DE1592035A1 - Process for the production of potassium sulphate - Google Patents

Description

Dr. Walter Beil

Alfred Hoeppener _f8

Dr.HansJo2d; iinW (iff J «· May 1967

Dr. H «ms Chr. Beil

Recruitment. Frankfurt a. M. -Highly

Our No. 13 788

Sincat SocietS Industriale Catanese S * p * A
Palermo / Italy

Process for the production of potassium sulphate

The present invention relates to a method of extraction of potassium sulfate in particular from raw kainite ore as a starting material, . Ί

It is known that the crude kainite ore always contains considerable amounts of sodium chloride; the content of the ore is generally in the range of 20 to 40%, so that the potassium sulphate and the others, besides kainite, are avoided profit j cash salts contaminated by Hatriumsalze wtrden _f ea is necessary to grösöten rope in the kainite containing iiatrlumehlorids before or during treatment to desstlben entfern0n #

3) The most widespread method for this iZweelc consists in the Kainitejpz of a flotation zn «ntsrwtrf« », namely

suitable Samraleragenaien, wofeti the biggest sellers of the! © .trlamehlerids in the Flotatioiigaiüöketlindtn Virbebt »Bas üur & h flotation cu3gev * lQh * ¥ iNi Kminiii tnthllt generally no eh © tv / a 5

_B ADO _RI G.NAL ΟβΙβ * | /

This Vorfiotationeververfahren is very expensive, -was- however "up to now unavoidable, as there are no other equivalent technical processes known for separating the sodium chloride, were »- ''; - ·" ■ - ■■. ■ V- ■ .....

In the Italian patent specification No. 672 661 "a! /" Is described for the production of potassium and magnesium salts using kainite as starting material. According to this process, the kainite is ^{leached at temperatures above 90 °} C. with a brine, the composition of which is used for -The later Langbeinitbildung is favorable, which is cooled in the presence of its mother liquor to a temperature below 40 ⁰ G, depending on the final magnesium chloride concentration of the brine as well as the saturation conditions for potassium chloride and magnesium sulfate, one gets by this cooling 1 «Schoenit (or Leonit) and Potassium chloride or "2, Schoenit (or Iieonit and MgSO..7H ₂ O or 3Y potassium chloride and MgSO ^, 6HgO and / or MgSO .., 7H ₂ O,

This process achieves the best yields of potassium, since the salt mixtures obtained before the cooling process were in equilibrium with their brines and have a low potassium content, which is attributable to the high MgClp content of these brines, which also has the important consequence that the solubility the NAOL in the sols is severely limited "the amount of sodium chloride, which can be removed from the process circulatory system through the drained brine, istfe therefore very begrenalP, ⁰ that therefore in the process cycle system with the Kainit introduced Nagl * quantity is very limited · Otherwise the potassium and magnesium alloys would be contaminated with sodium salts. In practice, the kainite may not contain more than 2.5 $ sodium chloride if the kainite to KO1 and MgSQ ^ * 6HgO and / or MgSO ^ ,, 7HgO is converted, while the same kainite ^{may not contain more than 5 $ iia- 1} trium chloride if iian gbeinit is converted to Sohoenite and KOl or Sohoenite and MgSO ^ 7HgO.

This therefore has the consequence that the Vorflotatio »on its own does not represent a sufficient improvement and does not belong to the

original

Italian patent inscription No. 672 661 described kainitbehäiiaiüngsverfahren leads mentioned high potassium yields, if conversion of langbeinite in KOl and MgSO, .6UgG and / or ₄ ^ H ₂ O is to be achieved. In contrast to this, if, according to this patent, langbeinite is to be converted into Schoenit and KGl or Epeomit, the greatest possible improvement in kainite that can be achieved by flotation corresponds exactly to the process requirements that prescribe very careful flotation.

The same patent describes an alternative to the previous flotation process for kainite: the langbeinite obtained by hot leaching of raw kainite can be converted into a mixture of KCl, NaOl and MgSO in a cold process. _β 6H ₀ O and / or MgSO..7H ₀ O are converted. The magnesium

4 ^ t '£ ■ Classification

Sulphate can be separated from the chlorides by sieving or 6 * wm », while the potassium chloride is separated from the sodium chloride by flotation. This latter process gives potassium chloride with a content of less than 5% NaOl, which is carried out in the circuit Flotation is, however, rather expensive because of the large amount of sodium chloride, the weight ratio between K01 and NaOl is generally about 0.5.In order to avoid the contamination of magnesium sulphate due to the presence of NaCl, it is also necessary that the ore be ground to any degree of fineness is' which is higher than that which was _r which ground in a form suitable for the leaching process, in one hot leaching lent required is. the sodium chloride, which is present in the Kainiterz contains a not to be underestimated percentage of relatively large crystals * Since there is practically no modification While the re'i 'is subject to different process stages, the larger''■■ crystals are found in the magnesium sulphate »It is therefore necessary | to make the grinding of the ore more effective, so that the grain grip of the sodium chloride is reduced. This requires a more expensive milling process, ^

consists in obtaining potassium sulfate and dissolving oil from kainite as a starting material to use a process that ensures a very high potassium yield, 009842/1428

• '■' BAD ORIGINAL

Another object of the present invention is to extract potassium sulfate from kainite alone, without the use of any external source of potassium chloride. ^; ■ '

Another object of the present invention is the recovery * of potassium sulfate using yoix crude.m kainite as a starting material *! P | me au ^ f, df, s straightening the ore. procedure to fall back

the gr

out of the cycle during continuous operation remove·

These and other goals are met by the method of the present Invention achieved. According to this method, it is possible to obtain potassium sulfate using raw kainite as a starting material through the following procedural stages.

