benzaldehyde i. aldehydes) as ethers (c , ethyl acetate, butyl acetate, amyl acetate, cyclohexanone) as diethyl ether, di-n —amyl ether, and glycol ethers such as di-ethylene glycol All of the above mentioned solvents lad are classified as water immiscible However, most of the mentioned solvents VO actually have relatively high solubility in water This can result in contamination of both the water streams and the final product with traces of solvent High solubility in water usually requires extraction of the dissolved solvent from the streams aqueous distillation, which is expensive and complex. For example, n-butanol has a water solubility of about 900 grams per liter at room temperature. Many of the solvents mentioned have other disadvantages in addition to the above High solubility 0 Jie Flammability and explosive hazard, eg di—isopropyl ether In addition to the above; Many of the mentioned solvents show a very low extraction capacity of phosphoric acid below a certain cut-off value. This means that the feed stream with phosphoric acid must initially be characterized by a high concentration, which usually requires concentration of the acid by evaporation of goty

-11- As phosphoric acid as water. In addition to the above, only partial extraction of stereotypes onto a solvent with a cut-off concentration is possible for extraction of ABN from these solvents. Lies one of the ethers in general, characterized by 651615 and . methyl isobutyl ketone in phosphoric acid and for this reason it is not suitable phosphoric acid to extract das selected at a concentration of value from low concentration sources. phosphate to extract 0 phosphoric _ to purify phosphate commonly in industry tributyl phosphate is used as a non-flammable, toxic tributyl phosphate liquid-liquid extract. It is 0 grams per liter at a low temperature of 0.4 and has a very low water solubility of about tributyl chamber. In addition to the above; Solubility decreases with increasing temperature. The phosphoric has a reasonably constant distribution as well, ie the ability to extract doles phosphate 0 tributyl 1 at a low concentration. Due to the relatively high density of phosphoric acid down to acid it is commonly mixed with a diluent, such as, aliphatic kerosene to improve the physical separation 56 of the insoluble phases. So that it is preferred over phosphoric acid salts Tributyl extraction phosphate allows Jie and so that it is preferable to dissolved soy sulfates or dissolved Jie chlorides 1 The presence of dissolved salts or acids leads to the enhancement of . sulfuric acid or hydrochloric acid phosphoric by a salinity mechanism that can allow almost complete extraction of phosphoric acid extraction. acid so that it is preferred over nitric 20106 tributyl phosphate However, nitric acid is extracted from phosphoric acid which makes selective extraction of phosphoric 8610 00 nitric not possible. In general, solvents with low solubility in water are extracted from, solvents with increased selectivity for . phosphoric acid so that it is preferable to amyl alcohol acid with high solubility in water and is still extracted in the form of Jie phosphoric acid tributyl phosphate. nitric acid shared large amounts of goty

-1 PM -

As a solvent for the extraction of phosphoric acid in that the low solubility in water allows work

Without the need to distill the solvent from the water streams which is expensive and aggressive.

We mentioned above that most suitable solvents have relatively high solubility in water, eg

An example is most alcohols. However; Alcohols which have relatively long carbon chains are also characterized by very low solubility in water. For this reason the solvent is dal for extraction

phosphoric acid alcohols - with a long carbon chain, for example heptanol, has

The solubility in water is less than 77, and less than LY is preferred if the solubility is less than

At such a level, the amount of solvent after the water stream becomes reasonably low so care should be taken

Dealing with it using inexpensive and simple equipment is too much.

0 The Russian patent 849 ;?; mentioned in the technical background section proposed the use of an ally solvent of tributyl phosphate in a kerosene diluent. However, in many experiments conducted by the present inventors, it was concluded that the process according to the patent The Russian EVEAER has major defects that make it practically unenforceable and therefore not applicable on an industrial level in an economic aspect.

tributyl phosphate Yo 4 kerosene using a diammonium phosphate solution according to the procedure described in Russian Patent 4744849 results in the formation of a sharp emulsion when the solvent removed contacts with the phosphoric acid solution, for example it is reused in a process Extraction - recursive extractions. The cause of emulsion formation has been studied further. It has been shown that after contact with a solvent consisting of

kerosene stributyl phosphate 0 Using diammonium phosphate solutions of varying concentrations, very small crystals were found in the solvent. The crystals were so small that they could only be seen under a microscope. The tested concentrations were according to the Russian patent 4?, as well as higher or lower concentrations, and in a wide range of phase ratios.

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-14- hours for fine crystals to stabilize YE it generally takes more than SUK (use of the solvent again (sale) hours has been shown. After the crystals have settled, $A and sometimes more can be added without forming any emulsion. Thus, the presence of crystals in the phosphoric acid section of the ligation extraction led to problems of emulsion formation in the extraction section, when the solvent was recycled. In other words, an astonishing formation of microcrystals in a later manufacturing process led to problems in an earlier manufacturing process, mediated by solvent recycling. The separation time was in minutes. The extremely long separation time of an operational liquid-liquid extraction system is usually less than that required for the concentration of fine crystals, making the process virtually unfeasible, at least for applications of economic importance and industrial efficiency. However, the emulsion is not observable in the debridement section and the emulsion does not form until 0 . phosphate The solvent removed is reused to extract more of the above. Test experiments did not succeed in removing fine crystals by washing with water, or it was not possible to dissolve . monoammonium phosphate or other phosphoric acid solution with Be crystals._ with the mentioned aqueous solutions and an emulsion was formed when it came into contact with the solvent, as well as after severe washing. , phosphoric acid Vo was one of the ingredients in the fine crystals, phosphoric acid. It was also shown that it was probably depleted in kerosene in tributyl phosphate, which did not result in ay contact due to any formation of fine crystals and the addition of diammonium phosphate with a phosphoric acid solution, and for this reason. phosphoric acid, therefore, the emulsion did not form upon the following contact with . ammonium phosphates, it is believed that fine crystals may be composed of 0 compounds in a kerosene solvent, tributyl phosphate as a modifier to dodecanol, an addition that did not solve the problem of emulsion formation. Changing the diluent from kerosene solvent as a diluent did not solve the problem of forming an aliphatic heptanol Jie into an aromatic thinner or using an emulsifying alcohol as such. goty

1. In tributyl phosphate it has been shown, however; Surprisingly, a solvent consisting of monoammonium can be delivered with a saturated solution of phosphoric acid kerosene loaded with any formation of microcrystals in the solvent. In the tests, a 5-phosphate solvent was used, about monoammonium phosphate, and the percentage of H3PO4 was loaded with 6.4 - ? molar of the solvent used immediately after decontamination (sale) molar at room temperature. Yoo© can thus be used without emulsifying. Phosphoric 8010 is based on the conversion of diammonium phosphate, in contrast to dissolution using a solution. It has been shown that when monoammonium phosphate in a solvent becomes phosphoric acid, 110008101100010 phosphate (strip solution Juaill) The remaining ally phosphoric acid solution The stripping is based on the extraction equilibrium. In other words, the concentration of 0 ammonium strip in a phosphoric acid solution in the solvent is based on the concentration in the phosphoric solvent acid The equilibrium concentrations of ,1 are shown in Table 5. Kerosene as a function of Bl) by volume in 10, tributyl phosphate comprises 80 vol per cent of the saturated. Monoammonium phosphate is carried out in a phosphoric 8610 solution on the content of determination of concentrations during conjugation at room temperature and with an organic phase ratio to an aqueous phase of 15 3 that is based on the balance of monoammonium phosphate since the conjugation using a solution of The solvent requires more than one fixed phase phosphoric acid extraction, the complete decoction of we can note that decoction using solution 1 from table ld one. . However, it will suffice. It is possible to provide an organic phase ratio to an aqueous phase of monoammonium phosphate 0 for a molar content of TAT, a 0.15 dissolving ratio of phosphoric acid and a 1:1 loading of one stationary stage. From the table, phosphoric acid strip solution In the pure phosphoric acid solution, use the stripping process to concentrate during the stripping process. in embodiments 1 using an organic phase to aqueous phase ratio greater than goty

— \ \ — Preferably, the concentration of phosphoric acid can be increased during the degassing process by anywhere from two to more than © times of the original concentration. 04 M in solvent | 113004 molar in immiscible with water 1404 saturated Table 1. Equilibrium concentrations of phosphoric acid as a function of phosphoric acid content in a saturated monoammonium phosphate solution. © The dle advantage of using monoammonium phosphate over using phosphate solution 018111001100 is that monoammonium phosphate has a lower viscosity than diammonium phosphate, which enables phase separation to occur more quickly and with more AD. In general, due to the higher density, it was found that delamination using monoammonium phosphate is significantly superior to conventional delamination with water in terms of separation time and completeness of separation. In addition to the foregoing, it was shown that it is possible (ela) to connect phosphoric acid with a tributyl phosphate solvent loaded with a solution of monoammonium phosphate of any concentration at any ratio sh without forming precipitates Wh that the initial shall degree For a solution of monoammonium phosphate below the level at which the solubility of monoammonium phosphate 10 decreases by dissolving phosphoric acid . This means that liquid-liquid extraction in most Jia models is a two-phase extraction. For this reason the temperature of the goty solution should be

