SI20636A - Method of formulating alkali metal salts - Google Patents

Method of formulating alkali metal salts Download PDF

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Publication number
SI20636A
SI20636A SI9920082A SI9920082A SI20636A SI 20636 A SI20636 A SI 20636A SI 9920082 A SI9920082 A SI 9920082A SI 9920082 A SI9920082 A SI 9920082A SI 20636 A SI20636 A SI 20636A
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Slovenia
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liquid
ammonium
sulfate
sodium bicarbonate
bicarbonate
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SI9920082A
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Slovenian (sl)
Inventor
Robin Phinney
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Airborne Industrial Minerals Inc.
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Publication of SI20636A publication Critical patent/SI20636A/en

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D7/00—Carbonates of sodium, potassium or alkali metals in general
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D7/00—Carbonates of sodium, potassium or alkali metals in general
    • C01D7/02—Preparation by double decomposition
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
    • C01D5/06—Preparation of sulfates by double decomposition
    • C01D5/08—Preparation of sulfates by double decomposition with each other or with ammonium sulfate
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D1/00—Fertilisers containing potassium
    • C05D1/02—Manufacture from potassium chloride or sulfate or double or mixed salts thereof
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D7/00—Fertilisers producing carbon dioxide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Fertilizers (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Treating Waste Gases (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

Methodology for formulating sodium bicarbonate and potassium sulfate. In one embodiment, sodium sulfate and ammonium bicarbonate are reacted to form sodium bicarbonate with the remaining liquor or brine treated with sulfuric acid to remove carbonates with subsequent precipitation of potassium sulfate. A further embodiment employs ammonium bicarbonate, ammonia gas or carbon dioxide to precipitate sodium bicarbonate. The result of the methods is the production of high quality fertilizer and food grade sodium bicarbonate.

Description

AIRBORNE INDUSTRIAL MINERALS INC.,AIRBORNE INDUSTRIAL MINERALS INC.,

KanadaCanada

METODA ZA OBLIKOVANJE SOLI ALKALIJSKIH KOVINMETHOD FOR FORMING ALKALINE METAL SALTS

Področje tehnikeThe field of technology

Predmetni izum se nanaša na metodo za oblikovanje soli alkalijskih kovin, natančneje se predmetni izum nanaša na metodo generiranja natrijevega bikarbonata, ki je zadosti kakovosten za prehrano, ter kalijevega sulfata, ki je zadosti kakovosten za gnojilo.The present invention relates to a method for forming alkali metal salts, more particularly to the present invention relates to a method of generating sodium bicarbonate of sufficient quality for consumption and potassium sulfate of sufficient quality for fertilizer.

Ozadje izumaBACKGROUND OF THE INVENTION

V zvezi z metodo za oblikovanje soli alkalijskih kovin je znano stanje precej obsežno. Natrijev bikarbonat je bil na primer pripravljen na toliko različnih načinov, kot jih je bilo poznanih. Ne glede na to so bile predhodne enote delovanja za sintezo bikarbonata ovirane zaradi neučinkovite rabe energije, zaradi česar se neposredno povečajo stroški sinteze. Dodatna omejitev uporabe znanih postopkov je dejstvo, da enot delovanja, ki so potrebni za pripravo soli, ne uporabljajo učinkovito.With respect to the method for the formation of alkali metal salts, the known state is quite extensive. Sodium bicarbonate, for example, was prepared in as many different ways than was known. Nevertheless, previous units of action for the synthesis of bicarbonate were hampered by inefficient use of energy, which directly increased the cost of synthesis. An additional limitation to the use of known processes is the fact that they do not use the operating units required for salt preparation effectively.

Tipično se oblikuje en sam visoko-kakovosten proizvod, ob tem pa pripadajoči stranski proizvodi, ki niso dovolj kakovostni za komercialno uporabo, ali bi bila potrebna prevelika investicija, da bi ti stranski produkti lahko bili komercialno uporabni.Typically, a single high-quality product is designed, with associated by-products of insufficient quality for commercial use, or excessive investment would be required to make these by-products commercially viable.

Predstavnik znanega stanja je ameriški patent št. 3,429,657, ki je bil podeljen 25. februarja 1969 in katerega prijavitelj je bil D'Arcy. V navedenem viru se razpravlja o metodi za regeneracijo in produkcijo natrijevih soli. Po viru se slanico, ki nosi kalij, reagira z natrijevim perkloratom, da bi se precipitiral kalijev perklorat. Kalij se odstrani z io ionsko izmenjavo z natrijem, prosti kalij pa se nato med drugim lahko spoji s kloridom, sulfatom ali nitratom.A representative of the known state is U.S. Pat. No. 3,429,657, which was granted February 25, 1969, and the applicant was D'Arcy. The above source discusses a method for the recovery and production of sodium salts. According to the source, the brine carrying the potassium is reacted with sodium perchlorate to precipitate the potassium perchlorate. Potassium is removed by ion exchange with sodium and free potassium can then be combined with chloride, sulfate or nitrate, among others.

Industrijska uporabljivostIndustrial usability

Predmetni izum je uporaben v industriji umetnih gnojil.The present invention is useful in the fertilizer industry.

Opis izumaDescription of the invention

Eden od namenov ene od izvedb predmetnega izuma je prikazati metodo za proizvodnjo natrijevega bikarbonata, ki je zadosti kakovosten za prehrano, ter kalijevega sulfata, označeno s tem, da ta metoda obsega naslednje stopnje:One of the purposes of one embodiment of the present invention is to provide a method for the production of sufficiently good quality sodium bicarbonate and potassium sulfate, characterized in that this method comprises the following steps:

a) pridobitev vira tekočega natrijevega sulfata;a) obtaining a source of liquid sodium sulfate;

b) pridobitev vira amonijevega bikarbonata;b) obtaining a source of ammonium bicarbonate;

c) spravljanje natrijevega sulfata in amonijevega bikarbonata v stik;c) contacting sodium sulfate and ammonium bicarbonate;

d) obarjanje natrijevega bikarbonata in formiranje tekočine;d) precipitation of sodium bicarbonate and formation of a liquid;

e) obarjanje natrijevega bikarbonata in formiranje tekočine s kontaktiranjem tekočine iz stopnje d) z natrijevim sulfatom;e) precipitating the sodium bicarbonate and forming the liquid by contacting the liquid from step d) with sodium sulfate;

f) nasičenje tekočine iz stopnje e) z natrijevim sulfatom; s g) filtriranje trdnih snovi iz tekočine iz stopnje f);f) saturation of the liquid from step e) with sodium sulfate; g) filtering solids from the liquid of step f);

h) spravljanje tekočine iz stopnje g) v stik z žvepleno kislino, da se precipitirajo karbonati;h) bringing the liquid from step g) into contact with sulfuric acid to precipitate carbonates;

i) ohlajevanje tekočine iz stopnje h) na 0°C, da nastane precipitat Glauberjeve soli;i) cooling the liquid from step h) to 0 ° C to form a Glauber salt precipitate;

j) ogrevanje tekočine iz stopnje i) na med 30°C in 40°C; inj) heating the fluid from step i) to between 30 ° C and 40 ° C; and

k) precipitiranje kalijevega sulfata s kontaktiranjem tekočine iz stopnjek) precipitation of potassium sulphate by contacting the liquid from the step

j) s kalijevim kloridom.j) with potassium chloride.