1) The ground raw material is leached at over .90 ⁰ C with recycling of the epsomite brine obtained in stage 3; a longbeinite dispersion is therefore obtained which consists of a solid phase containing langbeinite and sodium chloride and a longbeinite brine ».

2) The angbeinite dispersion becomes t, whereby the largest Part of the sodium chloride is separated from the dispersion. \ - «, classified ^

3) The first »« »Langbeinitdieperaion is in ■. The presence of a: Sohoenitsole from step 7, * uf silent temperature cooled from 35 to 20-Q, wherein a ftite Phait is obtained which au "a mixture of glycol, hoof It, MgSQ ^ eH ₂ O and / or KGSO, ^ 7HgO and an Epomiteole consists * :! ■ ^; · _; .

4) The Magnasiumeujfat wirdvon din Qhloridwi thereby separated that one or eiohttt it eitbt while JBpeoai dit ^ eole teilwei * out it tu stage 6 and teilwtiee ru Scales'"ΐ Burückgtführt

..ι η π

ii

is · The magnesium sulfate is ttiiwtiasst tu grade 6 ^ t leads and Partly from the Kreliliufiyittm "tn-tftrat.

009842/142 bad original

5) The potassium chloride is separated from the NaOl by flotation.

6) The second part of Langbeinitdispersion is subjected at a temperature above 80 ⁰ C to a treatment with a portion of the Epsomitsole obtained in stage 4, as well as with a portion of Magnesiumaulfate obtained in stage. 4 A reaction takes place between the brine and the magnesium sulphate, the potassium still present in the brine being partially recovered and the potassium precipitating in the form of metastable langbeinite, while the sodium chloride present in the introduced langbeinite dissolves. A solid phase consisting of Langbeinite is then obtained, which is fed to stage 7, and a metastable Langbeinite brine which is withdrawn.

7) The langbeinite obtained in stage 6 is treated between 20 and 40 ⁰ O with the sulfate brine obtained in stage 8, a solid phase consisting of schoenite (or leonite) and potassium chloride and a schoenite brine which is returned to stage 3 being obtained Will. ,:; ■ ,, '

8) The Schoenit obtained in step 7 and potassium chloride are mixed with the potassium chloride obtained in step 5 in the presence of Reacted water, resulting in potassium sulfate and a sulfate brine, which is returned to stage 7

In the present invention, a very high yield of potassium sulfate is obtained, based on the ratio of the circulatory system in the form of K ₂ SO. verlassendem and ■ the circulatory system in the form of kainite zugeführtea kgO from dea ■ If zwisohen generally yields 87 and 90 # erreohnen * This yield is significantly higher than the known in the »Eisten process for producing potassium sulfate under Veywen- '■ dung of kainite is required undjiwar both multi-stage conversion-up method, as well as the simple and subsequent double decomposition of kainite in Sohoenit and enschlitflaender U ^ wa ^ dlung dee Soboenit in KjSO ,, in which no 'supply of KCI from another source as a starting material,% t $ Ve0 im. Generally, a yield of about potassium 6OJt which "us the ratio between on the Kreislaufeyete" in ϊοηο of

0QM42 / 1V

and the EpO entering in the form of kainite is calculated. By single and double conversion of jfiainit to Schoeiit "anschiiessender double _r conversion between schonite and introduced into the circulatory system of KCI's results" I have a potassium yield, which is generally between 70 and 75 $. _{and sit3h is calculated from the ratio between the K 2} O leaving the circulatory system in the form of KgSO ^ and the K 2 O entering the circulatory system as Kainite and KCl,

According to the present invention it has been found that an optimal yield of KgSO. using only Kairiit obtained as a starting material, if you look at the individual process steps especially combined. The duroh the hot process Langbeinite dispersion obtained is first divided into two parts · The first part is the conversion to KCl and epsomite (or MgSOj.6HgO) subjected to the second of the to Schoenit and KCl.

The KCl obtained from the first part is worked out by double conversion with the Schoenit and KCl obtained in the second part to obtain K ₂ ^S0 4 ▼. The part of the epsomiteole to be drained has a very low potassium content; it can also serve for the extraction of the potassium therein · Of the three Sole types dee in a cold process duroh conversion obtained in a hot process Langbeinits obtained werden'können (ie mother liquors from the conversion to Sfchoenit and KOL, mother liquors from the conversion tu Sohoenit and MgSO. * 7HgO and mother liquors from the conversion to KCl and MgSO. · 6Η ₂ and / «of MgSO ^ .7HgO) the third type, the epsomiteolt, has the highest MgOlg- ^G « and therefore the lowest potassium content. Discarding this SoIt su is therefore very advantageous with regard to the potassium yield. The brines, which are in equilibrium with a solid phase consisting of KOl and MgSO ^ 6HgO and / or MgSO..7HgO, have a magnetic

| ^ | 52 toi »65 Mtl per 1,000 mol of water), the

SiOhUiOh hönssjifi ¹ · * ls, dtr ohiitWn sohon height · 8thalt (from 45 to 52 moles per 1,000 moles of f | Siiir) 4 · «Soltn, di · look with a fisttn phis · from Sohotnite and KCl sd« r Sohotnite and MgSO ^ * 7H ₂ O is oltiehgiiiiolit btiindtn,. >. _BAD original

H ' -Jji «; · ■' ·. ■ '■ "

The disposal of the part of the Epsomite brine that is to be discarded is carried out after a process which is the goal of the "Italian talent". is · Following this procedure. _{; wiril.} d € f rgröfste part of the mother liquors and the sols of committees ... ^ enthaj |; frenen KCl obtained in that these sols ... in eiaer- E-einperatur of at least 60 C., with! anhydrous,, MgSO ₄ , MgSO ,, 6H ₂ O or MgSO., 7H ₂ O is converted. The greater part of that contained in the brine is found in this pedanting. Potassium in the form of metastable kainite when working at 60 to 80 /, but as metastable iiangbeinite when working above 80 ^ 0. ; : ·

According to the present invention it was found that this Geivinnungsverfahren for the partial precipitation of potassium in, form of metas1ä) ilem Iiangbeinit is advantageous for the following reasons *

'■ "■ ·" Cliias
1 · The Iiangbeinit obtained in the hot e disperse ion has a temperature above 9O ⁰ C temperature you "has thus already 'part of the heat necessary for the implementation of the recovery Ever driving, therefore, the necessary for the process heat demand is equivalent to only those calories for heating of the epsomite and the epsomite brine and to carry out the endothermic conversion are required

2 · In stage 4 of the process cycle, the MgSOa hexahydrate and heptahydrate required for the process are obtained.