— \ \ — Elemental monoammonium phosphate, if saturated, preferably below 0°C and preferably below 0 5°C. In addition to the above; The temperature of the monoammonium phosphate solution during the degassing process should not fall below the level determined by the difference between the solubility of the monoammonium phosphate© and its concentration in the solution DA precipitates are formed. However; If the monoammonium phosphate solution is not saturated the temperature can also be higher than 0 5 °C. (gas) The advantages of using monoammonium phosphate for connection are that the connection in most models includes only two phases, one organic and the other aqueous, without the formation of sediment. This enables operation with conventional liquid-liquid extraction equipment Jie pulse columns, mixer stabilizers or other slanted liquid-liquid extraction equipment such as, stirred columns, non-stirred columns, direct mixers, centrifugal contactors, etc. Further studies were performed using mixtures of mono- or di--ammonium phosphates to elute a solvent consisting of tributyl phosphate in kerosene. of emulsion composition <ie)(NH4)2HPO4 1404no (on a molar basis) on a molar basis) oT goty

Table 7. Emulsion formation during degassing with mixtures of NH4H2PO4 and (NH4)2HPO4. Table ¥ shows whether or not an emulsion is formed during degassing of a solvent consisting of 880 vols in tributyl phosphate (ZL) and 10 vols in 100 kerosene, with a loading of 4.. - H3PO4 0.6 © Molar, with mixtures of 1114112004 and 8114(211004). The concentration of phosphate in all solutions used for elution was adjusted to Teo Molar. It can be noted that delamination with mixtures of mono- or 01-28101001000 phosphates results in the formation of emulsions, when the solvent that was detached after that is reused to extract phosphoric acid, at a content of diammonium phosphate higher than 775 on a molar basis. Dissolving 0 - with a solution consisting of monoammonium phosphate having a content of 7700 ily phosphate on a molar basis does not result in the formation of fine crystals in the solvent and no emulsion is formed during the extraction of phosphoric acid thereafter. According to some observations it is believed that at a low content of Diammonium phosphate, precipitation occurs in the aqueous phase. In other words, phosphoric acid is initially cleaved from the solvent into the Sl phase and then 1 crystals of monoammonium phosphate are formed in the aqueous phase and for this reason microcrystals are not formed in the solvent. At a high content of diammonium phosphate, fine crystals (sale) are formed in the solvent Ss if monoammonium phosphate nucleation crystals are artificially added during the conjugation process. Amines are elude tri-n-octylamine (fie immiscible with water with very low water solubility 0) > 00 ppm) which are suitable for the extraction of phosphoric 0 . The test of tri-n-octylamine (+ 77 000860800 as an average, 755 aliphatic kerosene as a diluent) as a solvent for the extraction of phosphoric acid and elution using ammonium 5 gave results that were similar to the results obtained \gle for tributyl phosphate. Resulting in the removal of an amine solvent loaded with a solution of diammonium phosphate, the formation of a goty emulsion

1 is sharp, which makes the process unworkable. The delamination of an amine solvent loaded with a solution did not result in any formation of an emulsion upon reuse of the solvent. Monoammonium phosphate and NHAH2PO4 7506 750 loaded with a mixture of amine solvent were arranged on the delamination of an amine solvent For implementation, while ALE did not result in the formation of the emulsion, which made the process not (NH4)2HPO4 emulsion formation (NH4)2HPO4 7700 and NHAH2PO4 A+ leaching an amine solvent loaded with 0 when the solvent was reused. A1601800 is a water immiscible solvent with a relatively low solubility in water characterized by a low concentration The solubility of phosphoric acid is with a reasonably constant coefficient of distribution down to g per liter which is more than twice the solubility of 1 The water around heptanol is larger than the ax atoms of the alcohols in the water.In general, tributyl phosphate 0 reduced by increasing the number of phosphoric acid carbon has a lower solubility in water, but a low water solubility recovery as well with sufficient heptanol carbon atoms, however, comparability is comparable to heptanol for AT to allow operation without the requirements of carbon atoms. solvent droplet. A disadvantage that is less efficient than heptanol phosphoric acid is that the extraction of tributyl phosphate is about heptanol obtained with (Al phosphoric acid) to a large extent. Vo loading however; although . tributyl phosphate is half of what was obtained using in the event, but it can also be used to extract tributyl phosphate without heptanol. The fine crystals must remain in the solvent. Diammonium phosphate with a solution of Yo phosphoric acid directly to extract heptanol (use solvent sale) and for this reason can be used without the formation of any emulsion. There was no interrelationship between viscosity, density and crystal formation, and the remaining fine tributyl phosphate was formed in the solvent. Amines are characterized by a lower density compared to the viscosity of heptanol. diammonium phosphate is also emulsified upon removal with a goty solution

E01 "lef compared to tributyl phosphate, and no emulsion is formed upon decanting with a solution of diammonium phosphate and re-(ual) with phosphoric acid. Based on the amazing results presented, led above, the Shee preparation can be clarified To produce pure ammonium phosphates The equipment includes extraction, aud section and end treatment arrangements The different parts are closely interdependent with respect to the composition of the liquids used The extraction section performs a liquid extraction Liquid-liquid extraction of phosphate between a feed liquid comprising phosphoric acid and the solvent.The solvent has a water solubility of less than 77. This enables the production of precipitates of ammonium phosphates at satisfactory 0 levels. In addition to the above, the feed liquid must be WA to a large extent of nitrate ions, since suitable solvents generally extract 8010 nitric so that it is preferred over phosphoric acid. The aud extracts a liquid-liquid extraction of phosphate l iquid-liquid extraction of phosphate between the phosphate-laden solvent and the strip solution. The phosphate Vo depleted with a solvent is connected back to the extraction section to extract more phosphate . The strip solution is an aqueous solution of ammonium phosphates. According to the previous results, at least one of the two conditions must be met. The first condition is that at least 7860 of the 0005008165 ammonium 4 strip solution introduced is monoammonium phosphate . The second condition is that the solvent is a water—immiscible alcohol . By using this equipment, Jie provides a strip solution loaded with phosphate in a way that is suitable for industrial production. The loaded strip solution is then treated in various ways to obtain a well-defined MAP and/or a defined DAP. Jus fie these end-treatment equipment use a source of ammonia. YO The adding arrangement device is connected to the ammonia source and is entered as goty

-?1'- 328 in at least a particle stream of the strip solution. And the heat is generated Jia this addition_ from ammonia and for this reason a cooling arrangement is provided to remove that heat. The equipment also includes a precipitate remover that separates MAP separating crystals or DAP from the loaded strip solution©. Finally, a recirculating system is connected between the precipitate remover and the stripping section to allow sale to use the strip solution from the strip solution as the strip solution Juaill inlet in the stripping section 100m5110. The current method disclosed in the present order lad above enables the production of or di— -00000 ammonium phosphate | 0 Pure and well defined in the same single unit without the need to concentrate phosphoric acid by evaporating water. This is obtained by a combination of liquid-liquid extraction and chemical precipitation by which emulsions and ore formation are avoided as a result of unstable precipitation due to the specific properties of the nitrate solution and/or solvent. In preferred embodiments, operational problems such as formation of precipitates during solvent degassing, and production of ammonium phosphates Yo precipitates with unsatisfactory levels of bound solvent are also avoided. Figure 1 shows a Sly workflow diagram of the steps of a method for producing 5M solid ammonium compounds. The procedure begins at step 700. In step YY, phosphate is extracted from a feed liquid comprising phosphoric acid by liquid-liquid extraction in a solvent. The solvent has a water solubility less than AY and in addition to Yo the above the feed liquid is largely free of nitrate 1005 The solvent is removed in step 711 from at least part of the content from phosphate by liquid extraction - Jil in the strip solution. The percentage of ZA is at least ammonium phosphates in the introduced strip solution 000008100000170 phosphate and/or the solvent is water—immiscible alcohol . Juad Yo strip solution loaded with stripped phosphate goty

a and solvent at least partially depleted in phosphate in step 7164 in step YY sale) The solvent, at least partially depleted in phosphate, is cycled to extract more phosphate in extraction step Y In step J, YY. 801010018 is added to at least a Soa stream of the stripping solution. In oo step 1777, the heat generated when ammonia is added is cooled in at least a partial stream of the stripping solution. strip solution, in whole or in part. The blues are removed from the strip solution loaded in step 77. In the figure, steps 754-771 are mung as next steps. However, since they describe the Different cycles, their relative dependencies in time and process fluids can vary from model to model.However, BS 0 steps 4-778 7?, are performed in all models in one way or another.In step 776?, the Recycling of the strip solution after de-crystallization step 4 77 to be used as output from the strip solution in decontamination step .711 and the procedure ends in step 754. Following will be introduced number Examples of current ideas to describe the benefits and possibilities of diversity. One of the embodiments on the 001 equipment for the production of pure ammonium phosphates, Vo in this model is monoammonium phosphate, is illustrated in detail in figure LY Jl is fed liquid feed containing 1 phosphoric acid to ad 01 prepared to perform liquid-liquid extraction of phosphate between feed liquid 1 and solvent ©. The solvent © is immiscible with water and has a solubility in water of less than 77. The solvent © that is immiscible with water in this particular embodiment is tributyl phosphate | 0. in aliphatic kerosene. Ghat is obtained from feed liquid with 1 phosphoric acid by ingesting a substance containing phosphorus with a mineral acid. Phosphorus-containing material can be rock phosphate or other phosphorus-containing material Jie ash rich in Jie phosphorus incinerated sewage sludge ash, abattoir waste ash incinerator, ash from dung, etc. The mineral acid used should be goty

