DE1915645A1 - Additive to reduce or prevent caking of sodium chloride or mixtures of substances containing sodium chloride - Google Patents

Description

Annex to the patent application dated 25 c 3. 1969
Be / where

"Additive to reduce or prevent the caking of sodium chloride or sodium chloride containing mixtures of substances "

Numerous substances or mixtures of substances are already known which enable a reduction or prevention of the caking of sodium chloride, in particular the soluble ferricyanides or ferricyanides mentioned in German patents 954 691 and 881190 occupying a special position, since these compounds are in the Technique in preventing sodium chloride from caking together. Furthermore, it was proposed in DAS 1,052,966 (see British Patent 818,385) to add a dissolved complex cyanide of iron, cobalt, nickel, ruthenium and the like to the sodium chloride, the cation according to column 3, lines 11 - IJ each may be, which forms with the anion in aqueous solution an ionizing salt, d, h _#, that these compounds must be soluble in water more or less. In the professional world, therefore, the attempt to use water-soluble complex cyano compounds has hitherto been the basis.

009882 / .1768 BAD ORiOINAL

These mentioned additives and also numerous additives, which prevent the caking of the sodium chloride are soluble in water and can be washed out by moisture or atmospheric precipitation. You are therefore as an anti-caking additive for scatterable products during storage Not suitable for outdoors.

^ The aim and object of the present invention was therefore a Find additives that both the baking tendency of sodium chloride or salt mixtures containing sodium chloride and which cannot be washed out.

According to the invention it has been found that these requirements include a method for reducing or preventing the caking of sodium chloride with the use of alkali hexacyanoferrate as an additive, in which the salt with a solution (colloidal solution), suspension or * emulsion of the additive consisting of hexaeyanoferrate and a Zinc salt, is added. A solution or colloidal solution, suspension or emulsion of the additive - ,,. means, consisting of 0.5.10 ^ moles to 1.0. 10 ^c moles * preferably 0.2. 10 "^ to 1.0. 10" ^ moles of alkali hexaoyano ferrate (II) and 1.5. 10 to 1/0. 10 moles, preferably ■ 1.5. 10 " ^-5 to 1.0. 10" ² moles of zinc compounds calculated on zinc used in a molar ratio of 1 ι 0.8 to 1; 1.4 as an additive. -

009882/1 76 ^ ^Ot} a ' ¹ "

The reaction product of soluble alkali metal hexacyanoferrate and a zinc salt is called zinc milk in the following. The use of water-soluble zinc salts is advantageous here, preferably zinc chloride., ^ sulfate or acetate or Mixtures of water-soluble zinc salts, instead of a soluble » Borrowed zinc salt can also use a zinc compound which in combination with alkali hexacyanoferrate, if necessary, liter addition of a 3jö solution sver with tiers a colloid soluble Reaction product or a reaction product in suspension or emulsion form results, As soluble hexacyanoferrate we · » the alkali hexacyanoferrate, which are known per se as anti-caking agents, are preferably used. Is particularly useful the use of Kai iumhexa cyano ferr at (XI), which is also the best properties in terms of reducing the tendency to bake shows.

According to the invention it was also found that the specified Molar ratios must be adhered to if washing out is to be avoided or a reduction in the tendency to bake storage in the open air should be guaranteed. For example, it was found that with a molar Ratio of (Fe (CN} g to Zn over 1; 1.4, for example 1 ; 1.5 already when assembling the components #iB flaking occurs and that the anti-caking effect is significantly reduced, ..

V ^.

Hf §14

.Try * those in the laboratory μϊκ | in the. Free gefnäg Fiep ^ incumbent invention were carried out, include (} |! WiGhtsfeji | iältnisse γο | ΐ Q ₄ QSS to gg, y ^ ^ pzygs else Q, l pis 0.5 g iCa.liumhe.xaGyan'Qferrat (II) and QjQH bi§ 7 ^ 5 g | ¥ Qrz ^ gs ^ ßi & e Q _? | to Q ₄ ,? g Zinkchlfardd ρϊ? ρ Jig

Natriyinciilprid ¥ been raised. The YortGile qes erf4 || s du | igsgejtj ^ ßen procedure are from the. naphstph ^ nd - & jj, fggs f | ihptg? a examples ynd 0? abel | ep clearly ^ ersipii || ißh.

hali) a ¥ ersuphe§ with several gghiplite || ¥ pn KaliUinhgxaGfai \ Qfe.i? Rat ff || § | leiri gin iieytliphe ^ ^ uswasphen cie§ gysatzpiittpls zii , If ^ nii this washing uiid sppit «| er ^ ir ^ fan of ius. § | z |

pre _; ien %%%

leiphj

zoneiiwetse erfo.lpen _?

pusatErnittel treated Sa | z ||| the Obereri pdgr only curdled amounts of i | ip ^ er additives ^ th. ^ so then the top layer or the top, Sch.lchtep leiphts additional time bacIcs can ^ while the one below Sphichten, an enrichment of these additives tons, piese w ^ .sserlc? sllohen cyanide

BATH

certain disadvantages as an anti-crack additive for spreadable products in storage, the outdoors stray.