τ * *

3 # The metastable langbeinite thus obtained vertinigt with the first in the Stuf · I obtained "angbeinit and can 'it with the same at this stage" for conversion, "u - ■ schonite and KOL are processed ·

The Langbeinite obtained by leaching Käinit is divided, namely for the conversion process eu KOl and Efteomit and the conversion process to Sohoenite and KCl It should also be taken into account that, during the potassium recovery step, Lfengbeinite is obtained in sufficient quantity to the total for the · ν £ β? 4β «3: 4: β1% οη double conversion required To secure quantities of Schoenit and KOl «

009842/1428 _ßAD original

From the following description it appears that the method for the extraction of potassium as another characteristic of the present invention a fundamental importance for the removal of sodium chloride.

The sodium chloride is made according to the present invention.

which is removed from the circulatory system in three procedural stagesϊ by «fcae

Classification
hot of the entire Langbeinite dispersion, the successive washing of a part of the Langbeinite dispersion and the flotation of the KCl which is obtained in the processing of the other part of the Langbeinite dispersion.

It was found that the one obtained in the hot leaching process Jjangbeinite is obtained in the form of small crystals, which can easily be obtained by simply sieving most of the sodium chloride yb can be. In this way it is possible to use the in to remove the sodium chloride present in the Langbeinite dispersion at a cost of $ 70 to $ 80 »

Only small crystals of sodium chloride remain in the Langbeinite dispersion .

They are therefore in the ^above emic of Kol and MgSO..6HgO and

MgSO ^ .7HgO, obtained by processing © ines Tjails of Langbeiiiit *

dispersion, found again. During the cold or reach

Seven drifts - these crystals together with the potassium chloride

, down and a little & narrow magnesium sulphate * through the sieve * A subsequent flotation process enables »easy separation of the potassium chloride from the residual sodium chloride and magnesium sulphate, which are removed from the circulatory system.

The part of the LangteeiRite dispersion intended for the conversion of sohoenite is in turn purified in a different way. It has been found that the spsomiteols supplied to the potassium production step are subject to an advantageous conversion during this step, thanks to the poor dissolving power of the hexa- or heptahydrate of the i-WpaesIupiaulfat and eier precipitation of Iian ^ beinit is changed iliie <5uBH3miiGnsöt2üng and experiences a beuierkeru ^: n '«iM ^ p Löauii ^ iiverniöyeii ^ t \": eniiber KatriumohJ.orid. Oank ei.ner ά ^ v ^ vx i, -ch Ju -iß-liohkt * .it £ j {jtoii-: oi.'Uij _t ; iat OB- possible that still U \ fi ^ ü J. \ ^ ',;\>. · .: ^ ϊ \

009842/1428 bad original

· to solve existing sodium chloride The latter ^'x eil of the sodium chloride is therefore characterized removed from the circulatory system that subtracting the metastable Langbelnitsole.

The hot ones. Leaching the Kainit Langbeinitdiapersion obtained has a salt content of about 70 percent _# - S "The dispersion can be divided into two parts with the same salt content?; an ^x eil is intended for the production of KOL, epsomite, the other '-Ceil for the washing operation of the langbeinite and the extraction of potassium, Ea is preferred, however, to conduct a dispersion with a lower salt content in this last stage. According to a preferred embodiment of the present invention, the dispersion carried into the washing stage of the angbeinit contains 40 to 60, preferably about 50,% by weight of brine. In order to achieve such a content, the dispersion is prepared, for example by decanting, in such a way that a lower range of about 50% pesticide substances and an upper range consisting of brine is achieved. Part of the prepared dispersion is fed into a stage in which the washing of the angbeinite takes place, while the remaining part is combined with the brine and into the stage for conversion to KOl and MgSO * .6HgO and / or MgSO ^ .7H ₂ O is escorted.

The various process steps which are the object of the present invention are described in the following _f detail with reference to the embodiment illustrated in the chart drawing showing the method erfindungagemässe.

The continuous lines in this drawing relate to each other on the solid bubbles, the dashed ones on the brines.

First stage - leaching of kainite

Raw Kainitsrz is ssarstosaen into pieces that are smaller than 1 bl0 10 mm * Dm %%% is preferably white zer etoseen into pieces that are rockine ale 5 to B mia »

The gerfeieltterte Mm 11 is memmiwi il 12 of Bpeoiaitßole phase with a ^ & 19 _r 4i§ in step 3 arhölton wii-dp m the leach «1

at about 10O ⁰ O.

Classification

Second stage - des - "angbeinits

The Langbeinitdispersion obtained in step 1 13, consisting of langbeinite, sodium chloride and Langbeinitsole is led to ^Klas SiSfö? "Fe. 2 - ■. - '

This process is carried out in such a way that the solid substances with dimensions that are above particle sizes, which through a sieve of 144 to 576, and preferably 144 to 342

. ρ could
Stitches / cm are separated. The dispersion 14 containing most of the sodium chloride is removed from the circulatory system. The dispersion 15 contains the remainder of the Langbeinite dispersion, namely Langbeinite, the fine fraction, the sodium chloride and the Langbeinite brine.

