DE1077611B - Process for the electrostatic preparation of mineral mixtures containing kainite - Google Patents

Description

GERMAN

The kainite (KCl · MgSO ₄ -2.75 H ₂ O) occurs in the natural potash deposits often as an accompanying, but also as a main mineral.

The present invention relates to a method for separating kainite from salt mixtures in which it is present from degradation or extraction, in particular from mixtures in which, in addition to kainite, rock salt (NaCl), sylvine (KCl) and kieserite (MgSO ₄ -H ₂ O ) can be included. The usable components of the mixtures, i.e. the kainite itself, the sylvin and possibly also the kieserite, can be obtained in high percentage form.

The process according to the invention is carried out by digesting the pulp which has been broken down by dry comminution Material chemically conditioned with small amounts of certain reagents that are used in subsequent Passage through the electrostatic high voltage field splits the mixture into the desired ones Cause factions. One proceeds in such a way that one follows the conditioning in the first stage of the process a raw separation of the kainite from the other components is carried out, using a kainite pre-concentrate, possibly another pre-concentrate of another usable component and a medium good receives that in a further process section (possibly several) after a second conditioning processed into high-percentage products and repellent residues.

Before conditioning, the material to be processed is preferably ground to -0.75 or -1.0 mm. The type of conditioning agent depends on the mineralogical composition of the salt mixtures. The following goods can be processed: kainite-sylvin-rock salt mixtures, kainite-sylvin-rock salt-kieserite mixtures (= Kainite hard salt mixtures) and kainite rock salt mixtures. For kainite mixtures containing sylvin one works with conditioning agents for the purpose of separating the Sylvins, which consist of compounds or a mixture of compounds which lead to a Group of substances include the organic carboxylic acids, the sulfonic acids, acidic sulfuric acid esters or their salts, amides and anhydrides and the esters of carboxylic acids and such organic substances and salts thereof which, without being carboxylic acids, sulfonic acids or acidic sulfuric acid esters, are acidic Have properties. These remedies are hereinafter referred to as "Sylvin-influencing remedies".

If there is no sylvin in the initial material (e.g. in kainite rock salt mixtures) or has the sylvin already been separated in a first stage of the procedure (that is the case with kainite preconcentrates and intermediate goods), then one uses for conditioning (for further Separations) Means that consist of compounds or a mixture of compounds that make up a group

for electrostatic processing
of mineral mixtures containing kainite

Applicant:

Potash Research Institute G. mb H.,
Hanover, Georgstr. 29

Dr.-Ing. Hans Autenrieth, Hanover-Kirchrode,

and Dr. rer. nat. Gerd Peuschel, Benthe (Harm.),

have been named as inventors

of substances, which include the chlorinated phenoxyacetic acids, the benzoic acids substituted by chlorine or hydroxyl and the chlorinated phenols. These Agents cause the rock salt to be separated from the sulfatic components in the electrostatic field as well as a separation of the sulphatic salts from one another, hence in the following they will be referred to as "rock salt and sulphate." influencing means «.

The optimal amount of conditioning agent to be applied is determined in each individual case by simple preliminary tests to determine. Quantities of 25 to 300 g / t of reprocessed material were found to be sufficient.

Conditioning is carried out at room temperature in such a way that the conditioning agent is in solution is sprayed or dripped onto the material or applied in substance and mixed thoroughly with it. When applied in substance, the reagent can be in vapor form or in the molten state - in this case the material to be processed must open while it is being mixed a temperature above the melting point of the conditioning agent - or also be in powder form. Crucial for the

4-5 preparation success is in any case an intimate mixing and thus a completely homogeneous distribution of the conditioning agent on the surface of the Salt particles in the material to be processed. By any known method, conveniently by passing through a warm gas (air) stream, the material to be processed is brought to the separation temperature, and at the same time any solvent used is removed during conditioning. The most favorable separation temperature can also be achieved by simple

909 760/72

attempts to determine. It is between 40 and ISO ⁰ C, preferably between 60 and 100 ⁰ C.

The material conditioned in the manner described is then used for preconcentration on an electrical separator abandoned any design and fractionated at a field strength between 2 and 8 kV / cm.