m \ — to digest preferably from phosphoric ji hydrochloric acid Ji , sulfuric acid 0 to obtain selective extraction of phosphoric acid . The concentration of phosphoric acid in the leaching solution can be very low, eg below IV of 0205 or even lower than 74 of P205. Dilute phosphoric acid solutions are typical for sludge ash leaching solutions. When treating dilute leaching solutions, it is characteristic that the solution also contains dissolved salts or acids that are not extractable, so that they are preferred over phosphoric acid, but they have the effect imparted by the salt, which enables the extraction of LG phosphoric acid approximately at low concentrations. Naturally; Leach solutions with a higher concentration of phosphoric acid can be treated according to the invention. There is no limitation on 0 maximum concentration of phosphoric acid. In alternative embodiments, the feed liquid may be supplied with 1 phosphoric acid in other ways. The particular manner in which the feed liquid 1660 is supplied with phosphoric 1 0 does not greatly affect the main ideas in the present disclosures, since the feed liquid is primarily WA of nitrate ions, according to what was explained in detail above. 1 Since the main objective of the ideas presented in the present disclosure is to allow the production of ammonium phosphates compounds without any dala for the concentration of phosphoric acid by evaporation of water, it is clear and more informative that the concentration of phosphoric acid is the maximum concentration that can be obtained practically by acid digestion. The digestion of phosphate rock with sulfuric acid according to the La di-hydrate process results in a phosphoric acid concentration of about 7748 of Y.0205. Optionally, the leaching solution is pre-treated to remove ionic compounds. Jie iron fluorine , iron , etc. The extraction section includes 01 first extraction inlet to provide 1 feed liquid and a second extraction inlet VY second extraction inlet to provide solvent Lo and ad extraction 01 includes a first extraction outlet first extraction outlet goty

q — \ — Jal 0 Soluble purified product or feed liquid? at least partially depleted in phosphate, and a Jal V¢ second extraction outlet, the solvent? Loaded with phosphate. According to the above discussion, any organic solvent that can © remove phosphorus from aqueous solutions can be used. (Sa) The extraction mechanism of phosphorus should be phosphoric acid solubilization or both ion bonding and solubilization. The organic solvent composition should be selected according to the phosphoric acid feed concentration, presence of additional acids or salts, etc. to obtain high loading capacity and practicability Efficient operational extraction Tributyl phosphate is used in aliphatic kerosene as the preferred solvent in the present embodiment 0 Preferably the temperature of the water immiscible solvent 5 is lower than sedan Te because the lower shall degrees Generally support phosphoric acid extraction.The liquid-liquid extraction process in extraction section 01 is preferably a continuous liquid-liquid extraction process using Blom ile extraction equipment preferably Jie pulse columns.However, any Other liquid-liquid extraction equipment such as, Addie columns 1 non-stirring columns, mixers, direct mixers, centrifugal contactors etc. The purified product is directed by dissolution 7 i.e. feed liquid At least partially depleted in phosphate, to further processing Jie reuse For dissolution, etc. Optionally clean solvent not miscible with water? Which is phosphoric 82610 Sas Ye in Al solution to remove co-extracted impurities. solvent load dependent? On the concentration of phosphoric acid in the feed liquid, 1 feed liquid and the concentration of dissolved salts and acids, a phase ratio of the immiscible solvent with water © entrance to the feed liquid, 1 feed liquid, as well as, a number of contact stages during extraction in ‎ aud extraction .01 she especially in the current model is that the output of goty can be obtained

For Je produced by ammonium phosphates even with very low loading of phosphoric acid in the solvent LF can the loading of phosphoric acid in the solvent be? Less than 77 of P205, as well as a high yield of solid ammonium phosphates can be obtained by increasing the concentration of phosphoric acid during the connection process. Naturally, © solvent loading could be 9 higher. The sole of the standard feed solution obtained from the digestion of phosphate rock with sulfuric acid according to the dihydrate process results in loading phosphoric acid at a rate of about 77 out of 0205 in the water-miscible solvent? Referring to FIG. 7, the phosphorus-loaded immiscible Fell is then supplied to the stripping section 01. The stripping section is bee Yo for liquid-liquid extraction of phosphate between the solvent? Loaded with phosphate and the strip solution 4. The strip solution ¢ is an aqueous ammonium phosphate solution. In the present embodiment, all ammonium phosphates 4 are the strip solution Juaill entered; to aa distal monoammonium phosphate . Vo comprises the emission aud 01, a first evacuation inlet, 71 connected to a second extraction outlet, ?0, to provide the solvent? Loaded with phosphate. The stripping section also includes 00 second connection inlet VE to provide the strip solution, inlet 4. In addition to the aforementioned, section 01 contains a first unplugging outlet, YY, to transfer the solvent 0 that is at least partially depleted in phosphate, and a second unplugging outlet, YY, to transfer the output from the solution 5010 solution | 1. The first unplugging outlet is YY is connected to a second VY extraction inlet to recycle the solvent 0 spent at least Wn in phosphate to extract more phosphate. In the extraction inlet .01 preferably ad Delamination Yo A continuous liquid-liquid extraction process using liquid-liquid extraction equipment preferably Jie pulse columns or mixer stabilizers. However; goty can

Use any other liquid-liquid extraction equipment such as, stirred columns, non-stirring columns, mixers, etc., direct centrifugal contactors, centrifugal breakers, according to the current model, preferably monoammonium phosphate solution at Produce monoammonium phosphate is a solution of ¢ ammonium phosphates in percent by weight and a pH of about 710 notation, for example has a concentration of about 9

Y.o in the solvent is low, the concentration of phosphoric acid is increased leading to loading in cases where 1. During the stripping process using an organic to aqueous phase ratio greater than phosphoric acid can be. phosphoric acid, which requires many stages of contact to obtain complete delamination. During the delamination process, between two times to more than five, phosphoric acid usually increases the concentration of 0 in the current model, 1 strip solution, times the original concentration. The output of the solution consists of the tip

NH4H2PO4 If a solution of 113004 NH4H2PO4 from a mixture of 6 strip solution is used to connect. Filament solution output is provided 4+ end treatment arrangements of the current model 50 end treatment arrangements include 1 In addition to the above; 10 source of ammonia device is connected to an ammonia source 71 the addition device Te is initialized to an ammonia source 01 adding arrangement adding at least VY in a partial stream 10 source of ammonia to add ammonia From an ammonia source in this embodiment, part of the pure solution is deflected. strip solution of the strip solution to be made, 5 0 precipitate remover coming out of the sedimentation unit 4 strip 50 000 000 to 00 ammonia source “ammonia is described in more detail below, and is added On a solution of 11 of the present form, the micro-stream includes ALYY that partial-stream the solution is converted into a solution, ammonia? No, by adding monoammonium phosphate YY diammonium phosphate from goty

DZD Adding ammonia to the VV partial stream of an aqueous ammonium phosphate solution results in heat generation. Thus this process is exothermic and in the present model used to produce “alt, , monoammonium phosphate” the resulting solution is loaded with VY 800070018 from a mixture of 11114112004 which furthermore becomes heated. For this reason, a cooling arrangement, 000 cooling arrangement, is prepared to cool the heat generated when adding ammonia from a source of 010 ammonia in the partial stream 11 of the strip solution. It is preferable to (remove this heat resulting from the neutralization by a thermal Jobe ly oY heat exchanger) a cooled solution of a mixture of diammonium phosphate 3 monoammonium phosphate 1 e cooling equipment cooling arrangement 0 .. according to what will be explained lad follows in more detail, It is preferable to cool a solution of a mixture of monoammonium phosphate and diammonium phosphate 7 more than the addition of ammonia The addition of ammonia to a saturated NH4H2PO4 solution VY results in an exponential increase in the susceptibility limit The solubility of the ionic species in Lalla solution requires the addition of ammonia to reach a certain level, allowing the ammonium phosphates Yo 1e to be cooled below the temperature of the strip solution without forming any precipitates In this way, heat exchange can be carried out without the formation of scales on the heat exchangers.According to the references, it is known that the equation of phosphoric acid to diammonium phosphate results in a higher heat release (1501 kilocalories / kg) than NH3. gaseous reactant, or 998 kg Yo kcal / kg NH3 liquid reactant) compared to the equation monoammonium phosphate to 111 (0130000001000 phosphate kilocalorie / kg NH3 gaseous reactant, or 101 kilocalories / kg NH3 liquid reactant). Which means that by adding ammonia to a saturated 010008100700107 phosphate solution, the total heat generation is less compared to the production of monoammonium phosphate by direct neutralization of phosphoric acid with ammonia. goty py Heat exchange procedure using oa, Y in addition to the above, according to a preferred embodiment according to the figure to ALLY ammonia using the effect of conversion quenching (Se) quenching B 800000018. In this way _ gaseous that has been Obtaining ammonia after that using (Key) gaseous ammonia to remove the heat of neutralization. It is used as a feed stream with 8000001018. Naturally, heat exchange can be carried out by exchanging heat with air. Jie other liquids such as water or gases 5