This centrifuged dispersion is preferably made by decanting separated by a heavier part thereof, which is preferably a solid content of about $ 50 and the ßest amount received as $ ole. Am rope 1.6 of the decanted dispersion is sent to stage 6, where the langbeinite is washed and potash is recovered. The remaining part will go together with the brine caught. The decanted diluted dispersion 17 is led to stage JJ, where the Langbeinit becomes potassium chloride and Epsomit (or MgSO *, 6HgO) is converted.

If no dilution is carried out, the dispersion becomes 15 divided into two parts 16 and 17 with an equivalent brine content.

Third stage - conversion of the langbeinite to potassium chloride and

Bpaomit ___ '

Part 17 of the Labgbeinitdispersion is combined with the Schoenitsole 18 and cooled in step 3 at 35 ° to 20 ⁰ O. This cooling, "is preferably carried out in successive stages," in order to ensure the best conditions for heat generation.

The mixture of KOX _f NaOl and MgSO ^ tfiHgO- and / or HgSO ₄ ♦ 7H ^ O is obtained in the same way "!" Suggests the ancestral imperial door near the lower center of the above-mentioned ßeroiohs, i.e. * iu bsi aO ° 0,

AD ORIGINAL

008842/1418

so the magnesium sulfate tends to condense in the form of epsomite * If the temperature is close to the upper limit, then MgSO. * 6HpO tends to precipitate · It therefore becomes

"O

a process temperature of about 20 ° is preferred, so that the magnesium sulphate in boron from Epsomit is deposited »

Fourth stage ~ seven or

The dispersion 19 obtained in stage 3 is one in stage 4

Classification
Sieb- or - & ieiiwiagsv-experienced. This sieving is usually carried out by means of a sieve that has 94 to 576, preferably .64 to 1-44 · meshes / cm »

That from MgSO..6K ₂ O and / or MgS0. _e 7H "0 existing overhead screening material 23 is divided into two parts: the first part 25 is removed from the circulatory system, while the second part 24 is directed to stage 6.

The. Chlorides are released from the. Epsomitsoie separated, which is divided into two parts: the first ' ^i! Part 12 is returned to stage 1, while the second part 20 is sent to the Iiangbeinite washing stage and to potassium recovery.

55 to AQfo of the Epsomitsoie are preferably led to level 6 i

Fifth stage - flotation of potassium chloride

The proportion of potassium chloride and sodium chloride becomes Stage 5 where the flotation of the potassium chloride takes place * Preferably aliphatic amines are used as flotation * ·

'27 "medium ver / ehdet, the flotation residues / f the essentially

consist of .Hatriumchlorid be discarded "stage - Wa aclien of _n 3Jan ^; 'bfainit tmd

Part 16 of the liangbeiriite dispersion, which has preferably undergone the processing explained under point 2, is combined with part 20 of the Epüomitoole and. if the scrape rat is above 80 ^{0 0} it is a '-Ceil' M-AkB from level 4-Hez ---, -. yfir ^; -: stod <-> r iifjjjtahjd ^^ at dec -u ^ cfuaiuraanXfMt,.: "bco mlf.lt.

98-42 / 1428

BATH ORIGINAL

The process is preferably carried out within a temperature range of 95 to 105 ° C. A part of the potassium present in the brine is precipitated during this stage in the form of metastable langbeinite, while the _{sodium chloride introduced together with the Lan (3} -beinite dispersion dissolves.

After completing the procedure, the metastable Langbeinitsole 22 passed into the dewatering device, during the 21 is passed to stage 7 for conversion to Schoenit.

The langbeinite is preferably separated from its Sole by simple decantation, so that a concentrated material _m J_T a content of about 40-60 $ brine is obtained. The concentrated metastable Langbeinite dispersion 21 _{% obtained in this way} is passed into stage 7 «

Seventh stage - conversion of the angbeinite to schoenite

Langbeinite or a metastable Langbeinitdispersion increased density 21 is subjected in stage 7, along with the originating from stage 8 sulphate brine 29 conversion to schoenite and cooled to 35 to 20 ⁰ C. The method is preferably carried out ^{at about 20 ° C.} Finally, a solid phase 30 is obtained, which consists of Schoenite and KCl, and a Schoenite brine which is returned to stage 3.

Eighth stage - double implementation

The mixture obtained in Step 7 for 30 from schoenite and KCl is reacted with the product obtained in Stage 5 Kaliuraohlorid flotation in the presence of water at a temperature between 20 ⁰ C and 40 ⁰ C, but preferably 30 ⁰ C,.

Instead of passing the flotation potassium chloride 28 into stage 8, it is preferably fed into the conversion stage 7, as in the attached drawing is shown. In this case, that includes at the end of stage 7, solid body 30 received all of the "potassium chloride and schoenite required for metathesis 8"

Potassium sulfate 32 and the Sulphate brine 29 »The brine is returned to stage 7,

009842/1428 bad original

159203b

To the composition of the various stages of the process brines used to be checked so that they get the most appropriate level of concentration for each stage it is possible to modify the content of the brine entering each stage by adding suitable amounts of water so that the brine has a predetermined optimal content. These encores are not essential, but allow maintenance the best process conditions in terms of kinetics and the yield in each individual process.

These additions also make it possible to meet the procedural conditions to any change in the kainite content of the ore supplied to adjust. The concentration of the various brines can be increased in this way, in spite of the properties of the ore supplied occurring fluctuations, are kept at optimal values.

The following examples are intended to form the basis of the present Explain the invention.

example 1

¹ · leaching of Kainiterzes at 100 ⁰ C 100 g Kainiterz, the crushed into large pieces 6 now, were 66.39 g and consisted of kainite and 33.61 g NaCl, were taken one hour at 100 ⁰ C with 87.30 g from stage 3 recirculated brine treated.