The removal of the fractions happens, for. B. in the case of a three-stage separator advantageously as follows: In each of the three separator stages, first three fractions are removed, of which the middle one forms the feed material for the next stage. This creates seven factions: three on the right, three on the left and one in the middle. These fractions are combined according to their composition and amount in such a way that two or three fractions are obtained, which are either salable products or starting materials that are particularly favorable for further processing or repellent residues. With regard to goods to be further processed, this means that, by appropriately combining different fractions, medium goods are created whose composition matches the feed material of a separator stage and which are then expediently returned there. In the way z. B. in the examples described below with reference to the drawing, the intermediate goods B, C ₁ D and E (positions 10, 11, 14 and 15) obtained and returned to the process.

With the type of fractionation described and the conditioning also described above, three fractions are obtained from a kainite-sylvin-rock salt mixture in the first three-stage separation: a kainite pre-concentrate (see drawing, position 4) in which the kainite, depending on the feed and the conditioning agents used is enriched by 5 to 50%, a Sylvinvorkonzentrat (position 6), in which the sylvite by 8 to 58 ° / concentrated ₀ and a middlings a (position 5) which contains less kainite and sylvite as the output product .

After a second conditioning with the rock salt and sulphate-influencing agents, the kainite pre-concentrate goes to the second separation (item 8), which provides a kainite post-concentrate (item 9) with 80 to 95% kainite and two intermediate goods B and C , which are already in the fraction collection described way can be fed back into the process (see also drawing).

The sylvine pre-concentrate becomes the sylvine recovery 4-5 which is carried out in accordance with German Patent 1,056,551.

The intermediate goods A is conditioned with the rock salt and sulfate influencing agents and then separated into a residue (item 16) and two intermediate goods D and E (items 14 and 15), which are returned to the process in the manner shown in the drawing.

In the case of a kainite rock salt mixture as the starting material, the same procedure is basically used. Man Here, however, it is conditioned with the reagents that influence sulfate and rock salt even before the first separation.

To prepare a kainite-hard salt mixture, the material is conditioned in the first process stage with the above-mentioned sylvine-influencing agents. During the first separation there is a kainite enrichment on one side and a sylvin enrichment on the other, the kieserite becomes the kainite, the rock salt is generally distributed between the concentrates and the medium. The sylvine pre-concentrate is sent to the sylvene recovery. The second kainite concentration is carried out after the preceding conditioning with the above-mentioned sulfate and rock salt-influencing reagents. Here, the kainite in a second concentrate in an enriched approximately 90 ° / ₀ pure product and largely separated rock salt from the two sulphatic components. A satisfactory separation of the sulfate salts kieserite and kainite can also be carried out in one or more process stages - without further conditioning - so that high-percentage kieserite concentrates can also be obtained by the process according to the invention.

example 1

A crude salt consisting of 44.4 ° / ₀ kainite, sylvite 8% and 47.6% rock salt, was ground mm to the full mechanical disintegration to a particle size below 0.75. For the first conditioning of the goods, the agents given in column 2 of table 1 were sprayed in solution in the amounts given in column 3 onto the goods in a mixing machine or applied in powder form.

During the spraying or application and for 15 minutes after that, the material was in one mechanical mixer thoroughly mixed and then the crude salt to those mentioned in column 4 Bring separation temperatures, at the same time any solvent used evaporated. That The mixture conditioned in this way was then separated with a three-stage roller separator to which it was connected via a Shaking chute was abandoned. The separation took place at field strengths between 2 and 8 kV / cm, with the The next separator stage usually had a higher voltage than the previous one.

The process of separation is explained below with reference to the drawing. In the first stage of the process, the crude salt (item 1) was divided into three fractions in the first separation (item 3), namely into a kainite preconcentrate (item 4), the kainite and KCl contents and yields of which are shown in Table 1, columns 5 to 8, are given, into a medium good (item 5), the kainite and KCl contents and yields of which are listed in columns 9 to 12, and in a sylvine pre-concentrate (item 6), which contains the kainite listed in columns 13 to 16 and sylvene contents and yields. For further processing, the sylvine pre-concentrate went to post-concentration, which was carried out in accordance with German patent 1,056,551. At this point, the kainite preconcentrate could already be partially used as a product with 90 percent or more kainite and equally high yields. The high-proof products were mainly those that had been conditioned with powdered reagents prior to separation. The kainite and KCl contents and yields of the salts treated with powdery agents are listed under the serial numbers 13 to 21. The less highly enriched kainite preconcentrate and medium A went to the second stage of the process.