The addition of ammonia should be preferably proportional to loading 010501816 in a water immiscible solvent?. The degree of conductivity decreases and the pH level increases with the decrease in the concentration of phosphoric acid in the solvent. Thus the addition of Ade ammonia pH and/or dap conductivity in solvent 7 can be controlled with a suitable Vs sensor. Another alternative is to monitor the pH and/or conductivity in the 1 strip solution or reuse circuit before or after adding ammonia

with suitable sensors. In alternative embodiments, it is possible to add ammonia from a source of ammonia Lisl directly to the strip solution 1 to form monoammonium phosphate Yo from the remaining phosphoric acid. However; The neutralization of phosphoric acid with ammonia is highly exothermic and results in the formation of a high degree of heat which must then be removed in the process. aly heat generation about yo degrees celsius per 1 molar equation of phosphoric acid to 00050816 monoammonium in liquid ammonia and about yo degrees per 1 molar equation of phosphoric acid to monoammonium phosphate with fizzy ammonia Yo. The direct equivalence of the 1,0-nade solution, which contains about 1 molar of phosphoric acid, results in an increase in temperature of about 88 °C when gaseous ammonia is used. The solubility of ammonium phosphates is highly dependent on temperature. For example, the solubility of monoammonium phosphate at 51 °C is 560 YO g per 100 100 ml of water and at 100 YO the solubility increases to about 170 YO g per 100 100 ml of water. . This implies that if ammonia is added directly to goty

Dew" 1 strip solution that contains phosphoric acid, there will be no precipitation of ammonium phosphates due to higher solubility at a higher temperature. In fact, it is possible to cool the 1 strip solution after adding ammonia By heat exchange, and with cell) Since the solubility of phosphates 20701001000 is dependent on temperature, this procedure may result in crystallization of ammonium phosphates based on the use of heat exchangers that reduce the efficiency of heat exchange and require removal Frequent scaling which is undesirable and makes it difficult to operate continuously.For this reason, it is preferable, according to the model of form LY, to have an immediate precipitation of monoammonium phosphate 0 resulting NEY from that when mixing the pure solution strip 1 solution with the cooled recycled diamond phosphate solution 51 in the Lye mixing reactor It has been shown that if the strip solution 1 and the recycled diamond phosphate solution 51 have the same temperature, the increase in temperature during tr Sepp monoammonium phosphate about ? Celsius only per molar of Yo phosphate precipitated. For a concentration of phosphoric acid of ©.? 1 molar in the strip solution The temperature increase is only about 1°C in the mixing reactor .010 compared to the temperature increase of about AN°C for the strip solution equation Directly with gaseous ammonia, this temperature increase is easily dealt with by Jie. According to the above mentioned lad, the cooled recycled diammonium phosphate 0 solution 51 can be controlled to have a lower temperature than the 5010 solution 1 temperature, which can compensate for the temperature increase during The precipitation of monoammonium 16 , which was obtained by combining the strip solution 1 with the recycled diamondmonium phosphate solution (0) In other words, the cooling arrangement is sles cooling arrangement to maintain the temperature of the Yo strip solution The loaded strip solution is below the saturation temperature of monoammonium goty

—yvo- from . monoammonium phosphate and thus crystals of phosphate are deposited in which no precipitation occurs. In ammonium phosphates the preferred cooling procedure is carried out in a stream of 0+ cooling arrangement. On the Vo cooling arrangement preferred model, the addition arrangement includes cooling in various ways. The cooling equipment can work ed) Cooling can also be done to it, i.e. ammonia for example in a coastal stream to which a 51© arrangement will be added or in a 0+ cooling arrangement before mixing. Alternatively, the refrigeration equipment could operate to it. Finally, the ammonia combination may also be cooled in the liquid stream to which 57. Typically a heat exchange medium © 0 will be added. The refrigeration equipment is 3) ammonia or Peltier other 000,000 Jie elements Aha however; Any refrigeration equipment, thermal conductivity, etc. 0 may also be used in Mmonoammonium phosphate in such a way that, according to the present embodiment, the same precipitation occurs. In this way, To is avoided without any requirements for cooling the mixing reactor Fo the mixing reactor, which improves the heat exchangers on the ammonium phosphates heat exchangers crystallizes the heat exchange efficiency of the process and makes the continuous operation easy and strong without That requires removal. Repeated shell heat exchangers of heat exchangers Vo in a solution of NHAH2PO4 crystals 700 out of the mixing reactor 91 slurry cally aly to unit Ve out of the mixing reactor 71 _ saturated. Feeding is done with slurries, NH4H2PO4 precipitate? mentioned above. The precipitate remover 0 precipitate YY loaded strip solution is configured to separate crystals 1; 51 remover from the solution

Jie Separation can be performed by any solid-liquid separation technique Fe leaving the mixing reactor 0 filtration; hardening Centrifuges; Etc. on 50 end treatment arrangements In other words, the downstream equipment includes Ve reactor, Yo diammonium phosphate mixing reactor, Diammonium supply and Yo supply facility are connected to the second discharging outlet 7? For the disclaimer section Ve mixing in diammonium phosphate to mix a solution vo ©?. The mixing reactor is configured as phosphate Yo goty

1 + strip solution to output 1 of stripping section BLY This model, the cooling arrangement 00 is configured to maintain the temperature of the solution 1 ? that leaves the mixing reactor 71 below the saturation temperature for monoammonium phosphate. This causes the precipitation of Monoammonium phosphate crystals from the monoammonium solution © p00050081_saturated. For this reason, the precipitate remover .50 in this model is adapted for separating crystals of monoammonium phosphate 0. The device for supplying diammonium phosphate ©? In this model, the addition device, LV, the addition device, Ve, in this model, includes an input connected to an output from the sedimentation unit (al) 500 precipitate remover to supply partial current 71 to the tip solution 4 exiting from the 0 removal unit The precipitate remover 40. The addition equipment is prepared to add 38 of the source 01 ammonia into the partial stream 71 of the strip solution 07 coming out of the sediment removal unit 50 precipitate remover, thus forming a solution that includes on diamond phosphate. The adding arrangement shall be load-configured to return the solution comprising the diammonium phosphate to the diammonium LY phosphate Vo mixing reactor The cooling arrangement shall be configured to keep the degree of the loaded strip solution sia below pha dap the saturation of monoammonium phosphate, thus crystals of monoammonium phosphate are precipitated. The separated crystals may be dried in a £1 dryer and/or granulated according to known processes forming 0 final product of monoammonium phosphate. Since the bound solution is a saturated mMono-ammonium phosphate solution, the water content of the separated crystals is low. Separate crystals can also be separated with other components such as nitrogen and potassium, forming different fertilizer products. It turns out that the residual solvent in the precipitated crystals, according to the present model, is very low since Yo corresponds only to the solvent dissolved in the solution attached to the separated crystals. is the goty solubility

unless

Solvents that are not miscible with water tributyl phosphate Jie water is low as a consequence

Solvent levels below 10 ppm in the crystals precipitated after separation.

In addition to the above; According to another embodiment, it is possible to remove traces of the dissolved solvent from the aqueous solution

Before the deposition of ammonium phosphates. This can be done by adding the oxidizer Jie over © hydrogen peroxide, etc. to oxidize the HBT solvent to SB carbon dioxide and phosphoric acid . with this

The method is even possible to reduce the presence of residual solvent in the product. In addition to the above, so if

There were other contaminants such as fluorine etc. that are co-extracted with phosphoric

0 can be removed from the strip solution by sedimentation, extraction, etc. prior to

. ammonium phosphates precipitation of compounds

0 Referring to an example of Fig. 1, an aqueous solution of ammonium phosphates is divided into ? Out of unit A) the sediment 50 precipitate remover is divided into two parts. One partial stream of Wl monoammonium phosphate solution is recycled; again to a second discharge inlet YE of the discharge section Ye and thus the equipment includes an Av recirculation system connected between the outlet of the precipitate remover 56 and the second discharge inlet Vi

1 mentioned for the aforementioned disclaimer section 01, where the sale system Av is configured to reuse the solution 51010 ; of the precipitate remover +¢ as the input strip solution. A partial stream, 71 seconds, of a solution of SW ammonium phosphates, according to what has been mentioned, is previously treated with ammonia by adding gaseous or liquid ammonia.

ammonium introduced into the entire system to form ammonia crystals the amount of 0 is used during these processes is very small. To achieve ammonia, the loss ratios are in . 5 to 80000018 sale In order to add an amount of Ve balance in the process, it is preferable to configure the tip addition device in the phosphate solution, which is dependent on the amount of material 1710. The addition device .01 of the external YY connection section From the aforementioned second strip exit, 1 strip solution

monoammonium depends on the relative amounts of ammonia sale and the added amount of Yo

goty

M phosphate and/or diammonium phosphate being produced, see models described Lad Below is one example of the production of ammonium phosphates according to the model from Figure 1. The flows correspond to the production of Monoammonium phosphate from sewage sludge ash Sanitary facility with a capacity of 0 70,0600 tons of ash per year. Feeding at a flow of i.e. 117 cubic meters per hour of water immiscible solvent© cally of Av per cent tributyl phosphate and 10 volume per cent kerosene and fed at a flow of 5.7 cubic meters per hour of solution Leaching of treated ash 1 containing 155 kg of 132004 per cubic meter in a side-liquid extraction section 0 featuring six contact stages. These outflows from the Jie extraction section amount to 1,711 0 cubic hours per hour of a water immiscible solvent? It contains 65 kg 113004 per cubic meter (0.75 jie cubic meters) per hour of purified by dissolution, expelled from it, Y phosphate. and a flow of 1.0 cubic meters per hour of recycled solution; It contains 710; kg of 404L dissolved per cubic jie in a second liquid-liquid extractor, and the discharge section includes 0.01 V0 five-stage contact. The outflows from the discharge aud are 1717 71 cubic meters per hour of a water immiscible solvent depleted of phosphate © and jie 5.1 cubic meters per hour of an aqueous solution + containing VAY kg H3PO4 and 5407 kg of NH4H2PO4 per cubic meter, all in dissolved form. Feeding is done with a flow of 1.; cubic jie per hour of 0 1 strip solution and a flow of 7.7 cubic jie per hour of ammonium phosphates (©) containing 417 kg of (NH4)2HPO4 per cubic meter in the reactor Mixing Fe The outflow from the mixing reactor Ye is 1.4 cubic meters per hour of cally slurry of 714.4 NH4H2PO4 solid in a solution containing 407 kg 0114112104 dissolved per cubic jie. The slurry is fed to a solid-liquid separator such as a precipitate goty.