Nadaljnji namen ene od izvedb predmetnega izuma je prikazati metodo is za oblikovanje natrijevega bikarbonata, ki je zadosti kakovosten za prehrano, ter kalijevega sulfata, označeno s tem, da se metoda sestoji iz naslednjih stopenj:It is a further object of one embodiment of the present invention to provide an iso method for the formation of sufficiently high quality sodium bicarbonate and potassium sulphate, characterized in that the method consists of the following steps:

a) pridobitev vira tekočega natrijevega sulfata;a) obtaining a source of liquid sodium sulfate;

b) pridobitev vira amonijevega bikarbonata;b) obtaining a source of ammonium bicarbonate;

2o c) spravljanje natrijevega sulfata in amonijevega bikarbonata v stik;2o c) contacting sodium sulfate and ammonium bicarbonate;

d) precipitiranje natrijevega bikarbonata in formiranje tekočine;d) precipitation of sodium bicarbonate and formation of liquid;

e) precipitiranje natrijevega bikarbonata in formiranje tekočine s kontaktiranjem tekočine iz stopnje e) z natrijevim sulfatom;e) precipitating the sodium bicarbonate and forming the liquid by contacting the liquid from step e) with sodium sulfate;

f) nasičenje tekočine iz stopnje e) z brezvodnim natrijevim sulfatom;f) saturating the liquid from step e) with anhydrous sodium sulfate;

g) filtriranje trdnih snovi iz tekočine iz stopnje f);g) filtering solids from the liquid of step f);

h) spravljanje tekočine iz stopnje g) v stik z vsaj eno od naslednjih snovi: amonijev bikarbonat, amonijev plin ali ogljikov dioksid, da se s precipitira natrijev bikarbonat;h) contacting the liquid of step g) with at least one of the following substances: ammonium bicarbonate, ammonium gas or carbon dioxide to precipitate sodium bicarbonate;

i) ohlajevanje tekočine iz stopnje h) na 0°C, da nastane precipitat natrijevega bikarbonata in natrijevega sulfata; ini) cooling the liquid from step h) to 0 ° C to form a precipitate of sodium bicarbonate and sodium sulfate; and

j) precipitiranje kalijevega sulfata s kontaktiranjem tekočine iz stopnje i) s kalijevim kloridom.j) precipitation of potassium sulphate by contacting the liquid of step i) with potassium chloride.

Ugotovljeno je bilo, da se po oblikovanju natrijevega bikarbonata doseže občuten uspeh pri odstranjevanju natrijevega sulfata v obliki Glauberjeve soli in natrijevega bikarbonata, tako, da se tekočino ohladi na 0°C. Topnost Glauberjeve soli v sistemu se opazuje s faznim diagramom is amonijevega sulfata - natrijevega sulfata. S povišanjem količine natrijevega sulfata v bikarbonatnem obroču s povišanim recikliranjem Glauberejve soli obstaja tendenca zmanjševanja topnosti bikarbonata in povečanja učinkovitosti postopka.It has been found that, after the formation of sodium bicarbonate, considerable success has been achieved in the removal of sodium sulphate in the form of Glauber salt and sodium bicarbonate by keeping the liquid at 0 ° C. The solubility of the Glauber salt in the system is observed by the phase diagram of ammonium sulfate - sodium sulfate. By increasing the amount of sodium sulfate in the bicarbonate ring by increasing the recycling of Glauber's salt, there is a tendency to reduce the solubility of bicarbonate and increase the efficiency of the process.

Glede konverzije začetnih reagentov v kalijev sulfat je bil uspeh zlasti 2o dosežen tako, da se je ohranjalo molsko razmerje kalijevih in amonijevih ionov pet (5) ali višje. To razmerje omogoči visoko učinkovitost konverzije v drugi stopnji postopka.With regard to the conversion of the starting reagents to potassium sulfate, success in particular was achieved by maintaining the molar ratio of potassium and ammonium ions to five (5) or higher. This ratio allows for high conversion efficiency in the second stage of the process.

Kratek opis slikShort description of the pictures

Slika 1 je diagram poteka postopka, ki prikazuje prvi del enega od postopkov po predmetnem izumu;Figure 1 is a flowchart showing the first part of one of the methods of the present invention;

Slika 1a prikazuje drugi del postopka, ki je prikazan na sliki 1; s Slika 1b prikazuje tretji del postopka, ki je prikazan na sliki 1;Figure 1a shows the second part of the process shown in Figure 1; s Figure 1b shows the third part of the process shown in Figure 1;

Slika 2 je diagram poteka postopka, ki prikazuje prvi del variacije postopka po predmetnem izumu;Figure 2 is a flowchart showing the first part of a variation of the process of the present invention;

Slika 2a prikazuje drugi del postopka, ki je prikazan na sliki 2; inFigure 2a shows the second part of the process shown in Figure 2; and

Slika 2b prikazuje tretji del postopka, ki je prikazan na sliki 2.Figure 2b shows the third part of the process shown in Figure 2.

Podobne številke na slikah označujejo podobne elemente.Similar figures in the figures indicate similar elements.

Načini izvedbe izumaMethods of carrying out the invention

Če se sedaj sklicujemo na slike, slike od vključno 1 do vključno 1b is prikazujejo postopek po prvi izvedbi predmetnega izuma.Referring now to the drawings, the drawings 1 to 1b inclusive show the process of the first embodiment of the present invention.

Vir tekočega natrijevega sulfata 10 raztopljen v sveži vodi in centratni vodi 12, ki jo opisujemo v nadaljevanju. Raztopino se v posodi 14 meša pri temperaturi 40°C, da se doseže specifična težnost 1,30. Raztopino se filtrira v filtru 16, ki lahko primeroma obsega 5 mikronski filter. Trdne snoviThe source of liquid sodium sulfate 10 dissolved in fresh water and centrate water 12, which is described below. The solution is stirred at 40 ° C in container 14 to achieve a specific gravity of 1.30. The solution is filtered in a filter 16, which may for example comprise a 5 micron filter. Solids

2o 18 se odstrani, medtem ko se filtrat 20 prenese v prvo posodo za kristalizacijo natrijevega bikarbonata 27.2o 18 is removed while the filtrate 20 is transferred to the first sodium bicarbonate crystallization vessel 27.

Začetne snovi - voda, amoniak in ogljikov dioksid, ki so vse označene s številko 24 - se reagira v posodi 22, da se sintetizira amonijev bikarbonat. Oblikovani amonijev bikarbonat se centrigufira v centrifugi 26, pri čemer je trdni produkt doveden v kristalizacijsko posodo 27. Reciklažna zanka 28 recirkulira trdne snovi amonijevega bikarbonata in tekočino v reakcijsko posodo 29. Rezultat kombinacije v posodi 29 je s oblikovanje natrijevega bikarbonata. Mešanico se filtrira s filtrom 30 in centrifugira. Natrijev bikarbonat se v posodi 32 spere z vodo in centrifugira v centrifugi 34, trdna snov pa se zadrži kot natrijev bikarbonat, ki je dovolj kakovosten, da se ga lahko uporablja za prehrano. Sveža voda se vrne v posodo 14.The starting materials - water, ammonia and carbon dioxide, all of which are numbered 24 - are reacted in vessel 22 to synthesize ammonium bicarbonate. The formed ammonium bicarbonate is centrifuged in centrifuge 26, the solid product being fed into the crystallization vessel 27. The recycle loop 28 recirculates the ammonium bicarbonate solids and the liquid into the reaction vessel 29. The result of the combination in vessel 29 is the formation of sodium bicarbonate. The mixture was filtered with a filter 30 and centrifuged. Sodium bicarbonate is washed with water in a container 32 and centrifuged in a centrifuge 34 and the solid is retained as sodium bicarbonate of sufficient quality to be used for nutrition. The fresh water is returned to the container 14.