39.77 g long leg, 30.68 g NaCl, 1.99 g unconverted kainite and IH, 86 g long leg brine was obtained.

2. Classification and preparation of the long-leg dispersion at IQO ⁰ C 187.30 g of the long-beecinite dispersion obtained in stage 1 were treated in a classifier, a suitable regulation of this classifier allows the separation of the particles and dimensions that are above partial sizes which are passed through a sieve with H4 stitches / cm.

26.37 g of waste was obtained after centrifugation and washing, which consisted of 1.99 g of kainite and 24.38 g of NaCl? 16O, 93 g Langbeinltdlsperslon from 39.77 g Langbeinit, 6.30 g NaCl and 1Η, 8β g Lang-, · ',. ,

BATH

00 98 42/1438

beinitsole formed the a. The Langbeinitdispersion was dekantiert- at 10O ⁰ C.

85.84 g lower higher density residues and 75.09 g mainly sieved material consisting of long leggings received after decanting,

3 · Decomposition to KOl and MgSO . , 7H p O at 20 ^° C

75.09 g of Iiangbeini.tflole and 51.14 g of Iangbeinite dispersion of higher density (23.69 g of langbeinite, 23.69 g of brine, 3.76 g of iiaCl) were added in successive stages up to 20 ° C. together with 70.42 g Schoenit mother liquor from stage 7 and 2.47 g of water are cooled. The dispersion obtained in this way was conditioned ^{at 20 ° C. for four hours.}

14.64 g of KOl, 9.01 g of NaCl, 39.07 g of MgSO ^ .7HgO and 136.40 g of Epeomit mother4 ^< 14is- & igke44 _T liquor were obtained.

4, -5 · sieving and flotation at 20 ⁰ O

The dispersion obtained in Stuf © 3 (199.12 g) was through a Sieve with 94 meshes / cm placed, on which the largest part of the magnesium sulfate remained as residue, the length of which after centrifugation and washing was 29.30 g,

Through the sieve were 14.64 g of KOl, 9.01 g of NaCl, 9.77 g of MgSO., and 136.40 g of Bpsomite mother liquor,

17 »29 g of Sylvit concentrate (Η, 20 g KOl, 3» 09 g NaOl) and 16.13 g waste products (9 * 77 g ■ MgSO ₄ .7H ₂ 0, 5.92 g NaCl, 0.44 g KOl) were obtained by flotation of the screened material, non-flotable waste was removed,

6, washing the processed lengbeinite dispersion and extracting the potassium ... ^ " ; ^ ₁

34 _f 70 g of the abj | e throwns! »Angbeinitdlapersion higher density from stage« 0 were for one hour at 100 ° 0 with 4.9 »10 g

17.90 g MgSO ^ * 7Hg6 and 3.34 g water

ORIGINAL

; ■ - '"' ■■ ■■. ■ '■ - ■■■'" IiAII-IlXd- / 1 iHH · '' · ■■ "■ · '· - -

lye

20.29 g of angbeinit and 84.72 g of langteinite mother-of-pearl, the Q, containing 89 wt% potassium and 2.02 wt% sodium were obtained. 50 $ of the lower long leg with higher density was studied

lye

fe 7 headed. The mother £ Me-SMrg-fce *% (64.43 g) was put into circulation taken

7c conversion of langbeinite in schoenite at 20 ⁰ C

40.58 g of the. thrown off - ^ angbeinite dispersion of higher density, which contained 20.29 g Langbeinit, were with 17.29 g Sylvit concentrate, 58 »31 g sulphate mother liquor from stage ~ 8 and 0.57 g water" treatedβ

The dispersion obtained in this way was conditioned ^{at 20 ° C. for 3 hours}

There were 30.41 g of Schoenit, 15.94 g of KCl and 70.42 g of Schoenit mother liquor received which was returned to stage 3 »

8, double conversion at 30 ° C

4, 35 g ^ estst off substances from step 7 -during 3 hours were treated at 30 ⁰ C with 35.32 g water *

23.37 g of moist K ₂ SO. (Composition / K = 40.65, Mg = 0.77,

Cl = 1, f | _d SO ₄ = 51.60, K ₂ O = 5.95 wt .- ^) and 58.3.1 g of sulfate filide obtained after centrifugation. The Sul

Fat mother liquid was returned to stage 7. After drying, 22.68 g of K ₂ SO with a KgO content of 50.47 Gev ;. The potassium yield, the ratio between the eäfi the circulatory system in the form of ^ p ^ A ^yer l ^ate deni and calculated the circulatory system in the form of Kainit supplied K ₂ O was 89, i> 2 $. ,

Example 2 ■

1 · Leaching of the kainite ore at 100 ° C

100 g of Kainiterzi, which had been crushed into particles below 6 mm, mainly consisted of 64.91 g of kainite and 35.09 g of MaCl, was recycled with 85.35 g of recycled material for one hour at 100 ° C. treated grain brine

BATH ORIGINAL

38.71 g of langbeinite, 32.27 g of NaCl, 1.95 g of unconverted kainite and 112.42 g of langbeinite brine were obtained. 2 · Classification of the Langbeinite dispersion at 100 ° C. 18 5.35 g of the langbeinite dispersion obtained in stage 1 were treated in a classifier. Proper regulation of this classifier permits the separation of particles with dimensions in excess of particle sizes which could pass through a 144 mesh / cm sieve.