4+0 remover , which separates 971 kg of NHAH2PO4 solid 1 crystals per hour for further processing. Water is added to the separated liquids to replace the water adhering to the separated crystals. A flow of 1.4 cubic meters per hour of separated fluid 9 containing 07 kg of dissolved NHAH2PO4 per cubic meter is divided into two streams. One of the two streams ¢© is recycled and is 1.; m³ per hour and contains 507 kg of dissolved NHAH2PO4 per Jie³ and is used to deflect a water-miscible solvent bearing phosphoric acide?. The second flow is of 7.7 cubic jie per hour containing 407 kg 114112104 solute per cubic jie loaded with 207010018_ mixed with 114 kg per hour of anhydrous ammonia. After heat exchange neutralization is removed, a flow of 7.3 cubic jie per hour 51 now containing 0 417 kg (NH4)2HPO4 dissolved per cubic jie is fed into the mixing reactor ve as described previously. According to the previous example, although the solvent loading © is only 10 kg of phosphoric 0 per cubic jie, a yield of 407 kg of solid AMMONIUM phosphates per cubic meter of solution is obtained Blade 1 strip solution at die Vo room temperature without cooling the mixing reactor with a heat exchanger. The goals behind the current model were many. One of Judy's goals was to avoid operational problems such as emulsions and raw material composition. In particular, the goal was to form a regenerative solvent without being contaminated by microcrystals. The goal of the AT is to provide ammonium 5 compounds with very low contamination from the binder, water-miscible solvent. 0 The objective of the AT of the present invention is to provide a high production yield of ammonium 5 compounds by immediate precipitation without the need for cooling during sedimentation. Another objective of the present invention is to allow an improved phase separation during removal of phosphoric acid from the solvent. The AT objective further comprises of the present invention in dali) recycling of the solvent without the need for further dalled by liquid-liquid extraction or distillation. Another object of the present invention is the goty

It provides a cost-effective way to produce ammonium phosphates without the need to clean ammonia from fumes. All these objectives were achieved by a model from Figure 7. Compared to the method according to the Russian patent “EYEAER”, the current model has additional Whey. The precipitation of monoammonium phosphate according to Russian patent 849 EY is based on the formation of a mixture of three phases: a solvent, crystals and an aqueous solution. The formation of precipitates during the planing process requires the use of special equipment that processes all three phases. It is for this reason that conventional liquid-liquid extraction equipment cannot be used. In addition to the above; Three-phase operation can enhance ore formation which can lead to operational problems. In addition to the above, in the experiments conducted, it was found that separation of the residual solvent from the monoammonium phosphate crystals by feeding 0 with a mixture of the three phases mentioned above into a commercial centrifugation results in higher than necessary levels of the residual solvent in the crystals (< 0 Yoo ppm tributyl phosphate ). Separation of the three phases by gravity results in some less residual solvent in the crystals but the purity of the crystals has been shown to depend on the organic to aqueous volume ratio of the mixture of the three phases. Using an organic to aqueous volume ratio required according to the Russian patent YEA _ to obtain 1 stoichiometric leaching/precipitation of monoammonium phosphate in the chemical elements, the level of residual solvent in the crystals is still too high even when using gravity separation <0001( parts per million of tributyl phosphate). 13 was the desired end product, the precipitated monoammonium phosphate can be converted to diammonium phosphate by feeding the precipitated monoammonium phosphate Y. ammonia y into a reactor containing a solution of diammonium phosphate according to the process described in UK Patent No. SY V0 In addition to the above; An example of a direct production setup of diamondmonium phosphate is shown in Figure LY. Extraction Section 01 and Section 010 are the same as those shown in Figure 7, however, the 00 end treatment arrangements have been modified to some degree. Yo Availability of supply equipment Diammonium phosphate *? Ditto Sa comprising goty gy monoammonium to precipitate |01 into the mixing reactor diammonium phosphate

Yo diammonium phosphate However, the specifics of the supplying device with . phosphate monoammonium phosphate follows. Lad is now supplied to some extent, which will be discussed. Precipitated monoammonium 1?, possibly adding to some remaining solution of ammonia DAP is fed as a slurry to the shunt reactor, 77. phosphate © In other words, YY DAP takes place in a reactor converting 10 source of ammonia into a stream produced by the addition of ammonia 90180000001010 phosphate initialization of the bearing production part, for example by means of a removal unit Precipitation strip solution Juaill according to what is done, 01 as in this form, or directly from the dissemination section 50 precipitate remover diammonium phosphate precipitation of ammonia to be discussed in a later form. It results from the addition of Ve 0180000001010 in a solution of phosphate 01810010010700 ?? LM crystals provide 000 cooling arrangement by VY Ll cooling equipment. 68 by heat exchange to a temperature preferably below 90°C. Crystals are separated from the main solution 59 in 54 diammonium phosphate separating crystals 0120001001010 The first £7 portion of the solution is recycled .49 DAP 0 7 separating unit?. The second part (0) of the separated DAP is recycled to conversion reactor 41686 to form intermediate compound 71 separated £0 to mixing reactor diammonium phosphate precipitated ammonia solution. In this way, the addition of 1000800110000 diammonium phosphate to monoammonium phosphate and the heat exchange during the conversion of . monoammonium phosphate in the production of the intermediate compound phosphate | 0 only sha in such a way that Lad is brought to Lachlaw the form of form ? may be incorporated into the reactor 56 precipitate remover separated in the MAP sedimentation unit from the crystals in such a way, it is from Possible (MAP) The remainder remains in the form of YY Conversion Well-defined diammonium phosphate and Monoammonium phosphate well-produced in the same unit. Yo goty

An Al model for the simultaneous production of well-defined monoammonium phosphate and well-defined diammonium phosphate faa is shown in Figure 4. Here, the partial current, AY, is entered for the pure solution + loaded with phosphoric acid ; monoammonium phosphate in the DAP mixing reactor 7?. A solution or slurry of AY tri-ammonium phosphate © is added. Using the correct mixing proportions and the appropriate temperature, a slurry of AY YY phosphate is formed. It is preferable to configure the cooling arrangement to maintain the temperature of the strip solution The bearing is below the saturation temperature for diamond phosphate, where crystals of diamond phosphate precipitate. The YY slurry comprises precipitated crystals of diammonium phosphate as well as a saturated solution of diammonium phosphate 0. The diamond phosphate crystals 44 are removed in a DAP sludge removal unit ??, leaving a saturated solution of diamondmonium phosphate ©4. A saturated solution of diammonium phosphate ©?; To the ipl adding arrangement leads Ve ammonium is added ... from Te SG ammonium (or from source 0 used in the production of monoammonium phosphate). A slurry consists of tri- ,AY ammonium phosphate 0 which is cooled in the oF heat exchanger to provide the tri- AY ammonium phosphate slurry used in the YY DAP mixing reactor. Diammonium phosphate production will sequentially collect volumes of non-sale diammonium phosphate solutions to be recycled and return to the stripping section. At the same time, the monoammonium phosphate production part loses corresponding volumes, which 0 at least in part that problem in the form Jay, AT has to replace. Model 0 ©?_ connected to the diammonium phosphate stream is shown here. The supply device B has been omitted. From that, the supply device Yay is used. monoammonium phosphate

Jad 4 diammonium phosphate produced by Yo diammonium phosphate for this purpose, micro-stream Ye to mixing reactor ©) diammonium phosphate in this embodiment a solution of © 4 ammonium phosphates from a solution of 840 Yo goty