io Tekočina iz filtra 30 ima specifično težo 1,25, njena vsebina pa vključuje približno 10,4% natrijevega sulfata, 17,1% amonijevega sulfata, 8% natrijevega bikarbonata in v presežku amonijevega bikarbonata za reagiranje z Glauberjevo soljo (ki bo opisano v nadaljevanju). Tekočino se reagira v posodi 36 pri 40°C, pri čemer se Glauberjeva sol oblikuje v fazi is ohlajanja postopka, o kateri bo govora kasneje, da nastane natrijev bikarbonat iz presežka amonijevega bikarbonata v kristalizacijski posodi 29. Alternativno je mogoče amonijev bikarbonat dodati drugi stopnji (posoda 36) v obliki trdne snovi, razredčene trdne snovi ali raztopine. Tekočini iz posode 36 se doda trdni natrijev sulfatu iz vira 41 v posodo zo 40, da se oblikuje nasičena raztopina natrijevega sulfata / amonijevega sulfata. Lahko je prisotnega dovolj amonijevega bikarbonata, da se reakcija zaključi v raztopini, lahko pa se ga nekaj doda, rezultat česar je tekočina, ki ima specifično težo 1,285. Razredčena trdna snov iz posode se filtrira s filtrom 42. Trdne snovi natrijevega bikarbonata 48 se odvedejo v posodo 32 in tekočina 44 gre v nadaljnjo obdelavo z dodatno separacijo natrijevega bikarbonata, ki je vrnjen v posodo 32. Tekočina 44 se nato odvede v posodo 46 (slika 1A). Prostornino pretoka v tokokrogu s bikarbonata je mogoče nadzorovati z odparjevanjem očiščenega natrijevega sulfata v dovodeni snovi, da se proizvede trden natrijev sulfat, kar omogoči nasičenost tokokroga.io The liquid from filter 30 has a specific gravity of 1.25 and its contents include approximately 10.4% sodium sulfate, 17.1% ammonium sulfate, 8% sodium bicarbonate and excess ammonium bicarbonate to react with Glauber's salt (to be described in below). The liquid is reacted in vessel 36 at 40 ° C, the Glauber salt being formed in the cooling phase of the process discussed later to form sodium bicarbonate from excess ammonium bicarbonate in crystallization vessel 29. Alternatively, ammonium bicarbonate can be added to the second stage (container 36) in the form of a solid, a diluted solid or a solution. Solid sodium sulfate from source 41 is added to the liquid from vessel 36 in a container 40 to form a saturated sodium sulfate / ammonium sulfate solution. Sufficient ammonium bicarbonate may be present to complete the reaction in solution, but some may be added resulting in a liquid having a specific gravity of 1.285. The diluted solid from the vessel is filtered by filter 42. The sodium bicarbonate solids 48 are removed to the vessel 32 and the liquid 44 is further treated by additional separation of the sodium bicarbonate returned to the vessel 32. The liquid 44 is then discharged into the vessel 46 ( Figure 1A). The flow volume in the bicarbonate circuit can be controlled by evaporation of the purified sodium sulfate in the feed material to produce solid sodium sulfate to allow the saturation of the circuit.

Če se vrnemo na sliko 1A, posoda 46 vsebuje žveplovo kislino, s katero se obarja karbonatne spojine. Tako obdelane tekočine so ohlajene io na 0°C v ohlajevalniku 48, da se pridobi Glauberjeva sol, ter filtrirane v filtru 50. Pridobljeno Glauberjevo sol se vrne v posodo za kristalizacijo natrijevega bikarbonata 36.Returning to Figure 1A, container 46 contains sulfuric acid to precipitate carbonate compounds. The liquids thus treated were cooled to 0 ° C in cooler 48 to obtain the Glauber salt and filtered in filter 50. The resulting Glauber salt was returned to the sodium bicarbonate crystallization vessel 36.

Filtrat vsebuje 25,25% po teži amonijevega sulfata in do 11% po teži natrijevega sulfata ter se ga dovaja v posodo 52, ogreva na med 30°C in is 40°C ter združi s trdnimi snovmi 65 iz filtra 66. To raztopino se prenese v posodo 54, kjer se reagira trdni kalijev klorid, da se oblikuje 20% po teži raztopine amonijevega klorida, ki prav tako vsebuje približno 20,2% po teži amonijevega klorida, 6,7% po teži kalijevega klorida, 4,9% po teži natrijevega klorida, 2,3% po teži (x)2SO4, kjer je x = Na, K, in trdne mešane kristale kalijevega sulfata z 10% - 20% amonijevim sulfatom.The filtrate contains 25.25% by weight of ammonium sulphate and up to 11% by weight of sodium sulphate and is fed into a container 52, heated to between 30 ° C and 40 ° C and combined with solids 65 from filter 66. This solution is transferred to a container 54 where solid potassium chloride is reacted to form 20% by weight of ammonium chloride solution, which also contains about 20.2% by weight of ammonium chloride, 6.7% by weight of potassium chloride, 4.9% by weight of sodium chloride, 2.3% by weight of (x) 2 SO 4 , where x = Na, K, and solid mixed crystals of potassium sulfate with 10% - 20% ammonium sulfate.

Raztopina se filtrira na filtru 56, pri čemer trdna frakcija vsebuje po teži približno 5% kalijevega klorida, 80% - 85% kalijevega sulfata in 10% 15% amonijevega sulfata. Trdno frakcijo se v posodi 58 kombinira z vodo in slanico kalijevega klorida iz posode 60. Trdna snov kalijevega klorida se centrifugira in filtrira v filtru 62 ter rekristalizira z raztopino kalijevega klorida pri 25°C. Preostali amonijev sulfat se preoblikuje v kalijev sulfat. Mogoče je doseči več kot 98% stopnje kalijevega sulfata.The solution is filtered on filter 56, the solid fraction containing by weight about 5% potassium chloride, 80% - 85% potassium sulfate and 10% 15% ammonium sulfate. The solid fraction in vessel 58 is combined with potassium chloride water and brine from vessel 60. The potassium solid is centrifuged and filtered in filter 62 and recrystallized with potassium chloride solution at 25 ° C. The remaining ammonium sulfate is converted to potassium sulfate. More than 98% of the potassium sulfate level can be reached.

s V nadaljnjih enotah postopka se tekočina ali filtrat iz stopenj kalijevega sulfata in specifično s filtra 56 obdelajo v skladu z enotami postopka, ki so razvidne iz slike 1c. Tekočino se odpari v odparjevalniku, da se koncentrira tekočina amonijevega klorida, tako da se po ohlajanju v raztopini na minimum zmanjšajo kalijev klorid in preostali sulfati, io Raztopina se filtrira s filtrom 66, trdni material 67 pa se reciklira v posodo 54. Filtrat, ki vsebuje približno 22% do 30% amonijevega klorida, se reagira z apnom v reaktorju 68, pri čemer se sproščeni amoniak reciklira. Kalcijev klorid, ki se oblikuje, je mogoče dovajati v ustalilno posodo 70 ali v napravo za čiščenje 72, glede na to, kakšne so nameravane kasnejše is uporabe.s In further units of the process, the liquid or filtrate from the potassium sulfate stages and specifically from the filter 56 is treated according to the process units shown in Figure 1c. The liquid is evaporated off in a evaporator to concentrate the ammonium chloride liquid so that, after cooling in the solution, the potassium chloride and residual sulfates are minimized, io The solution is filtered with a filter 66 and the solid material 67 is recycled to the container 54. The filtrate which contains about 22% to 30% ammonium chloride, reacts with lime in reactor 68, with the released ammonia being recycled. The moldable calcium chloride can be fed into a stabilization vessel 70 or a scrubber 72, as intended for later use.

Ko je bil tako opisan postopek po tej prvi izvedbi izuma, bo sedaj opisan primer postopka.When the process of this first embodiment of the invention was thus described, an example of the process will now be described.