After centrifugation and washing, 27.7% waste was obtained consisted of 1.95 g of känit and 25.81 g of NaCl, while 157.59 g of langbeinite dispersion, which consisted of 38.71 g of langbeinite and 6.46 g of NaCl and 112.42 g Langbeinitsole consisted as torture material. The dispersion did not show any phases of different density

3. Decomposition to KCl and MgSO, .7H ₂ O at 20 ° C.

104.58 g of langbeinite dispersion of the Klaee £ # 4Bies »eft classified material (2 5.69 g of langbeinite, 4.28 g of NaCl, 74.61 g of brine) were added in successive stages together with 66.50 g of Schoenite mother liquor from stage 7 and 0.86 g of water at 20 ⁰ C cooled · The dispersion thus obtained was 4 hours 20 ° C tjei conditioned ·

14.50 g of KCl, 45.61 g of MgSO ^ .7H ₂ O, 9.01 g of NaCl and 102.82 g of Bpsomite mother liquor were obtained.

4-5 « sieving and flotation at 20 ^° C

The dispersion obtained in stage 3 (171.94 g) was passed through a 94 mesh / cm sieve to remove most of the residue to remove the magnesium sulphate, the amount of which after centrifugation and washing was 34 »21 g ·

The sieved material consisted of 14.50 g of KCl, 9.01 g of NaCl, 11.40 g of MgSO ₂ ^ H ₂ O and 102.82 g of epsomite mother liquor. Flotation of the screened material gave 16.72 g of Sylvitlon concentrate (13.75 g of KCl, 2.97 g of NaCl); the waste products (0.75 g KCl, 6.04 NaCl, 11.40 g MgSO, .7HgO) were removed.

^ß AD ORIGINAL

009842714 2 8

6. Washing of the angbeinite dispersion and extraction of the potassium

52.99 g of Langueirii.tcLispersion. from stage 2 (13.02 g Lan ^ beiiiit,

2.18 g_Ii.aCl, 37.79 g Ijazi-güeinitdispersion) were during a

Hour at 100 ^° C. with 17.47 g of epsomite mother liquor, 23.23 g

KgSO., 7H ₂ O and 5.79 g of water treated. ¹ ^ n received 18.84 g Langbeinit and 80.67 lbs Langbeinlt-Mutterl'Mige "

The Langbeinit, which was compressed to a solid substance of 50 $, was in Stage 7 passed.

61.83 g of the mother liquor, the 0.89 wt. - # potassium and 2.02 wt. ^ Containing sodium were withdrawn from the circuit.

7 «Conversion of - ^ angbeinite to Schoenite at 2Q ⁰ G

37.63 g. a processed, metastable ^ disperion, which

13.84 aj Langbeinit contained 16.72 g sylvite concentrate au3 stage 5 and 56.04 g * sulphate mother liquor from stage 7 treated. * Ϊ'-

The Diapereion thereby obtained was conditioned for 3 hours at 20 ⁰ C * is obtained 28.27 g Sohoenit, 15.67 g KOL and ■ 66.50 g schoenite-Iiütterlauge which was zurliokgeführt in Step 3 ·

8w Double conversion at 3O ⁰ O

43 "94 g of solid substances aui stage 7 were treated with 34» O5 g of water for 3 hours b © i 30 ⁰ O "After centrifugation, g feuehtee KGSO ^ ait finer Zusarnmensetzung received 2i _# 95 of K * 41.53 / Hg * 0.53s oil * 1.83, SO ₄ »30.72, HgO- 5.34 wt. And 56.04 g of SuIfat mother liquor, dl © returned to stage 6

Haoh the i'roolßnen one received 21.36 g KgSO ^, wao 51.47

KgO © ntaprioht Bi ^ Ausfeeute an Kfi & itm was n ^ oh Example Hr *

srj £? £) Qhnet and was 88.00 ^ ^J '

100 g KalnHtusiBf dae in uato »β fiä & jpö ·« · ·. -:. ■: Μ · §42 / ΐ4ΐΓ

and contained 70 g of kainite and 30 g NaCl, one hour at 100 ⁰ C with 87.30 g rUckgefUhrter brine from step 3 were treated while.

41.93 g long leg, 27.16 g NaCl, 2 ^ 10 g kahit and 116.11 g long leg brine.

2. classification and conditioning the Langbeinitdispersion at 100 ⁰ C 187.30 g of Langbeinitdispersion obtained in Step 1 were treated in a classifier · Bine appropriate regulatory This classifier allows the precipitation of particles with dimensions that exceed a part size which pass through a sieve with 144 meshes / cm.

After centrifugation and washing, 28.83 g of waste were obtained 21.73 g of NaCl and 2.10 g of unconverted kainite, while one 163.47 g of the Langbeinit dispersion, obtained from 41.93 g of Langbeinit and 5.43 g of NaCl and 116.11 g of Langbeinite brine as torture material.

The Langbeinitdispersion obtained as fine material in the classifier was decanted at 100 ⁰ C. A lower residue (89.51 fr g) of increased density and a material consisting essentially of a Langbeinite dispersion (73.96 g) were obtained.

3. Decomposition to KCl and MgSO ^ .7H ₃ O at 20 ° C 73.96 g of the langbeinite dispersion obtained as pain material in the classifier and 53.55 g of the heavier langbeinite dispersion (25.36 g langbeinite, 2.70 g NaCl, 25.49 g brine) were added in successive stages together with 73.10 g schoenite Mother liquor from stage 7 and 2.47 g of water were cooled ^{to 20 ° C.} The dispersion obtained was conditioned for four hours at 20 ° C.

15.34 g of KCl, 7.55 g of NaCl, 42.37 g of MgSO ₄ WH ₂ O and 137.82 were obtained

g Bpsorait mother barrel.