As the diammonium phosphate, leaving the descaling unit, in this model the DAP 7 precipitating unit dl is recycled, to be used in the production of monoammonium phosphate. In other words, the phosphate production part 131700001070 is configured to add ammonia to a stream containing monoammonium phosphate . This causes precipitation of diamond phosphate © crystals from the saturated diammonium phosphate solution. Diammonium phosphate supply equipment includes (usually connecting a diammonium phosphate, and connecting a portion of a saturated diammonium phosphate solution stream from the portion of the diammonium phosphate production in the form of available diammonium phosphate to the monoammonium phosphate production. In Additional model, the model may be joined from the figures ; and *, 0 such that the mixing reactor Vo includes dad of a diammonium phosphate solution from any equipment aay) b©00050081 diammonium©?. The quantity of phosphate solution 012010001000 ...of different parts can be controlled to conform to the required proportion of monoammonium phosphate crystals produced and crystals of .diammonium phosphate .The auxiliary model of the diamond phosphate production equipment according to the present invention Ye is described in the present disclosure With reference to the LT figure most of the parts are similar to the ¥ figure and the differences consist mainly of the type of solutions used in the different parts of the equipment. A feed stream solution containing 1 phosphoric acid is fed to a liquid-liquid extraction section 0. The solvent immiscible with water is in this form a long-chain alcohol, preferably 0-heptanol, so that a sharp emulsion can be formed during reconstitution. Use the solvent to extract phosphoricacid 0 according to previously described. The temperature of the immiscible solvent Too Ll is preferably less than 60 degrees Lge because lower temperatures are in favor of phosphoric acid extraction. Liquid-liquid recovery section 01 is preferably configured to carry out a continuous liquor-liquid extraction process using preferably Je liquid-liquid extraction equipment pulse columns. However, YO can use any other liquid-to-liquid recovery equipment such as, stirred columns, non-goty columns

— ¢ ¢ — stirrers, stabilizers with mixers, in-line mixers, centrifugal conveyors, etc. The product purified by solute 7, exhausted in phosphate, is directed to further treatment (sale) Jie for use in dissolution; etc. The solvent not miscible with water?a and optionally loaded with phosphoric acid is cleaned with an aqueous solution to get rid of the co-extracted impurities.

8 The water immiscible solution phase bearing phosphorus A is then mixed with the recycled diamondmonium phosphate solution as the f¢ strip solution in the stripping section 01. As above, the stripping section Yo is preferably prepared For continuous liquid-liquid extraction process using liquid-liquid extraction equipment such as a stirrer mixer is preferred. However, any other liquid-to-liquid recovery equipment such as, pulse columns, columns can be used

0 Stirred, Non-Stirred Columns, Mixer Stabilizers, In-line Mixers, Centrifugal Connectors, etc. In contrast to cleaning with a solution of monoammonium phosphate which we have found to be based on equilibrium extraction, cleaning with a solution of 000505816 diammonium is based on the conversion of phosphoric acid into a dissolved salt. The interaction is as follows:

(NH4)2HPO4 + 13004 = 2 NH4H2PO4 10 Not based on equilibrium extraction, diammonium phosphate Since cleaning with solution complete cleaning can be obtained in single contact stage. Therefore, when using a solution for cleaning, the preferred diammonium phosphate liquid extraction equipment is a single mixer-fixing unit.

0 The cuddle phosphoric acid that is not miscible with loaded water is cleaned according to the present embodiment with recycled phosphate 18000700000 solution; a preferably in such a way that the susceptibility of monoammonium phosphate lsh i.e. diammonium phosphate is not exceeded. This enables operation with only two phases while cleaning in a mixer mount.

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E. According to the current model, phosphoric acid calas is made from a water immiscible solvent loaded “A” using a solution of “diammonium phosphate A” and through it no precipitation of “diammonium phosphate § monoammonium phosphate” occurs. It has been shown that by controlling the phase ratio of the solvent ?a to the diamond phosphate solution 4 during cleaning 0 the precipitation of ls monoammonium phosphate can be eliminated to a certain level. The phase ratio of solvent IY to a diamond phosphate solution A in which precipitation of monoammonium phosphate does not occur depends on the loading of phosphoric acid 4 of the solvent immiscible with water?a and the concentration of the phosphate solution 0180707001007 ;a. This means that it is preferable to configure the phase ratio for each operational condition. The ammonium phosphates solution, i.e. the 0 strip solution, is the entry;a, in the test preparation of this model consisting of a recycled diamond phosphate solution having a concentration of about 500 percent by weight and a pH is about A Similar to cleaning with a solution of monoammonium phosphate , cleaning with a solution of diammonium phosphate can be used to increase the concentration of Yo phosphate in strip solution 1 strip solution compared to the original concentration in the unmiscible solvent with water? This is accomplished by obtaining an organic phase to water ratio of greater than 1 during the conjugation process. In general, a higher concentration of f¢ diammonium phosphate provides a higher organic-to-water phase ratio during cleaning. A higher concentration of phosphate 018000000000 can be obtained by operating at a higher temperature. The ratio of 0 organic to aqueous phase should not increase to the levels of the leds. Monoammonium phosphate is precipitated during the leaching process. The phase ratio at the specific operating conditions and temperature is calculated according to the solubility of the participating ionic species. To load phosphoric acid into the solvent, immiscible with water, IY, at a concentration of 1 M and a concentration of Diammonium phosphate; molar, an organic phase to Sle Yo ratio of ?:1 is sufficient not to form any precipitate. goty

PT

NH4H2PO4 from a mixture of + strip solution Referring to Fig. 1, the strip solution consists of NH4H2PO4 to (NH4)2HPO4 4s (NH4)2HPOA4 (NH4)2HPO4). The obtained strip is significant Therefore, because a sufficient quantity of 1 solution of monoammonium phosphate during the conjugation process is required so that no precipitates of ammonium Lk are formed with 1 strip solution, the conveying solution is mixed .010 in the conjugation section © at PH The pH of Joy (NH4)3PO4 is maintained on Jas phosphates

Vo at about pH -8. The slurry 1?a leaving the mixing reactor Vo mixing reactor a?1 is saturated. The slurry is (NHE)2HPO4 fed into a (NHA)2HPO4 solution consisting of crystals. ¢ + precipitate remover ? To the precipitate remover 0 out of the mixing reactor to separate the crystals 0 precipitate remover the precipitate All) In this embodiment, the precipitate Ve ¢£ is prepared from a solution of diammonium phosphate separating crystals solid-liquid sald) separation may be performed by any separation technique. A1 diammonium phosphate filtration; hardening Centrifuges; etc. Jia The separated crystals can be dried and/or granulated according to the known processes that constitute the final __. The separated crystals can also be mixed with the components of diammonium phosphate Vo product formed for various enrichment products. potassium other such as nitrogen and out of the sedimentation unit fa Wl diammonium phosphate solution is separated one part of the solution is recycled vy, 6?; into two parts; a precipitate remover to ammonia? a. 0;a is added to the SW diammonium phosphate aqueous delamination section by adding gaseous ammonia diammonium phosphate from a solution of IVY part two 0 ivy aqueous diammonium phosphate to the ammonia solution or liquid. The addition of Lov results in thermogenesis and slurry formation?7a. Neutralization heat is removed by heat exchanger A from a mixture of 80114(211004) and 80114(3004). The cured slurry must ammonia b

JY in water immiscible solvent phosphate with loading ammonia proportional addition as further described above. Fo to mixing reactor To) provide cooled slurry Yo

In another embodiment, the introduced strip solution is a mixture of (((NH4)2HPO4 3; NH4H2PO4 0) for the introduced strip solution, the proportion of NP and the concentration of phosphate ions prevents precipitation of monoammonium phosphate or diammonium crystals phosphate when in contact with the solvent loaded with A phosphate Section © Disclaimer If the mixture of the strip solution entered contains more than 7780 cay, (NH4)2HPO4 the solvent is a water—immiscible alcohol alcohol to avoid emulsification, as further described above.If the mixture of the introduced strip solution contains less than (NHA)2HPO4 7700, any non-water miscible solvent may be used.

0 If the inlet strip solution has a ratio N/P and a concentration of 0005008161005 that causes monoammonium phosphate crystals to precipitate upon contact with the phosphate-laden solvent in the stripping section, the stripping section shall be designated as a three-phase stripping section. The precipitate remover is then configured to separate the monoammonium phosphate separating crystals from the loaded strip solution exiting from

Vo sign up. This is a typical situation when only (NH4)2ZHPO4 is used in the introduced strip solution. In this case, water—immiscible alcohol must be used as the solvent. Laie The strip solution introduced is a mixture of (NH4)2HPO4 ; NH4H2PO4 It is preferable that the equipment includes a mixing control unit configured to control the composition of the strip solution.

6. Input solution 0 in 1. In the figure, monoammonium phosphate helps to produce Al A model is shown and the solvent (NH4)2HPO4 is composed of a strip solution This model consists of the solution The tip is that emulsions of long-chain heptanol-n Jie Jas do not form immiscible with water?a from phosphoric acid as previously discussed. While reusing the solvent to extract

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A strip solution using strip solution IY the solvent immiscible with loaded water is cleaned strip solution resulting in the formation of three phases: cleaned solvent A, strip solution 1 loaded and precipitated 10114112004 crystals. A cleaned solvent S is separated and reused at the outlet of the stripping section, i.e. the solution forms (SW) phase. phosphoric acid NH4H2PO4 1b now extracted from 10114112004 crystals in a saturated © strip solution. A slight problem with this model is that the 0114112004 crystals formed contain very high levels of residual solvent. In order to remove the aforementioned residual solvent, YU monoammonium phosphate Jaa is mixed with 1 strip solution. This washing helps in separating the residual solvent 7© washing volume. It is recycled in a washing volume to the extraction section. Vo _ with a higher aqueous to organic phase ratio and the remaining solvent 0 can be recycled after separating 17 saturated NHAH2ZPO4 slurries of 10114112004 crystals were fed into solution . in the descaling unit. 40 precipitate remover to descaling unit 11 monoammonium separating crystals 4 0 precipitate remover crystals are separated from the main solution. Providing a first part, ah Ve source of it, by adding ammonia from ammonia source, adding 170 addition. The solution consisting of 814 (211004) is formed; a. This neutralization reaction generates 1 + ammonia cooling of the refrigeration equipment oF gall which is cooled by the exchanger Sha also using the (sale) solution in the heat exchanger, pall is done after Lo. Arrangement 4a in cleaning. Diammonium phosphate 0 separated 4 monoammonium phosphate from the YT solution using the second part (sale) is made from the remaining solvent, as described above.