PRIMER 1EXAMPLE 1

NEVTRALIZACIJA BIKARBONATANEUTRALIZATION OF BICARBONATE

PRED POSTOPKOM KALIJEVEGA SULFATABEFORE THE POTASSIUM SULPHATE PROCEDURE

Začetne snovi - 1 liter pri 1,3 specifične teže 360 g/l Na2SO4 Initial Substances - 1 liter at 1.3 specific gravity 360 g / l Na 2 SO 4

1. fazaPhase 1

Proizvodnja NaHCO3 Production of NaHCO 3

Izhod slanice pri zaključku reakcije:Brine output at reaction completion:

130 g Na2SO4 10,4% Na2SO4 130 g Na 2 SO 4 10.4% Na 2 SO 4

213.8 g (NH4)2SO4 100 g NaHCO3 907 g H?O213.8 g (NH 4 ) 2 SO 4 100 g NaHCO 3 907 g H? O

1350.81350.8

40°C41 ° C

17,1 % (NH4)2SO4 1,250 spec. teže pri 0,95 I17.1% (NH 4 ) 2 SO 4 1,250 spec. weighted at 0.95 I

8,0% NaHCO3 raztopina8.0% NaHCO 3 solution

Na ta način je pridobljenih 172 g NaHCO3 v obliki trdne snoviIn this way 172 g of NaHCO 3 is obtained as a solid

Ocena druge stopnje poraba 55 g NH3 A) 25,07 g NH3 + 64,9 g CO2 Grade 2 consumption 55 g NH 3 A) 25.07 g NH 3 + 64.9 g CO 2

142,5 g CO2 B) 51,2 g NH3 + 132,6 g CO2 142.5 g CO 2 B) 51.2 g NH 3 + 132.6 g CO 2

Druga STOPNJA 0,95 I slanice bo raztopilo naslednje:Second LEVEL 0.95 I brine will dissolve the following:

-1010-1010

A) 1 mol A) 1 mol B) 2 mola B) 2 moles Na2SO410 H2OAt 2 SO 4 10 H 2 O Na2SO410 H2OAt 2 SO 4 10 H 2 O (332 g) (332 g) (644 g) (644 g) 272 g Na2SO4 272 g Na 2 SO 4 16,2% Na2SO4 16.2% Na 2 SO 4 414 g Na2SO4 414 g Na 2 SO 4 20,7% Na2SO4 20.7% Na 2 SO 4 213,8 g (NH4)2SO4 213.8 g of (NH 4) 2 SO 4 12,8% (NH4)2SO4 12.8% (NH 4 ) 2 SO 4 213,9 g (NH4)2SO4 213.9 g (NH 4 ) 2 SO 4 10,7% (NH4)2SO4 10.7% (NH 4 ) 2 SO 4 100 g NaHCO3 100 g NaHCO 3 5,9% NaHCO3 5.9% NaHCO 3 100 g NaHCO3 100 g NaHCO 3 5,0% NaHCO3 5.0% NaHCO 3 1087q H2O1087q H 2 O 65,1% H2O65.1% H 2 O 1267q H2O1267q H 2 O 63,4% H2O63.4% H 2 O 1672,8 1672,8 1999 1999 1,275 specifične teže in 1,313 I slanice 1 1,275 specific gravity and 1,313 I brine 1 1,300 specifične teže in 1,5 I slanice 1,300 specific gravity and 1.5 I brine

Druga STOPNJA Sestava končne raztopineSTAGE 2 Composition of the final solution

A) A) B) B) 167,3 g Na2SO4 167.3 g Na 2 SO 4 10% Na2SO4 10% On 2 SO 4 200 g Na2SO4 200 g Na 2 SO 4 10% Na2SO4 10% On 2 SO 4 311 g (NH4)2SO4 311 g (NH 4) 2 SO 4 18,9% (NH4)2SO4 18.9% (NH 4 ) 2 SO 4 412 g (NH4)2SO4 412 g (NH 4) 2 SO 4 20,2% (NH4)2SO4 20.2% (NH 4 ) 2 SO 4 131 g NaHCO3 131 g NaHCO 3 8% NaHCO3 8% NaHCO 3 160 g NaHCO3 160 g NaHCO 3 8% NaHCO3 8% NaHCO 3 1087 a H2O1087 a H 2 O 63,1% H2O63.1% H 2 O 1267 a h2o1267 ah 2 o 61,8% H2O61.8% H 2 O 1644,5 g raztopine 1644.5 g of solution 2039 g raztopine 2039 g of solution

-1111-1111

Proizvodnja NaHCO3 92,9 gProduction of NaHCO 3 92.9 g Proizvodnja 193,2 g NaHCO3 Production 193.2 g NaHCO 3 Specifična teža 1,265 in pridobi se Specific gravity 1,265 and is obtained 1,285 specifične teže in pridobi se 1,6 I 1,285 specific gravity and 1.6 I is obtained 1,31 I slanice 1.31 And brines slanice brine NEVTRALIZACIJA BIKARBONATOV NEUTRALIZATION OF BICARBONATES 412 g (NH4)2SO4 412 g (NH 4) 2 SO 4 200 g Na2SO4 +200 g Na 2 SO 4 + 160 x 98 = 93,3 g H2SO4 160 x 98 = 93.3 g H 2 SO 4 160gNaHCO3 160gNaHCO 3 84(2) 84 (2) 1267 g H?O 1267 g H? O

2039 g (1,61)2039 g (1.61)

1,285 specifične teže io To postane:1,285 specific gravity io It becomes:

412 g (NH4)2SO4 335 g Na2SO4 1267 g H?O412 g (NH 4 ) 2 SO 4 335 g Na2SO4 1267 g H? O

2014 g pri 1,265 = (1,61) is je potrebno dodati Na2SO4 za nasičenje 1,30 specifične teže 1,61 x 1,30 = 20802014 g at 1,265 = (1,61) and it is necessary to add Na 2 SO 4 to saturate 1,30 specific gravity 1,61 x 1,30 = 2080

Zato:Therefore:

412 g (NH4)2SO4 412 g (NH 4) 2 SO 4

2o 400 g Na2SO4 2o 400 g Na 2 SO 4

-1212-1212

1267 g Η?0 2079 g v celoti (1,61)1267 g 0? 0 2079 g total (1,61)

Ohlajevanje Cooling 412 g (NH4)2SO4 412 g (NH 4) 2 SO 4 28,7% 28.7% 116 g Na2SO4 116 g Na 2 SO 4 8,0% 8.0% 907 g H?O 1435 g raztopine907 g H ? About 1435 g of solution 63% 63% Začetne snovi Initial substances NH4CI NH4CI 330,8 g 330,8 g 21.9 21.9 KCI 130 g KCI 130 g 8,6% 8,6% NaCI NaCI 94,7 g 94.7 g 6,3% 6.3% x-SO4 x-SO4 50 50 3,3% 3.3% HgO HgO 907 g 1512 g 907 g 1512 g 60,0 60.0 pri 33% NH4CIat 33% NH 4 CI potem: - 2,8% KCI potem: -2,0% K2SO4 then: - 2.8% KCI then: -2.0% K 2 SO 4

Zato: 330,8 = 1002 g .33Therefore: 330.8 = 1002 g .33

-1313-1313

Evaporacijsko breme = 907 - 623 = 284 gEvaporation burden = 907 - 623 = 284 g

0,79 t/t Na2SO4 dodati 0,51 za spiranje0.79 t / t To 2 SO 4 add 0.51 to rinse

1,291 H2O /1 Na2SO4 1,291 H 2 O / 1 Na 2 SO 4

K2SO4 reakcijaK 2 SO 4 reaction

a) K2SO4 iz (NH4)2SO4 = 412 x 174 = 543 ga) K 2 SO 4 from (NH 4 ) 2 SO 4 = 412 x 174 = 543 g