To save space, the following abbreviations are used in the following tables:

Phenyl-E = Phenylacetic acid Fat. Na salts = Na salts from Henkel First run fatty acids Phth. A. = Phthalic anhydride Phth. S. = Phthalic acid B. S. = Benzoic acid DPhOE = Dichlorophenoxyacetic acid TPhOE = Trichlorophenoxyacetic acid DClB = Dichlorobenzoic acid ClPhOE = Chlorophenoxyacetic acid DOB = Dioxybenzoic acid

5 6

Table 1

Crude salt: 44.4% kainite, 8% sylvine and 47.6% rock salt First stage of the procedure: Kainite-Sylvin separation

Conditioning agents Φ Tem Kainite pre-concentrate the end
prey KCl the end
prey Quay
nit Factions KCl the end
prey Sylvine pre-concentrate the end
prey KCl the end
prey Serial substance pe Quay
nit 7o 7o 7o 7o Medium good A 7th 7th Quay
nit 0 /
la 7th 7o No. 3 rature 7th 5 I β 7th 8th 9 the end
prey 11 12th 7o Ii 15th 16 2 7o 13th 1 4th 10

a-nitroso- / 3-naphthol ..

Saccharin

Phenyl-E

Fat. Na salts. Cinnamic acid cinnamic acid alkyl sulfate .... Alkyl sulfate ....

Phth. A.

Phth. A.

Phth. S.

Phth. S.

Phth. A.

Phth. A.

Phth. A.

Phth. A.

Phth. A.

B. S.

Na benzoate cinnamic acid

100 80 50.1 91.0 2.8 22.8 41.6 6.4 3.6 2.5 10.3 2.6 65.7 100 80 55.1 91.0 0.5 5.0 26.4 6.1 4.6 6.5 10.3 2.9 51.8 100 80 48.2 82.0 0.6 5.6 53.4 10.4 2.8 3.3 23.6 7.6 47.5 100 80 50.6 89.6 0.7 6.9 35.7 6.9 2.7 2.8 13.0 3.5 62.8 100 80 87.8 74.6 1.0 3.9 24.2 23.9 1.4 7.9 4.2 1.5 41.3 100 80 88.2 89.6 0.9 5.2 12.1 8.5 1.2 4.6 3.9 2.7 31.8 100 80 81.4 54.3 0.3 1.5 34.9 43.2 1.7 12.5 7.8 2.4 45.4 100 80 71.8 89.1 1.4 9.7 13.5 7.9 0.6 2.1 7.6 3.0 38.8 100 80 81.4 66.0 0.8 3.7 28.6 32.3 0.2 1.1 5.8 1.7 57.8 100 80 81.9 60.4 1.4 5.8 31.0 38.0 0.4 2.5 5.8 1.7 55.9 100 80 91.4 38.9 1.2 3.0 40.1 50.6 0.4 3.0 10.2 3.5 48.6 100 80 53.7 72.3 1.3 9.3 45.2 '20, 8 1.9 4.6 16.1 6.8 38.5 300 120 94.3 93.2 1.1 5.2 29.3 3.8 6.5 4.1 2.5 3.0 15.9 300 80 92.5 91.8 1.1 5.2 8.8 5.2 <0, l 0.2 4.1 3.0 27.9 300 60 94.8 91.2 0.3 1.4 8.0 5.5 3.1 10.5 5.0 3.3 26.6 200 80 93.0 92.7 0.5 2.4 19.8 3.1 0.8 0.6 3.7 4.2 17.3 100 80 91.4 94.5 0.9 4.4 - - - 4.3 5.5 15.6 300 80 86.4 75.3 1.4 5.4 20.5 18.8 4.1 6.8 11.0 5.8 32.9 300 80 84.5 90.0 2.1 14.6 10.1 6.3 1.2 4.9 7.9 3.7 27.4 300 80 81.6 72.1 1.6 7.0 19.3 19.0 0.7 3.4 19.7 8.9 38.7

74.6 88.5 91.2 90.3 87.9 90.2 86.1 88.2 95.2 91.7 93.9 86.1 90.7 94.6 88.1 97.0 95.6 77.8 80.5 89.6

Before further processing, the kainite preconcentrate (item 4) was treated with the methods listed in Table 2, Column 4, specified conditioning agents, with 100 g / t good, in the manner described for the crude salt conditioned.