4th-5th Sieving and flotation at 20 ° C

The dispersion obtained in Stuf x 3 (203.08 g) was passed through a Sieve with 94 meshes / cm ² out, with the residue MfSO ^ -Heptp-

hydrate was obtained, the amount of which after centrifugation and

Washing was 31.77 f and then removed

ORIGINAL

009842/1421

The sieved material consisted of 15.34 g KCl, ty *>*> g NaCl, 10.60 g MgSO..7H ₂ O and 137.82 g epsonite mother liquor. 17.69 g Sylvit concentrate (14.94 g KCl, 2.75 g NaCl) and 15.80 g unusable material (10.60 g HgSO, .7H _o 0, 4.80 g liaCl, 0.40 g τ, « i \ sifted. _ 4 ^ material *

KCl) were obtained by flotation of the ^ Sii <ai & * ta »drf. The useless one Material was discarded.

6. Washing of the prepared Langbeinite dispersion and recovery of the potassium

35.96 g centrifuged Langbeinitdisperßion increased density (16.57. G ^ angbeinit, 2.73 g NaCl, 16.66 g brine) from Step 2 for one hour at 100 ⁰ C with 50.52 g Epsomitmutter were 3.01 g of water and 18.81 g of MgSO..7H ₂ O treated. 20.92 g Langbeinite, 87.38 g Langbeinite mother liquor with a content of 0.92 $ potassium and 2.05 Grew .- # sodium were obtained, 66.46 g mother liquor were derived, while that brought to a solids content of 50 $ heavier langbeinite dispersion was led into phase 7.

7. Conversion of langbeinite to schoenite at 20 ° C

41.84 ε heavier langbeinite dispersion from stage 6 (20.92 g Langbein.it, 20.92 g brine) were treated with 17.69 g sylvite concentrate and 62.07 g sulphate mother liquor from stage 8 ..

The dispersion obtained was ^{conditioned at 20 °} C. for 3 hours. 31.27 g Schoenit, 17.23 g KCl and 73.10 g Schoenit motherf

were received. The mother liquor was used in stage 3 returned.

8. Double conversion at 30 ^° C

48.50 g solid substances (31.27 g Schoenit, 17 »23 g KCl) * from stage
delt.

Step 7 were behan- for three hours at 30 ⁰ C with 37.70 g of water

24.13 g of moist KpSO, having the following composition: K = 41, f7, Mg = 0.53, Cl = 1.60, SO ₄ = 51.00, 5.30 and 62.07 g HgO ■ ßulfatmutterla _u ge were η ch after centrifugation

0098A2 / U28 bad original

lye

The sulfate mother obtained was returned to stage 7 "

23.49 g of K-pSO, with a KpO content of 51.44 ', σ were n: ch de: -, 'i' get dry.

The yield of i-alium was by the above method • on the basis of the dimensions of 89.59 '' given in example 1,

Example 4

1 · Leaching of the kainite ore at I uO ⁰ O

1 (3 g kainite ore, d; .- o to particles smaller than 8 nrc destroyed word-η and sub 64 »91 g kainite and 35.09 g iu; 01 consisted, one hour at 1uO ^c C together with 85 , 35 g of the brine returned to the <.us stage are treated.

30.7 g of angbeinite, 32.40 g of NaCl, 1.95 g of unconverted Kainite and 112.30 g of Laugbeinite Brine were obtained.

Classification and

2ο Prepare the Langbeinit dispersion at 100 G

185.35 g -Liangbeinitdisperisioii obtained in stage-1

P 2

was, were «e— '

N.-ch centrifuging and washing 3T, 11 g waste that consisted of 29.16 g WaCl and 1.95 g kainite, e *. 154.24 g <*** " as- LangbeinitdisperKion with a composition of 38.70 g Langbeinit, 3.24 g NaCl and 112.30 g Langbeinit brine rden »erüilteri. The Langbeinite dispersion was at 100 ° C

decanted,

80.71 g of prepared dispersion of increased density and 73.53 g of a material consisting mainly of latigbeinite brine were received,

3 · Decomposes to FCl and MrSO . «7H q O at 20 ^° C

73.53 g and 48.17 g Langbeinitsolo heavier Langbeinitdispersion (23.10 g Liuigbeinit, 23, H g Sole, 1.93 g NAOL) were in g on eiiinnderfol ^ Onden levels up to 20 ⁰ O Busainmen with 68.20 fin treated by a classifier. Bine suitable Regulieruni this ίΛ ^ Λ ^^ Α ·· * · ** · * ^di · excretion of the particles with

BATH ORIGINAL

-. 21 -

lye

c aua level 7 and 2.74 g HpO cooled

The dispersion obtained was conditioned for four hours at 20,

14.84 β KOl, 6.53 g HaCl, 40.33 g -IgSO ₄ ^ H ₂ O and 130.94 g epsomite mother liquor were obtained.

4, -5 · sieving and flotation at 20 ⁰ G

The diaper ion obtained in step 3 (192.64 g) was through a Sieve passed at 342 washings / cm. As a sieve residue was magnesium sulfate obtained, d "B after centrifugation and washing Was 28.27 g.

The sieved material consisted of 12.06 g of MgSU ₄ , 7HoO, 14.84 g of KGl _1, 6.53 g of HaCl and 130.94 g of epsomite mother, 17.22 g of Sylvit concentrate (14.34 g of KOl, 2.88 g WaCl) and 16.49 g of unusable material $ 12.06 g of MgβQ ₄ "7H ₂ ü, 0.50 g of KCl, 3.65 g of NaOl) were obtained by flotation of the sieved material. These unusable materials were removed"

6, washing of the processed Iuingbeinitdisperaion and recovery of the potassium .