132132

b) K2SO4 iz Na2SO4 = 116x174 = 142gb) K 2 SO 4 from Na 2 SO 4 = 116x174 = 142g

142142

c) izgube K2SO4 - -43 gc) losses of K 2 SO 4 - -43 g

SKUPAJ K2SO4 642 gTOTAL K 2 SO 4 642 g

Rekuperacija KCIRecovery of KCI

a) KCI začasno pretrgana reakcija = 685 x 2 x 74 = 582 ga) KCI Temporarily Broken Reaction = 685 x 2 x 74 = 582 g

174174

b) KCI, izgubljen zaradi omejitev = 50 gb) KCI lost due to restrictions = 50 g

c) zato: potreba po KCI = 623 gc) therefore: need for KCI = 623 g

Izkoristek K?SO4 = 642 x 100 = 93,7%Utilization K ? SO 4 = 642 x 100 = 93.7%

685685

-1414-1414

Učinkovitost konverzije KCI = 582 x 100 = 92,1 %KCI conversion rate = 582 x 100 = 92.1%

632632

TEMELJ: ena tona začetne snovi Na2SO4 FOUNDATION: One tonne of starting material Na 2 SO 4

Začetni materiali Starting materials Produkt Product Prva faza 0,1531 NH3 0,396 t CO3 2,52 t H2OPhase One 0.1531 NH 3 0.396 t CO 3 2.52 t H 2 O 0,481 NaHCOs 0.481 NaHCOs Druga faza 644 g Na2SO4 10 H2O 0,142 t NH3 0,368 t CO2 Second phase 644 g Na 2 SO 4 10 H 2 O 0,142 t NH 3 0,368 t CO 2 0,53 t NaHCOs 0.53 t NaHCOs Nevtralizacija bikarbonatov + Na2SO4 nasičenje 0,261H2SO4 0,18tNa2SO4 Bicarbonate neutralization + Na 2 SO 4 saturation 0,261H 2 SO 4 0,18tNa 2 SO 4 filtrirati, da se proizvede bistra slanica filtered to produce clear brine ohlajevalec na 0°C - BTUji cooler at 0 ° C - BTUji 1,8tNa2SO4 10 H2O1.8tNa 2 SO 4 10 H 2 O hladnejša slanica colder brine 1,14 t (NH4)2SO4 28,7% 0,32 t Na2SO4 8,0% 2.52 at H,O 63% 3,99 t skupno1.14 t (NH 4 ) 2 SO 4 28.7% 0.32 t At 2 SO 4 8.0% 2.52 at H, O 63% 3.99 t total KC1 = 1,76 t KC1 = 1.76 t 1,78tK2SO4 1.78tK 2 SO 4 odparitev do 33% NH4CIevaporation up to 33% NH 4 CI 0,92 t NH4CI slanica0.92 t NH 4 CI brine 1,29 t/t Na2SO4 1.29 t / t Na 2 SO 4 0,08 t KCI TRDNE SNOVI 0.08 t KCI SOLID SUBSTANCES

-1515-1515

0,051 K2SO4 1,73 t H?O 2,78 skupno0.051 K 2 SO 4 1.73 t H? O 2.78 total 0,28 t KCI 0,08 t K7SO4 0,36 t recikliranje 0.28 t KCI 0.08 t K7SO4 0.36 t recycling postopek z apnom pri 85% stran lime process at 85% away 0,29 t NH3 0.29 t NH 3 0,571 CaO 0,571 CaO Slanica: Brine: 0,955 CaCI2 0,08 t KCI 0,05 t K2SO4 1,73 t H2O 2,815 t pri 75 do 90 °C0.955 CaCI2 0.08 t KCI 0.05 t K 2 SO 4 1.73 t H 2 O 2.815 t at 75 to 90 ° C

Če se sedaj obrnemo k slikam od 2 do 2b, je na njih shematično prikazana alternativna shema postopanja. Po tej reakcijski shemi so tekočine nasičene z anhidritom pred proizvodnjo natrijevega bikarbonata.Turning now to Figures 2 to 2b, they schematically show an alternative flow chart. According to this reaction scheme, liquids are saturated with anhydrite prior to the production of sodium bicarbonate.

s V tej izvedbi je natrijev bikarbonat proizveden v kristalizacijski enoti 22 ter se splošno podvrže podobnim stopnjam, kot so navedene za slike od 1 do 1b. Slanica ali filtrat se v posodi 36 nasiči z brezvodnim natrijevim sulfatom in filtrira s filtrom 38, da se odstrani netopne snovi, ki se jih nato odvrže. Filtrat iz tega postopka se v posodi 80 reagira z amonijevim io bikarbonatom. Alternativno je mogoče filtrat reagirati z amoniakom ali ogljikovim dioksidom, da bi se precipitiral natrijev bikarbonat. Raztopino se filtrira s filtrom 82, natrijev bikarbonat pa ostane. Natrijev bikarbonat se združi z natrijevim bikarbonatom iz filtra 30 in se ju nato spere, centrifugira in osuši. Te stopnje niso prikazane.s In this embodiment, sodium bicarbonate is produced in crystallization unit 22 and generally undergoes similar steps as those shown in Figures 1 to 1b. The brine or filtrate is saturated with anhydrous sodium sulfate in vessel 36 and filtered with filter 38 to remove insoluble matter which is then disposed of. The filtrate from this process is reacted in vessel 80 with ammonium ioc bicarbonate. Alternatively, the filtrate can be reacted with ammonia or carbon dioxide to precipitate sodium bicarbonate. The solution was filtered with filter 82 and the sodium bicarbonate remained. The sodium bicarbonate is combined with the sodium bicarbonate from filter 30 and then washed, centrifuged and dried. These rates are not shown.

-1616-1616

Filtrat, ki ostane, ima naslednjo približno sestavo po teži: 10% natrijevega sulfata, 24% amonijevega sulfata in 8% natrijevega bikarbonata. Raztopina ima pri 40°C specifično težo 1,285.The residual filtrate has the following approximate composition by weight: 10% sodium sulfate, 24% ammonium sulfate and 8% sodium bicarbonate. The solution has a specific gravity of 1.285 at 40 ° C.

Iz te stopnje se raztopina filtrata ohladi v ohlajevalniku 84 na približno s 0°C, da se proizvede filtrat, ki vsebuje po teži približno 5% natrijevega sulfata, 28% amonijevega sulfata in 6% natrijevega bikarbonata. Raztopino se filtrira s filtrom 86, precipitirana natrijev bikarbonat in natrijev sulfat se reciklirata nazaj v posodo za kristalizacijo bikarbonata 32, medtem ko se filtrat v posodi 88 reagira s kalijevim kloridom, da se io sintetizira kalijev sulfat prve stopnje v obsegu čistosti od okrog 75% do 90%. Rezultat tega je visoko kakovosten kalijev sulfat, ki ima visoko oceno. Produkt se spere z vodo v konvencionalni stopnji spiranja 96, reciklat se odvaja v posodo 94.From this stage, the filtrate solution is cooled in cooler 84 to about 0 ° C to produce a filtrate containing by weight about 5% sodium sulfate, 28% ammonium sulfate and 6% sodium bicarbonate. The solution is filtered through filter 86, the precipitated sodium bicarbonate and sodium sulfate are recycled back to the bicarbonate crystallization vessel 32, while the filtrate in the vessel 88 is reacted with potassium chloride to io synthesize first grade potassium in a purity range of about 75% up to 90%. The result is high quality potassium sulphate which is highly rated. The product is washed with water at a conventional rinsing rate of 96, and the recyclate is discharged into a container 94.

Raztopino iz filtra 90 se evaporira v evaporatorju 98 (slika 2A), da se is koncentrira tekočina amonijevega klorida, pri čemer se po hlajenju minimizira kalijev klorid in sulfate. Raztopino se filtrira z uporabo filtra 100, pri čemer se precipitiran kalijev klorid in (x)SO4, pri katerem pomeni x = K, Na, reciklirata v posodo 88.The solution from filter 90 was evaporated in an evaporator 98 (Figure 2A) to concentrate the ammonium chloride liquid, minimizing potassium chloride and sulfates after cooling. The solution is filtered using a filter 100 whereby the precipitated potassium chloride and (x) SO 4 , at which x = K, Na, is recycled into the container 88.