It provided in the second separation (position 6), which was carried out at 40 · 8O ⁰ C, three fractions: a

Kainite post-concentrate (item 9), the kainite and KCl contents and yields of which are given in columns 5 to 8, as the end product and two intermediate goods B and C (positions 10 and 11), depending on their contents listed in columns 9 to 16 and yields according to item 8 or item 13 of the course of the process were returned.

Table 2

Second stage of the process: post-concentration of kainite

Amount of conditioning agent used: 100 g / t good

Separation temperature 8O ⁰ C; Feed material: Kainite pre-concentrate from Table 1

Serial
No. Task
Quay
nit
° / o ab-
It
KCl
7o Physical condition
funds
substance Quay
Quay
nit
7o not after
the end
prey
7o 28.5
51.4
75.2
68.0
63.8
25.8
76.5
22.9 conceni
KCl
7o did
the end
prey
7o Quay
nit
0 /
/ 0 Fract
middle
the end
prey.
7o ions
good B
KCl
0 /
/ 0 the end
prey
7o Quay
nit
7th middle
the end
prey
7o good C.
KCl
■ 7. the end
prey
7o 1 2 3 4th 5 I β 7th 8th 9 10 11 12th 13th 14th 15th 16 1
2
3
4th 50.1
55.1
48.2
50.6
87.8
81.4
71.8
53.7 2.8
0.5
0.6
0.7
1.0
0.3
1.4
1.3 2,4-DPhOE
2,4,5-TPhOE ....
2.5 DClB
2,4-DPhOE
Phth. A. 79.7
95.3
91.5
90.5
93.9
92.6
83.8
84.7 0.3
0.8
0.3
1.0
0.5
1.4
0.6 1.0
3.9
1.2
3.6
0.9
7.3
0.8 43.9
48.0
7.7
24.5
61.4
82.1
38.4
44.8 46.4
33.8
5.3
14.0
10.8
22.3
12.6
42.7 0.3
0.8
1.2
0.3
1.3
1.5 1.4
3.5
5.3
0.3
2.4
7.2 40.3
14.0
7.6
10.1
52.6
35.1 16.0
5.8
1.5
2.3
6.2
6.7 11.9
0.2
1.5
0.3
0.8
1.4 21.4
0.5
1.7
0.4
0.6
1.3 5
7th
8th
12th o-ClPhOE
2,4-DCl-phenol ..
Na-p-ClPhOE ..
2,4-DOB +
Phth. A.

The mean good. (Position 5) was before the further second separation (position 13) that was performed at 8O ⁰ C, treatment with 100 g of in Table 3, column 4, gave three fractions: a residue (position 16) conditioned medium indicated (position 12 ). The 70 and two intermediate goods D and E (positions 14 and 15),

their kainite and KCl contents and yields in Columns 5 to 16 are entered. The middle goods were

according to their composition returned to either item 8 or item 13 of the process.

Table 3

Second process stage: preparation of mediums

Feed material: medium material A of Table 1 Added amount conditioning agent: 100 g / t feed separation temperature: 8O ⁰ C

Input Kainit

KCl

o / / o

Conditioning agents

Substance fractions

Cainite

Medium good D Vo the end Quay Medium good E KCl the end Quay Residue Vo the end prey nit the end Vo prey nit the end prey Vo 0 /
/O prey Vo Vo prey % Vo Vo

Yield Vo

10

11

13th

15th

24.2 12.1

34.9 13.5 28.6

31.0

1.4 1.2

1.7 0.6 0.2

0.4

2,4-DPhOE 2,4-DPhOE

Phth.A. 1: 1, 2,4-DCl-phenol 2,4,5-TPhOE .., 2,4-DOB +

Phth. A.

2,4-DOB +

Phth. A,

80.3

41.0 82.1 63.9

70.4 74.1

10.8

6.1 29.5

18.0 20.1 1.0

0.3
0.1

0.2
0.2

0.8

0.7
0.1

0.3
0.3

25.8

31.0
13.2

36.4
29.8

9.1 0.1 0.2 2.0 0.5 - - 10.2
2.4 0.5 1.0 1.9
1.6
2.5 0.8
0.6
0.6 0.2
1.0 0.5
2.2 9.8 - - 1.5 0.7 - - 13.4 0.5 0.9 2.0 0.6 0.2 0.4