32154 g of the heavier or thickened angbeinite dispersion (iü _f 6Q g iangbeinite, 15.63 g dispersion, 1.31 g ^ aCl) from stage 2 were one hour at 100 ⁰ O with 4 _t 0 4 g H ₂ O, 17.74 g MgSO ₄ ^ H ₃ O and 45 | 59 g Jäpsomit mother liquor treated »19.71 g Langbeinit and 80 _f 21 g metastable Langbein! tmut with a retained clay 0 ^ 89 ^ ew · - ^ Potassium and 1.48 Sow, - ^ Sodium were obtained »

thicken *

! • uff · v

60 _t ? B g of the mother chi were removed while dio iiangbeinitdiepereion was returned in stage 7.

7 · Conversion dt »Langbeinlt to Schotnit bti 20 ⁰ O

g aufbtroittt · Langbeinitdiep «r« ion at level 6 (19.71 g

;, 19 »43 g Sol ·) were treated with t7 _t 22 g Sylvltkonaentrut \ mä 56.01 aylfatmutttrlaug · au · Stuf · β. The obtained was conditioned for three hours to 20 ^° O. 28.24 i;

ft ^ iD / uii BADORIG'NAL

Schoenit, 15 »93 g KCl and 68.20 g Schoenit mother liquor were The mother liquor obtained was returned to stage '3 »

8 » Double conversion at 30 ⁰ G

44.17. g of solid substances from step 7 (28.24 g schoenite, 15.93 g of KCl) were treated with 34fO3 g of water for three hours at 30 ⁰ C. "

22.19 g moist KpSO, with the composition K = 41.73, Mg = 0.52, Cl = 2.37, SO. = 50.12 and Η _£ 0 = 5.26 wt - $ and 56.01 g of mother liquor were sulfate after centrifugation erhcilten ₀ The sulfate mother liquor was returned to step 7 "

21.61 g of KpSO, with a KpO-G content of 51.63% n.'ich get dry ", the yields of potassium due to the calculation given in Example 1 was $ 89.22,

Instead of dividing the langbeinit between procedures for conversion into KCl and epsomite and for conversion into schoenite and KCl to achieve the necessary for the metathesis to ivalium sulfate KCl and Schoenit quantities, it is possible to use a larger Quantity required for the conversion process to KCl and epsomite to take. and thereby to obtain an excess of KCl. To this One obtains KCl in addition to KpSO., It is also possible to manage the KCl excess or a part of the same with part of the MgSO, -Iiöxahydrat- or to implement heptahydrates, so that Schoenit is obtained, which together with the directly by the Conversion of the Langbeinite to Schoniet and Schoenit obtained from KCl is used for the double conversion,

■ It is obvious how the various procedures should be used to the ΐ remains; the coarse fraction under warm conditions » for example by sieving, Cyolon treatment or centrifugation of the greater part of the catalytic chloride contained in the angbeinite also leads to good results, provided that the procedures are used sensibly »

BAD ORfGiNAL

Claims (1)

PAT Έ Έ ϊ INSPECTION: Ι .. Process for the production of potassium sulfate using " of raw kainite as the starting material, characterized in that that he a) the crushed raw ore at over 90 C by means of an Epsomite brine recycled from Steife 3 to achieve a Langbeinite dispersion leaches from a solid, Langbeinit and ^ Phase containing sodium chloride and Langbeinitsole, .- '■■ -.-. classified b) the Langbeinite dispersion - and thus the largest part separates their ifodium chloride content, classified c) a first amount of the langbeinite dispersion at 35 to 20 ⁰ C in the presence of a Schoenitsole from ^ tufe 7 cools, whereby a solid phase is obtained, the "from a mixture of KGl, NaCl, MgSO ₄ COH ₂ O and / or MgSC ₄₀ YH ₂ O and a Bpsomitsole consists, -. '■ Classification d) the lagnesiurasulphate from the chloride through or through life separates, while the epsomite brine partially divides into level 6 and is partially returned to stage 1 and the magnesium sulfate partly back to level 6 and partly out removed from the circulatory system, e) the potassium chloride from the sodium chloride by lotation separates, .....:. , f) a second 'l ^! ecause the Langbeinitdispersion at a 80 ⁰ G lying temperature with a i'eil the Epsomitsole obtained in step 4 and a 'i'e.il the amount of magnesium sulfate obtained in step 4 while achieving a solid, aua Langboinit. consist of stage 7 directed phase and a metastable long-life brine that is removed> g) the langbeinite obtained in Step 6 at 35 to 20 ⁰ C with a solution obtained in stage 8 sulfate brine to give a (or "Leonit) and potassium chloride existing Fenten phase and a ficboenitsole treated from schoenite, the back in the step 3» 0Ü9842 / U28 ^ß AD ORIGINAL p h) Schoenite and potassium chloride from stage 7 with potassium chloride obtained in stage 5 in the presence of ^ water to obtain potassium sulphate and a sulphate brine which converts into the
Stage 7 is returned. 2o method n; .-. Ch claim 1, characterized in that the raw cainite ore is crushed into particles which are of a size less than 5 to 8 mm 3ο method according to the preceding claims, characterized the classification
draws that the Langbeinit is carried out in such a way that the solid substances are separated that are not through
a sieve with 144 to 342 meshes / cm could * 4 · Process nr-.ch the preceding claims. aer 'Krassierun ^
shows that the Langbeinitdispersion is below To achieve a thick dispersion containing 40 to 60% brine, one part of the egg is passed into the washing stage of the Langbeinite and into the potassium recovery stage, while the other part, together with the brine separated off during the preparation, is passed into the conversion stage for KGl and MgSO- * 6HpO
and / or MgSO. «7HpO is performed. 5. The method according to the preceding claims, characterized in that the separation of MgSO, .6H ₂ O and / or MgS0 ^ .7H ₂ 0
of KCl and BTaCl is pre-removed by sieving using a sieve with 94 to 144 mesh / cm · Pur Sincat Societfe Industriale Oatanese SpA
Palermo / Italy Lawyer
009842/1428 SAD OBiGiNAL