Filtrat iz filtra 100, ki vsebuje amonijev klorid, kalijev klorid in kalijev 2o sulfat, se odvede v evaporator 102. Natrijev bikarbonat podpira reakcijo in posledično se sprostota amoniak in ogljikov dioksid. Ta plina se nato očistita/se z njima rokuje tako, da se uporabljajo primerne tehnike.The filtrate from filter 100 containing ammonium chloride, potassium chloride and potassium 2o sulfate is taken to evaporator 102. Sodium bicarbonate supports the reaction and consequently the ammonia and carbon dioxide are released. These gases are then cleaned / treated using appropriate techniques.

Kalcijev klorid, ki nastane, se nato odvrže ali proda.The resulting calcium chloride is then discarded or sold.

-1717-1717

PRIMER 2EXAMPLE 2

NI NEVTRALIZACIJE BIKARBONATANO BICARBONATE NEUTRALIZATION

Začetne snovi - 1 liter pri 1,3 specifične teže 360 g/l Na2SO4 Initial Substances - 1 liter at 1.3 specific gravity 360 g / l Na 2 SO 4

1. FAZAPHASE 1

Proizvodnja NaHCO3 Production of NaHCO 3

Izhod slanice pri zaključku reakcije:Brine output at reaction completion:

130 g Na2SO4 10,4% Na2SO4 40°C130 g Na 2 SO 4 10.4% Na 2 SO 4 40 ° C

213,8 g (NH4)2SO4 100 g NaHCO3 213.8 g (NH 4 ) 2 SO 4 100 g NaHCO 3

907 g H?O907 g H? O

17,1% (NH4)2SO4 17.1% (NH 4 ) 2 SO 4

1,250 spec. teže pri 0,95 I1,250 spec. weighted at 0.95 I

8,0% NaHCO3 raztopina8.0% NaHCO 3 solution

1350,81350,8

Na ta način je pridobljenih 172 g NaHCO3 v obliki trdne snovi porabi 55 g NH3 In this way, 172 g of NaHCO 3 are obtained as a solid, and 55 g of NH 3 are consumed

142,5 g CO2 so Resaturacija z Na2SO4: slanica bo prenesla 150 g Na2SO4. Ta slanica se nato filtrira in uvede v drugo stopnjo NaHCO3 kristalizatorja.142.5 g CO 2 are Na 2 SO 4 Resaturation: Brine will withstand 150 g Na 2 SO 4 . This brine is then filtered and introduced into the second stage NaHCO 3 crystallizer.

-1818-1818

ZAČETNA SNOV INITIAL SUBSTANCE REAKCIJA REACTION IZHODNA SLANICA OUTPUT SALT PRODUKT PRODUCT 280 g Na2SO4 280 g Na 2 SO 4 35,9 g NH3 35.9 g NH 3 130 g Na2SO4 130 g Na 2 SO 4 177 g NaHCO3 177 g NaHCO 3 213,8g (NH4)2SO4 213,8g (NH 4) 2 SO 4 92,9 g CO2 92.9 g CO 2 353 g (NH4)2SO4 353 g (NH 4 ) 2 SO 4 100 g NaHCO3 100 g NaHCO 3 100g NaHCO3 100g NaHCO 3 907 g H?O 907 g H? O 907 q H?O907 q H ? Oh 1490,8 g 1490,8 g 1490 g 1490 g 1,151 pri 1,32 1,151 at 1.32 1,285 specifične 1,285 specific specifične teže specific weights teže heavier 1,151 1,151 th most common 23,7% (NH4)2SO4 23.7% (NH 4 ) 2 SO 4

Izhodna slanica se nato ohladi na 0°C.The outlet brine was then cooled to 0 ° C.

Sestava slanice je: 5,0% Na2SO4, kar pomeni 60 g Na2SO4 precipitira kot 136 g Na2SO410 H2O, precipitirati in odstraniti 76 g H2O.The composition of the brine is: 5.0% Na 2 SO 4 , which means 60 g Na 2 SO 4 precipitate as 136 g Na 2 SO 4 10 H 2 O, precipitate and remove 76 g H 2 O.

Zato: 907 - 76 = 831 g H2O.Therefore: 907 - 76 = 831 g H 2 O.

Sestava slanice pri 0°C in specifični teži 1,26 70 g Na2SO4 353 g (NH4)2SO4 100 g NaHCO3 831 g H?OBrine composition at 0 ° C and specific gravity 1.26 70 g Na 2 SO 4 353 g (NH 4 ) 2 SO 4 100 g NaHCO 3 831 g H? O

SKUPAJ 1354 gTOTAL 1354 g

-1919-1919

Okrog 1 litra slanice.About 1 liter of brine.

K2SO4K2SO4

a) 70 g Na?SO4 x 174 = 85.8a) 70 g Na? SO 4 x 174 = 85.8

142142

b) 353 g (NH4)2SO4 x 174 = 465,3 gb) 353 g (NH 4 ) 2 SO 4 x 174 = 465.3 g

132132

IZHODNA SLANICA:OUTPUT SALT:

283 g NH4CI283 g NH 4 CI 21,9% 21.9% 57 g NaCI 57 g NaCl 4,8% 4,8% 119 g (KNaHCO3)119 g (KNaHCO 3 ) 9,2% 9.2% 831 g H2O831 g H 2 O 1290 1290

Segrevati do 33,0% g NH4CI.Heat to 33.0% g of NH 4 CI.

Izpust NH3 in CO2 iz evaporatorja, vendar NH4CI izsoli KCI, ne pa NaCI. 15 KCI se rekuperira na enak način, kot je opisan v primeru 1.Releasing NH 3 and CO 2 from the evaporator but NH 4 CI solutes KCI but not NaCI. 15 The KCI is recovered in the same manner as described in Example 1.

TEMELJ: ena tona začetne snovi Na?SO4 FUNDAMENTAL: One tonne of starting material Na? SO 4

-2020-2020

Začetni materiali Starting materials Produkt Product Prva faza 0,15 tNH3 First phase 0.15 tNH 3 0,48 t NaHCO3 0.48 t NaHCO 3 0,396 t CO2 0.396 t CO 2 2,52 t H2O2.52 t H 2 O Druga faza 0,10 t NH3 Second phase 0.10 t NH 3 0,49 t NaHCO3 0.49 t NaHCO 3 0,26 t CO3 0.26 t CO 3 0,42 t Na2SO4 0.42 t Na 2 SO 4 ohlajeno na 0°C cooled to 0 ° C 0,4 t Na2SO4 10 H2O0.4 t Na 2 SO 4 10 H 2 O hladnejša slanica colder brine 0,19tNa2SO4 5% 0,98 t (NH4)2SO4 26% 0,28 t NaHCO3 7,4% 2,31 t H?O 61,4% 3,76 t skupno0.19tNa 2 SO 4 5% 0.98 t (NH 4 ) 2 SO 4 26% 0.28 t NaHCO 3 7.4% 2.31 t H? O 61.4% 3.76 t total KCI = 1,62 t KCI = 1.62 t 1,8tK2SO4 1.8tK 2 SO 4 odparitev do 33% NH4CIevaporation up to 33% NH 4 CI slanica trdne snovi solids brine kontrola krogotoka = 0,71 H2Ocircuit control = 0.71 H 2 O 0,98 t NH4CI 0,28 t KCI0.98 t NH 4 CI 0.28 t KCI spiranje = 0,5 t rinsing = 0.5 t 0,08 t KCI 0,08 t K2SO4 0.08 t KCI 0.08 t K 2 SO 4 v evaporator 1,2 t H2O /1 Na2SO4 v evaporator 1.2 t H 2 O / 1 Na 2 SO 4 0,15 t NaCI 0,36 t 0,19 t NaCI iz CO3 1,57 t H2O 2,97 t0.15 t NaCI 0.36 t 0.19 t NaCl from CO 3 1.57 t H 2 O 2.97 t postopek z apnom pri 85% lime process at 85% 1,01 t CaCI2 1.01 t CaCI 2 učinkovitosti efficiency 0,08 t KCI 0.08 t KCI