Example 2

Two crude salts I and II (drawing position 1) of the composition I: 43.0% kainite, 17.5% kieserite, 10.1% sylvin, 29.4% rock salt, and II: 21.5% kainite, 26.3 % Kieserite, 13.9% sylvine, 38.3% rock salt, were ground to a grain size of -0.75 mm, in the manner described in example 1 with the reagents mentioned in table 4, column 2, in the amounts shown next conditioned (item 2) and then separated according to the scheme shown in the drawing at 80 ^° C. (item 3). This resulted in three fractions: a kainite preconcentrate (position 4), which, in addition to kainite, mainly contained kieserite and mostly less than 10% rock salt, and two fractions containing varying amounts of sylvine, little kainite and kieserite (positions 5 and 6), which were the sylvine or Medium preparation were forwarded. The kainite contents and yields of the kainite preconcentrate (item 4) are compiled in columns 4 and 5, namely numbers 1 to 7 for crude salt I and numbers 8 to 10 for crude salt II conditioned with 100 g each of the conditioning agents listed in column 6 (item 7) and separated at 80 ° C (item 8). The two fractions obtained are: a kainite post-concentrate (item 9) and a medium BC (items 10 and 11 together), which, depending on its composition, was returned to either item 8 or item 13 of the process. The kainite contents and yields of the kainite post-concentrate are given in columns 8 and 9, those of the medium product SC in columns 10 and 11.

Table 4

Crude salt I: 43.0% kainite, 17.5% kieserite, 10.1% sylvite, 29.4% rock salt (consecutive numbers 1 to 7) Crude salt II: 21.5% kainite, 26.3% kieserite, 13.9% sylvite, 38.3% rock salt (consecutive numbers 6 to 10)

Separation temperature: 8O ⁰ C

First stage of the procedure: kainite preconcentration

Conditioning agents

substance

g / t

Second stage of the process: post-concentration of kainite

Conditioning agents
substance

Kainitnach the end Mitt concentrate prey Ge Ge Vo stop 8 / t stop 0 /
/ 0 Vo

Yield Vo

10

1 2 3 4 5 6 7 8 9 10

Phth. S. Phth. S. Phth. S. Phth. S. Na benzoate cinnamic acid mersolate D Phth. A. Phth.A. Cinnamic acid

300 71.9 95.5 300 68.7 94.6 300 72.7 94.6 300 78.4 87.4 300 69.5 98.6 100 74.9 92.7 100 70.4 66.6 300 52.4 79.8 300 40.5 98.0 100 61.2 90.7

2,4-DPhOE

2,4,5-TPhOE

2,4-DPhOE + Phth. A. 1: 1

2,4-DCl-phenol

2.5 DClB

o-ClPhOE

Na-p-ClPhOE

2,4-DPhOE + Phth. A. 1: 1
2,4-DOB + Phth.A. 1: 1 ..
2,4-DPhOE + Phth. A. 1: 1

100 93.4 50.8 56.7 100 88.8 58.2 50.5 100 94.0 86.2 20.8 100 96.0 79.9 26.0 100 90.6 82.5 31.1 100 95.7 82.2 30.1 100 89.3 59.7 23.4 100 62.8 65.3 41.5 100 81.0 50.3 27.9 100 74.2 83.2 18.2

Claims (2)

Patent claims: 1. Process for the electrostatic preparation of mineral mixtures containing kainite chemical conditioning and subsequent separation in an electrostatic field, characterized in that that following a possible preliminary separation from sylvin after conditioning of the crude salt with an agent consisting of a compound or a mixture of compounds which belong to a group of substances that include the carboxylic acids, the organic sulfonic acids, the acid sulfuric acid esters, the salts, amides and anhydrides of the substances listed and the Esters of carboxylic acids and such organic substances and their salts includes, without Carboxylic acids, sulfonic acids, or acidic sulfuric acid esters, have acidic properties that Processing material is subjected to conditioning with an agent that consists of a compound or a mixture of compounds belonging to a group of substances which the chlorinated phenoxyacetic acid ^ the chlorinated or hydroxyl-substituted benzoic acids, the chlorinated phenols and the salts of these compounds, and from the so conditioned material in the electrostatic field separated the rock salt and the kainite fraction in the absence of kieserite as high percentage kainite product obtained, in the presence of kieserite in further separation stages in a kainite concentrate and a kieserite concentrate is decomposed, while the possibly pre-separated Sylvin is processed into high-percentage products using known or older methods. 2. The method according to claim 1, characterized in that in the conditioning of the sylvin-free or agents freed from the sylvin are used as conditioning agents for the electrostatic separation of sylvin. 1 sheet of drawings © 90 »760/72 5.60