NH4H2PO4 In systems where Leaf is used a three-phase disassembly section may be used

N/P of the entrance, and where the ratio of the strip solution as the pure solution (NH4)2HPO4 4 at monoammonium phosphate causes precipitation of crystals of phosphate ions and concentration of Yo goty

It comes into contact with the phosphate-laden solvent in the stripping section. If the molar amount of NH4H2PO4 is equal to or greater than ; times the molar amount of 80/14(211004), any non-miscible solvent with water, eg tributyl phosphate, can be used in a suitable diluent. In another way, water—immiscible alcohol © is used as a solvent. In other words, the loaded solvent immiscible with water IF is cleaned with solution 5010a consisting of a mixture of NHAH2PO4 and (NH4)2HPO4 and in which the molar concentration of NHAH2PO4 is greater than >280 at Its relationship to the total molarity of the phosphate in the case of using a non-alcohol as a solvent. The stripping process results in the formation of three phases. Ve minor changes can then be made to the equipment. They are indicated using dotted lines in JRE LY to this end; A third part 79 of the separated monoammonium phosphate 4 solution is allowed to shorten the addition device, which means that after cooling in heat exchanger 45,07 the diammonium phosphate solution is mixed with a third part Y4 of the separated monoammonium phosphate 156 solution, forming a solution; A which ally is a mixture of 1114112604 Vo and 00114(211004). Preferably, the addition arrangement comprises the addition of a control configured to add the strip solution stream directly from the outlet of the precipitate remover 56 with a solution stream comprising diammonium phosphate from the OY heat exchanger to obtain the ratio required of 1/5 in the scale section Xo According to the aforementioned, in the case of the molar concentration of 101144112004 > ZA in relation to the total 0 molarity of the phosphate reused in the cleaning, the solvent may be a non-alcoholic solvent. In the said case, residual solvent problems in monoammonium phosphate crystals are significantly reduced and the saving of crystal washing can be eliminated. The use of a three-phase yo split section may also be combined with the production of either or both cook and cook. An embodiment is shown in Fig. 8. An Ao slurry of monoammonium (Yo phosphate) crystals in a saturated (@ammonium) mono solution is taken from a goty precipitate

meh alla; ¢ + remover To the mixing reactor YY DAP ammonia is added and the heat of neutralization is cooled, similar to the embodiment of Figure 7. However, in the embodiment of Figure A a sale) of the diammonium phosphate solution £ 0 of the DAP descaling unit 7 here Va of that to be used as the strip solution. If the quantity of diamond phosphate © crystals is too low to maintain the inlet strip solution, the AT monoammonium phosphate stream can be taken from the precipitate remover 5460, and ammonia can be added to convert the solution into a diamond solution phosphate. Optionally, a cooling arrangement is also connected to the said current.

(NH4)2HPO4 s NHAH2PO4 from a mixture of strip solution If the 0 precipitate (Aly) solution consists of 110008117001010 phosphate unit AY solution, part of the input can be mixed without passing through the strip solution In the pick-up solution 5001601011816 remover Here also, the add-on control method can be provided and configured to add the Ve stream of the add-on device by using a stream solver that includes 50 sediments A of the dropper directly from the outlet of the unit.

.01 required in the NP section to obtain a diammonium phosphate ratio of 0. If the solvent is non-alcoholic, the crystal washing device may also be omitted. The embodiments described above are to be understood as a few illustrative examples of the present invention. Those experienced in the art will understand that numerous modifications, combinations and changes can be made to the embodiments without departing from the field of monoammonium phosphate parallel production of both JB of the present invention. for diammonium according to the principles described above, and the production of 80000007 phosphate; 0 with a stripping solution consisting of triammonium phosphate by reacting a diammonium phosphate slurry and producing “phosphoric acid” 3 monoammonium phosphate in which diammonium phosphate is in combination with stripping using a phosphate solution in any case; The les domain is specified. monoammonium phosphate intermediate compound is

Yo the present invention by appended claims.

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Claims (2)