-2121-2121

0,61 tCaO 0.61 tCaO 0,34 t NaCI 1,57 t H2O 3,01 pri 75 do 90 °C0.34 t NaCl 1.57 t H 2 O 3.01 at 75 to 90 ° C

PRIMER 3 - NEVTRALIZACIJA BIKARBONATA - NI EVAPORACIJEEXAMPLE 3 - NEUTRALIZATION OF BICARBONATE - NO EVAPORATION

AMONIJEVEGA KLORIDAAMMONIUM CHLORIDE

5 Izpuščena raztopina: iz # 1 5 Solution omitted: from # 1 412 g (NH4)2SO4 335 g Na2SO4 1267 o H?O 2014 g pri 1,265 = 1,60 I412 g (NH 4 ) 2 SO 4 335 g Na 2 SO 4 1267 o H? O 2014 g at 1,265 = 1.60 I

Z ohlajevanjem na 0°C pridobimo filtrirano raztopino:Cooling to 0 ° C gives a filtered solution:

412 g (NH4)2SO4 412 g (NH 4) 2 SO 4 28,7% 28.7% 116 g Na2SO4 116 g Na 2 SO 4 8,0% 8.0% 907 g H2O907 g H 2 O 1435 g raztopine 1435 g of solution

To slanico se nato ogreje na 25°C, pri čemer se doda trdna snov KCI, da se proizvede K2SO4. Izhodna slanica iz K2SO4 tokokroga ima naslednjo sestavo:This brine was then heated to 25 ° C, with KCI solids added to produce K 2 SO 4 . The output brine from the K 2 SO 4 circuit has the following composition:

NH4CI 330,8 g NH4CI 330.8 g 21.9% 21.9% 20 KCI 130 g 20 KCI 130 g 8,6% 8,6%

-2222-2222

NaCI NaCI 94,7 g 94.7 g 6,3% 6.3% x-SO4 x-SO 4 50 g 50 g 3,3% 3.3% x = Na/K x = Na / K h?q h? q 907 o 907 о 60 60

1512 g1512 g

To slanico se nato ogreje in reagira z apnom, da se rekuperira amoniak in se izogne evaporatorju. KCI privlači CaCI2 slanica, namesto da bi bil rekuperiran v evaporatorju. To predstavlja 15 do 20% izgubo K na CaCI2 slanici. KCI in CaCI2 slanica se lahko reducirata do tako nizke količine kot io je 1,0%, tako da se CaCI2/KCI slanici doda trdni Na2SO4. Kalij se učinkovito zbira kot aprecipitat singenita (CaSO4 · K2SO4 · x H2O) pri 0 do 100°C, pri čemer so prednostne temperature od 20 do 30°C, tako da je ohranjana minimalna topnost SO4 in se reakcija odvija z razumno hitrostjo.This brine is then heated and reacted with lime to recover the ammonia and avoid the evaporator. The KCI attracts CaCI 2 brine instead of being recovered in the evaporator. This represents a 15 to 20% loss of K on CaCI 2 brine. KCI and CaCI 2 brine can be reduced to as low as 1.0% by adding CaCI 2 / KCI brine to solid Na 2 SO 4 . Potassium is efficiently collected as a syngenite precipitate (CaSO 4 · K 2 SO 4 · x H 2 O) at 0 to 100 ° C, with temperatures of 20 to 30 ° C being preferred so that the minimum solubility of SO 4 is maintained and the reaction proceeds at a reasonable rate.

is Sestava CaCI2 is CaCI 2 Composition

343,3 g CaCI2 343.3 g of CaCl2 22,5% 22,5% 130 g KCI 130 g KCI 8,5% 8.5% 94,7 g NaCI 94.7 g NaCl 6,3% 6.3% 50 g x SO4 50 gx SO 4 32.% (Na/K) 32.% (Na / K) 907 a H2O907 a H 2 O 59,5% 59.5% 1525 g 1525 g 100% 100%

-2323-2323

140 g Na2SO4 dodatka: izhodna slanica izhodna pogača140 g Per 2 SO 4 additives: outlet brine outlet cake

234,8 g CaCI2 234.8 g CaCI 2 17,8% 17.8% 15,25 g KCI 15.25 g KCI 1,1% 1.1% 31 Og CaSO4»K2SO.31 Og CaSO 4 »K 2 SO. 209 g NaCI 209 g NaCl 15,9% 15.9% + 100 g H2O+ 100 g H 2 O 50 g x SO4 50 gx SO 4 3,8% 3.8% 807 807 61,3% 61.3%

Izhodno slanico je mogoče odlagati v globokin vrtinah, izhodno pogačo pa je mogoče kot vezivni material vmešati v K2SO4 produkt ali pa jo nadalje predelati, da se odstrani CaSO4.The outlet brine can be deposited in deep wells and the outlet cake can be mixed into the K 2 SO 4 product as a binder or further processed to remove CaSO 4 .

Pogačo je mogoče reagirati z (NH4)2HCO3 iz začetne snovi postopkaThe cake can be reacted with (NH 4 ) 2 HCO 3 from the starting material of the process

NaHCO3, CaSO4 pa hitro reagira, da se proizvede slanica (NH4)2SO4 in K2SO4 ter filter CaCI3 precipitat, ki se ga odstrani. (NHa)2SO4/K2SO4 slanica se reciklira v K2SO4 kristalizator prve stopnje.NaHCO 3 and CaSO 4 reacted rapidly to produce brine (NH 4 ) 2 SO 4 and K 2 SO 4 and a CaCI 3 precipitate to be removed. (NHa) 2 SO 4 / K 2 SO 4 brine is recycled to a K 2 SO 4 crystallizer of the first stage.

Claims (15)

PATENTNI ZAHTEVKIPATENT APPLICATIONS 1. Metoda za oblikovanje natrijevega bikarbonata, ki je zadosti kakovosten za prehrano, ter kalijevega sulfata, s označena s tem, da ta metoda obsega naslednje stopnje:1. A method for forming sodium bicarbonate of sufficient nutritional quality and potassium sulphate, characterized in that this method comprises the following steps: a) pridobitev vira tekočega natrijevega sulfata;a) obtaining a source of liquid sodium sulfate; b) pridobitev vira amonijevega bikarbonata, da se precipitira natrijev bikarbonat;b) obtaining a source of ammonium bicarbonate to precipitate sodium bicarbonate; io c) spravljanje navedenega natrijevega sulfata in navedenega amonijevega bikarbonata v stik;io c) contacting said sodium sulfate and said ammonium bicarbonate; d) precipitiranje natrijevega bikarbonata in formiranje tekočine;d) precipitation of sodium bicarbonate and formation of liquid; e) filtriranje navedenega natrijevega bikarbonata;e) filtering said sodium bicarbonate; f) nasičenje tekočine iz stopnje e) z natrijevim sulfatom;f) saturation of the liquid from step e) with sodium sulfate; is g) spravljanje navedene tekočine v stik z amonijevim karbonatom, amonijevim plinom ali ogljikovim dioksidom, da se precipitira nadaljnji natrijev bikarbonat;g) contacting said liquid with ammonium carbonate, ammonium gas or carbon dioxide to precipitate further sodium bicarbonate; h) filtriranje precipitiranega natrijevega bikarbonata iz stopnje g);h) filtering the precipitated sodium bicarbonate from step g); i) kombiniranje precipitatov natrijevega bikarbonata iz stopenj e) in h)i) Combining sodium bicarbonate precipitates from steps e) and h) 2o in spiranje, da se ustvari natrijev bikarbonat, ki je zadosti kakovosten za prehrano;2o and rinsing to produce sodium bicarbonate of sufficient quality for consumption; j) ohlajevanje tekočine iz stopnje i) na 0°C, da nastane vsaj precipitat Glauberjeve soli;j) cooling the liquid from step i) to 0 ° C to form at least a Glauber salt precipitate; -2525-2525 k) obdelovanje tekočine iz stopnje j) z žveplovo kislino, da se karbonatni minerali konvertirajo v sulfatne minerale ter sprostijo plin ogljikov dioksid;k) treating the liquid from step j) with sulfuric acid to convert the carbonate minerals to sulfate minerals and to release carbon dioxide gas; l) ogrevanje tekočine iz stopnje k) na med 30°C in 40°C; inl) heating the fluid from step k) to between 30 ° C and 40 ° C; and 5 m) precipitiranje kalijevega sulfata s kontaktiranjem navedene tekočine iz stopnje I) s kalijevim kloridom.5 m) precipitation of potassium sulphate by contacting said liquid from step I) with potassium chloride. 2. Metoda po zahtevku 1, označena s tem, io da metoda nadalje obsega stopnjo separiranja precipitiranega kalijevega sulfata in spiranja s kalijevim kloridom.2. The method of claim 1, wherein the method further comprises a step of separating the precipitated potassium sulfate and washing with potassium chloride. 3. Metoda po zahtevku 2, označena s tem, u da metoda nadalje obsega stopnjo obdelave tekočine iz navedene stopnje separiranja precipitiranega kalijevega sulfata z apnom, da se sprosti amonijev plin.Method according to claim 2, characterized in that the method further comprises the step of treating the liquid from said separation step of the precipitated potassium sulphate with lime to release ammonium gas. 4. Metoda po zahtevku 3,4. The method of claim 3, 2o označena s tem, da metoda nadalje obsega stopnjo recikliranja navedenega amonijevega plina v stopnjo g).2o, characterized in that the method further comprises the step of recycling said ammonium gas into step g). -2626-2626 5. Metoda po zahtevku 4, označena s tem, da metoda nadalje obsega stopnjo evaporiranja filtrata iz zahtevka 4.5. The method of claim 4, wherein the method further comprises the evaporation step of the filtrate of claim 4. ss 6. Metoda po zahtevku 1, označena s tem, da ima navedeni natrijev sulfat specifično težo pri 40°C med 1,30 in 1,34.Method according to claim 1, characterized in that said sodium sulfate has a specific gravity at 40 ° C of between 1.30 and 1.34. ioio 7. Metoda po zahtevku 1, označena s tem, da ima navedena tekočina iz stopnje d) specifično težo 1,25 in po teži vsebuje 10,4% natrijevega sulfata, 17,1% amonijevega sulfata, med 8% in 12% natrijevega bikarbonata in v presežku amonijevega bikarbonata.Method according to claim 1, characterized in that said liquid from step d) has a specific gravity of 1.25 and contains by weight 10.4% sodium sulfate, 17.1% ammonium sulfate, between 8% and 12% sodium bicarbonate and in excess of ammonium bicarbonate. 8. Metoda po zahtevku 1, označena s tem, da navedeni natrijev sulfat iz stopnje e) vsebuje Na2SO4 · 10 H2O.A method according to claim 1, characterized in that said sodium sulfate from step e) contains Na 2 SO 4 · 10 H 2 O. 2020 9. Metoda po zahtevku 1, označena s tem, da ima navedena tekočina iz stopnje f) specifično težo pri 40°C 1,285.Method according to claim 1, characterized in that said fluid of step f) has a specific gravity at 40 ° C of 1.285. -2727-2727 10. Metoda po zahtevku 1, označena s tem, da je navedena tekočina iz stopnje k) nasičena tekočina natrijevega sulfata, amonijevega sulfata in natrijevega bikarbonata.10. The method of claim 1, wherein said fluid from step k) is a saturated liquid of sodium sulfate, ammonium sulfate and sodium bicarbonate. 11. Metoda po zahtevku 1, označena s tem, da se navedeni kalijev sulfat pridobi z izkoristkom najmanj 80%, s čistočo najmanj 98%.A method according to claim 1, characterized in that said potassium sulfate is obtained in a yield of at least 80%, with a purity of at least 98%. 12. Metoda za oblikovanje natrijevega bikarbonata, ki je zadosti kakovosten za prehrano, ter kalijevega sulfata, označena s tem, da ta metoda obsega naslednje stopnje:12. A method for forming sodium bicarbonate of sufficient nutritional quality and potassium sulphate, characterized in that this method comprises the following steps: a) pridobitev vira tekočega natrijevega sulfata;a) obtaining a source of liquid sodium sulfate; b) pridobitev vira amonijevega bikarbonata;b) obtaining a source of ammonium bicarbonate; c) spravljanje navedenega natrijevega sulfata in navedenega amonijevega bikarbonata v stik;c) contacting said sodium sulfate and said ammonium bicarbonate; d) precipitiranje natrijevega bikarbonata in formiranje tekočine;d) precipitation of sodium bicarbonate and formation of liquid; e) precipitiranje natrijevega bikarbonata in formiranje tekočine s spravljanjem v stik tekočine iz stopnje d) z natrijevim sulfatom;e) precipitating the sodium bicarbonate and forming the liquid by contacting the liquid from step d) with sodium sulfate; f) nasičenje navedene tekočine iz stopnje d) z natrijevim sulfatom;f) saturation of said liquid from step d) with sodium sulfate; g) filtriranje trdnih snovi iz navedene tekočine iz stopnje e);g) filtering solids from said fluid from step e); -2828-2828 h) spravljanje navedene tekočine iz stopnje f) v stik s žveplovo kislino, da se precipitira karbonate;h) contacting said liquid from step f) with sulfuric acid to precipitate carbonates; i) ohlajevanje navedene tekočine iz stopnje h) na 0°C, da nastane precipitat Glauberjeve soli;i) cooling said liquid from step h) to 0 ° C to form a Glauber salt precipitate; s j) ogrevanje navedene tekočine iz stopnje I) na med 30°C in 40°C; ins j) heating said liquid from step I) to between 30 ° C and 40 ° C; and k) obdelava navedene tekočine iz stopnje j) s kalijevim kloridom, da se precipitira kalijev sulfat;k) treating said liquid from step j) with potassium chloride to precipitate potassium sulfate; l) odparjevanje tekočine iz stopnje k), da se rekuperira kalij v vrednostih za recikliranje v stopnjo k); inl) evaporating the liquid from step k) to recover the potassium in the recycling values to step k); and 10 m) sušenje navedenega kalijevega sulfata.10 m) drying said potassium sulfate. 13. Metoda po zahtevku 12, označena s tem, da metoda nadalje obsega stopnjo obdelave tekočine, ki ostane iz is stopnje I), z apnom in amonijevim kloridom.Method according to claim 12, characterized in that the method further comprises the step of treating the liquid remaining from is step I) with lime and ammonium chloride. 14. Metoda po zahtevku 13, označena s tem, da se amonijev plin sprosti in reciklira.14. The method of claim 13, wherein the ammonium gas is released and recycled. 15. Metoda po zahtevku 12, označena s tem,15. The method of claim 12, wherein -2929 da se uporabljena raztopina kalijevega klorida reciklira v stopnjo k).-2929 that the potassium chloride solution used is recycled to step k).
SI9920082A 1998-10-13 1999-09-30 Method of formulating alkali metal salts SI20636A (en)

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