-1E - Elements of Protection -1 Equipment (V+ +) arrangement for the production of pure ammonium phosphates compounds, including: aud extraction, (01) stripping section prepared for a liquid-liquid extraction of liquid phosphates -liquid extraction of phosphate between a feed liquid,(1) comprising phosphoric acid, and a solvent (*): 0 said solvent (0) having a water solubility of less than AY of the feed liquid The aforementioned feed liquid (1) is essentially free of 1005 nitrate; the aud of the aforementioned extraction (01) has a first extraction inlet (11) to provide the aforementioned feed liquid ( 01 ) , second extraction inlet (VY) for supplying said solvent (*), Jad (VY) first extraction outlet Yee for feed liquid ( Y) at least partially depleted in phosphate and (V€) second extraction outlet st to transfer said solvent (7) loaded with phosphate ; aud shay Gee (V+) stripping section liquid extraction - Liquid phosphate, liquid-liquid extracti on of phosphate .between said solvent (V) loaded with phosphate Vo and strip solution Juaill (¢); Said aud includes a first extraction inlet, connected to said second extraction outlet, (V€) to provide said solvent (7) loaded with phosphate, second extraction inlet) ¢ (Y) to provide the inlet strip solution (4), a first extraction outlet (YY) to carry said solvent that is at least partially depleted in phosphate Y. and a second extraction outlet (YY) to transport the output from the strip solution strip solution (Y) Said first extraction outlet (YY) is connected to said second extraction inlet (VF) to recycle said solvent (©) at least partially depleted in phosphate to extraction more phosphate ; Said strip solution (¢) is an aqueous ammonium phosphate solution ; where at least one of: at least 0 of the 200001000_phosphates in said strip solution (¢) is monoammonium phosphate: and the aforementioned solvent (7) is water—immiscible alcohol; source of ammonia (10) included in the final treatment arrangements (end 0) treatment arrangements 4) connected At the aforementioned second contact outlet 9 “): an (V+) adding arrangement connected to a source of 0S ammonia (+7) Ve, a cooling arrangement (+) is added to cool the heat generated at 328 from the aforementioned source Sad ammonia (0) to at least said partial stream from said strip solution: a precipitate remover (+¢) configured to separate separating crystals from said strip solution: 0 The aforementioned add-on device (70) is shee to add (ammonia) the ammonia source mentioned to the The least partial current of the aforementioned strip solution before or after the sas precipitate remover (50): and an (A+) recirculating system connecting the aforementioned outlet of the precipitate remover unit) 2) and a second extraction inlet mentioned 3 (Y) of the mentioned Jatin section (01), 1 mentioned circulation system (Ar) bee to reuse the strip solution (9) from the removal unit precipitate remover (+¢) as the input strip solution (). “- the arrangement according to claim 1, and it is characterized by having at least 7860 phosphates Yo 20000001010._ mentioned in the strip solution. The mentioned entry (¢) is monoammonium phosphate. goty Arg "- the arrangement is according to the element of protection L, Y and is characterized ob by all the ammonium 5 mentioned in the solution M5106._The mentioned entry (;) is monoammonium phosphate, and additionally includes Supply device B (Yo) diammonium phosphate© and mixing reactor (0 10) Said mixing reactor (0 −) is connected to said second extraction outlet (YY) of said extraction section (Vo) and said supply device B (Ye) diammonium phosphate and the shea is to mix the diammonium phosphate solution (°) in a portion on JN of the outlet stream of the said strip solution (1) of the said strip solution: (01) 0 The aforementioned cooling arrangement (+) is designed to maintain the temperature of the strip solution under the aforementioned bearing below the saturation temperature of monoammonium phosphate, where monoammonium crystals are deposited phosphate from a saturated monoammonium phosphate solution: where the precipitate remover (+¢) is prepared for separating Yo crystals of monoammonium ph osphate mentioned. ¢— The arrangement, 8, of the element of protection “, and is characterized by the fact that the aforementioned (Yo) 018000000100 phosphate supply device includes the aforementioned addition device:(11) The said addition device (Vo) includes an input connected to the unit Al) precipitate (401) remover | 00 to supply the partial stream from said solution Tip: said addition equipment (70) is shee to add said ammonia from said 38 source (1) to the stream Sad of said strip solution said strip solution forming solution (01) and comprising diammonium phosphate; said addition device (70) being additionally adapted to return said solution (511) Yo and comprising diammonium phosphate to the aforementioned diammonium phosphate mixing reactor (01). goty E – o The arrangement, according to the protection element, Lf, is characterized by a diamond production part, bea phosphate, to add ammonia to a stream originating from the aforementioned strip solution (7) containing monoammonium phosphate, and causing In the precipitation of diamond phosphate crystals _ from a saturated phosphate solution 018070000070 o 1—the preparation according to claim ,1 is characterized by the said solvent being water—immiscible alcohol. Arrangement according to protection element 1 or 1, characterized by a mixing control unit. The aforementioned inlet strip solution (;) to have a ratio of NP and a concentration of phosphate ions that prevents precipitation of monoammonium phosphate or diammonium phosphate crystals upon contact with 1 of the aforementioned solvent (T) loaded with phosphate in the aforementioned extraction section (71). 4- The arrangement arrangement according to protection element 1 or LT is characterized by a unit Mixing control unit, configured to control a combination of the said inlet strip solution (8) Yo said mixing control unit is shea to control the said inlet strip solution (;) To have a ratio of NP and a concentration of 1005 phosphate, it causes monoammonium phosphate crystals to precipitate upon contact with the aforementioned solvent loaded with phosphate in the dual HS stripping aud. The said stripping section is the stripping stripping section 007 A three-phase sass precipitate remover is prepared to separate the aforementioned monoammonium phosphate separating crystals from the aforementioned strip solution emerging from the aud of the aforementioned extraction. goty E 4- The arrangement is according to protection element A and is distinguished by the fact that the aforementioned addition (V+) is prepared to add ammonia from the said ammonia source (10) to the partial stream of the aforementioned strip solution, which The solution shall be and include Diammonium phosphate ; © Said adding arrangement (Vo) includes said cooling arrangement (53(2) said said adding arrangement (Vr) furthermore includes said mixing control: said mixing control is disposed to mix a stream of solution The aforementioned strip solution is directly from the aforementioned outlet of the precipitate remover unit with the aforementioned Ve solution stream that includes diammonium phosphate to obtain the aforementioned NP ratios. ,1 The ol is characterized by all ammonium 5m mentioned in the strip solution The entrance mentioned is diammonium phosphate ; 0 The mentioned equipment includes: Controlling the flow of the strip solution The entrance (4 ), prepared to provide a flow of the strip solution, the aforementioned inlet is sufficient phosphate Caan of said solvent without causing precipitation of crystals; the feeding equipment (IY) triammonium phosphate is adapted for mixing triammonium slurry E 1( phosphate 0) in said output current from the pure solution strip solution (1) from the aforementioned resection section: (01) The aforementioned cooling arrangement (+) shall be prepared to maintain the temperature of the strip solution under the aforementioned bearing below the saturation temperature of the diamond phosphate , where crystals of diammonium phosphate are precipitated from saturated Yo phosphate solution 0130000001010: goty -1e- The precipitate remover unit (+¢) is equipped to separate the aforementioned separating diamond phosphate crystals. solution © 5016 _inlet, and shee is to provide an influx of the strip solution Said inlet (;) is low enough to cause precipitation of monoammonium aie phosphate The strip solution touches said inlet (4) With said solvent (7) loaded with phosphate in said stripping section (0"): dua said stripping section (Yr) aud is a three-phase stripping section: 0 removal unit The precipitate remover (+¢) is prepared to separate the aforementioned separating monoammonium phosphate crystals from the aforementioned strip solution (71) coming out of the aforementioned extraction section (Yr) and the washing volume. (YO) volume connected to the aforementioned second outlet (YY) of the aforementioned extraction section (701) and prepared to wash the precipitated monoammonium phosphate crystals from Masculinity in the aforementioned strip solution Ye zal (1) from the aforementioned extraction section (V+) by _phosphate_solution 0000810000000_ from the aforementioned outlet of the precipitate remover unit (+¢). 1 The arrangement arrangement according to any of the claims 1 to 11 is characterized by the fact that the aforementioned addendum 0 device (V1) is prepared to add an amount of ammonia to the said additive device (V+) ammonia to said adding arrangement, according to the quantity of phosphate substance Al-Naseel in the aforementioned solution Al-Naseel 5010 (7) exiting the second extraction outlet (YY) mentioned for the aforementioned section of the connection. (1) Yo? 1- A method for producing compounds Ammonium phosphates pure, including steps: goty Has - extraction of os phosphate (71011) feed liquid (1) comprising phosphoric acid by means of liquid-liquid extraction in solvent (*): said solvent (0) has a water solubility of less than AY liquid feed 71660 _mentioned (1) is essentially free of nitrate 1005 ; © - recovery (YVY) of said solvent of at least part of said phosphate by means of liquid-liquid extraction to Strip solution (4): The aforementioned strip solution (4) is an aqueous ammonium phosphates aqueous ammonium phosphate solution ; stripped phosphate 0 and said solvent (5) that is at least partially depleted in phosphate: - Recycle (YT) said solvent (0) that is at least partially depleted in phosphate to extract more phosphate in step The said extraction: where at least one of: at least 0 of the ammonium phosphates mentioned in the strip solution Yeo 1100 Na 50_ said entry (4;) is monoammonium phosphate: and the said solvent (0) is water—immiscible alcohol ; - Adding (4) YY ammonia to at least the partial stream that includes the said solution. (YY) crystals from said loaded strip solution, at least said partial lal to which ammonia is added is at least a partial stream of said strip solution before or after said decrystallization step ) 9 ") sale) - Cycle (YY) the SAN strip solution after said descrystallization step 8 to use it as the input strip solution (4) in said step for contact. goty —oA- ammonium and is characterized by at least 7860 of OY The method according to claim 6 - the mentioned entry (;) is the strip solution mentioned in the strip solution 5 . monoammonium phosphate ammonium phosphates and is characterized by that all VE method according to the protection element —Ye 5 mentioned in the aforementioned input strip solution (£) to be monoammonium phosphate, and by the following additional steps: Mixing (°V) diammonium phosphate solution with at least oa stream of strip solution The aforementioned (6) loaded with stripped phosphate: 0 Maintaining the temperature of the strip solution with the aforementioned bearing below the saturation temperature of monoammonium phosphate J: precipitation of monoammonium phosphate crystals »5 monoammonium solution; axiall phosphate The mentioned step to remove crystals (YY £) crystals includes the aforementioned chapter for crystals M of monoammonium phosphate. 7- The method according to claim 15, is characterized by adding the aforementioned 200000018__ to the aforementioned partial stream of the aforementioned strip solution, and forming a solution (0) that includes diammonium phosphate ; 0 Returning the aforementioned solution (01) that includes diammonium phosphate to the aforementioned strip solution (1) loaded with stripped phosphate Juaill. It is water—immiscible alcohol. The -VA Yo method according to claim element VE or VY is characterized by controlling the composition of the aad strip solution mentioned (4). goty q — g - the method according to any of Claims 11 to VA and is characterized by the aforementioned step procedure of adding to an amount of ammonia sale according to the amount of strip phosphate in the said strip solution (1) After the aforementioned extraction process. ‎goty.‎ _ h “= mn CTR Peat wv 8 3 + bm ahm sa : i a a a a a a a a a a a a a a a a a a a a a a a a a a a a aa EEE CI i —— The extended modified 1 0 a ْ : H i HN : 8 : 1 Seems: : ¥ % » Ton H § 0: H FE A SER aa CP CVUUURR Ch 1 : 0 Aa aa aa i {od H H i 1 H v d L : 08 0 EI Po AAAS . 1 N 1} i : AA AA AA 8 FE 1 8 a = H 8 EE } i RI Lome H i id = i 1 Po 5 0 0 ? i 0 ? ; 1 : i LLP RE —.— H i NEE CRE a x vos Eo 11 vo Co 3 v g 0 8 2 i to YYi 1 N HE 1 Pod { 1 i \ v i i] H 1 No ned for “EA - A 1 1 2 In Masala { 1 alam l ir 1 io 1 Poa . 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A Yrs CL awe od id H i H 3 Hayy Tahdam Mahh Ah Jahjal Ha Ahem A EVERY BY 1 Hali 5 3 i i : ix { J TE 1" D | jo ANA RY NOTA ANS AJ ep mar AN EAI rm om sean A Ama mad i 5 8 A A A A any : vd Po { 3 : i AM RE) Je ed IAPR TA A A S: } } 1070 SE y po ; NR TF EE I 3 H 0 1 SNE i Pov ; orl in HI § ; } To Vo 1 1 six [ kyiaae l l i H i Lp heeded 3 3 TRI 4 : 1 1 1 Ld / EE ECL SR or vol { 1 1 a ;: { NEE AIS i Ear SER Eo ; 3 : TS ut Laqn A ( | | Waq 01 A | Co Ny pg 1b 3 3 Rane Alsab 3 AE Oh Bot ES H i iS * <* e wd Ke lm xm : aan ann bar dain nas var WE Je i sea H x 3 + i 3 AR EW 1 1 H 1 t EEE cl sen mom mm a an savas jed wana vn od by : H H 8 : : ES maint a DG JJH ASR 3 WO nm mm mn ASA tn mm mn a SY SRL Sen some SR up to 3 {0 AA EE: SS no AD According to the SEE ETS ED 0 C, Figure A and F The validity period of this patent is twenty years from the date of filing the application, provided that the annual financial fee is paid for the patent and that it is not invalid or forfeited for violating any of the provisions of the patent system, layout designs of integrated circuits, plant varieties, and industrial designs, or its executive regulations issued by King Abdulaziz City for Science and Technology; Saudi Patent Office P.O. Box TAT Riyadh 57??11 ¢ Kingdom of Saudi Arabia Email: Patents @kacst.edu.sa