009882/1768

Example A. Manufacture of the additive

Zinc salt solutions were added to a 1/100 molar aqueous potassium hexacyanoferrate (II) solution, so that the molar ratio of (Fe (CN) ₆ ) to Zn was 1: 0.8; 1: 0.85; * 1: 0.9; 1: 0.95; 1: 1.0; 1: 1.1; 1 ι 1.2; and was 1: 1.4. 90 ml of these solutions or suspensions were placed in seven 100 ml measuring cylinders and observed for three weeks. Zinc acetate, zinc chloride and zinc sulfate were the preferred zinc salts. The three week test just mentioned was carried out for each zinc salt. In all three cases, a separation into a liquid and solid phase could not be determined even after three weeks. Investigating molar ratios of (Fe (CN) ₆ to Zn above 1.4 proved to be of little use, since flocculation of solids occurred even when the components were assembled.

An aqueous solution of potassium hexacyanoferrate (II) and zinc acetate in a molar ratio of 1: 1 was centrifuged at 6000 revolutions per minute. According to the analysis, the precipitate obtained has the following composition K ₂ Zn, (Fe (CN) g \ _2. 7 HgO, which corresponds to a molar ratio of 1: 1.5 for (Fe (CN) ₆ ^ ft- to Zn ²⁺⁾ .

009002/1788

BATH

Batppisi B

Bgi SRiel I.

üü Hl

4e. In

Rl IaB-.

r -zielb ^ pen ^ pr »tsphr4tt ^, * fipd fo | g§ji ^ BE ¥ GleiGhsver.si | ah genanjat. Bill

1 S # l Piß te Wi weglgli .taeA | s sftgp g_ a IR

in the salt ent

in molar ratios of % : 1; 'J.: ^, Γ iind 1: I ^

, t '(II) to Ziiikiacetit) for application

Zusafcs mg / kg follicle; g salt mg Kj ₁ (Fe (CN) ^ SIi ₉ QAe -; -.'-

Ä ■ iOQ mg

Sehioht "'Addition fflg / kg salt g Sala -'" ins K _A (Fe (i? Li} g -) -. 3% O / l6g 1} A "'100 rag ^ g

PgQ ■ .- ■■ ... 8 ^ 0 ..-- ■■ 77.7

ale

β As Unto «« * 846 70.0

. 2) A 100 mg

7X5 86.5

'67, 7

97.6-

for I) Is Ij continued) ϊ s 1.1 and for 3) 1 s X »*

3) A. 100 mg SlS B. EiRtanilefc G 0QS

BAO

Example 2

The investigations mentioned below illustrate the anti-caking effect of zinc milk. Dedusted rock salt was mixed with various amounts of potassium hexa cyano ferrat (II.) Or zinc milk and 3 % water each. Cylindrical test specimens were produced from these mixtures and were ^{dried at 90 °} C. for 4-8 hours. The crushing pressure of the moldings served as a measure of the anti-caking effect. These are listed in Table 2.

Table 2

C-sample means salt with 3 % water without the addition of anti-caking agents. -l _f QV

Shatter pressures kg / cm

27.75 3.10 2.70

. 0

0 0

Addition mg / kg salt mg K ₄ (Pe (CNJg)) 3H ₂ O O sample t! η 10 It ti 25th It ti 50 ti dd 100 It ti 150 200

- 10 -

00988 2/17 ^ 8

Addition mg / kg salt fragmentation pressure kg / cm ² O sample Jl, 09

10 mg calculated as ^ ₆₇

(()) O that im

0-? robe 50 mg 100 11 150 I! 200 Il

₂₁ (() ^) O ₀ ,

25 mc · Ό ti. η Oq

^G reaction product of ■ \ ^'v 50 mg Zn (CH ₃ COO) _2' 2.46

) J

, "K ₂ . (Fe (CN) ₆ J.35H ₂ O

^lüü (zinc milkR) ²

is included.

'1 17

200 "0.78

33.63

calculated as

K ₄ (Pe (CN) ₆ ) .3H ₂ O, which in the '" ² reaction product of 1.76

ZnSO ₂ , with _Q

K ₄ (Fe (CN) ₆ ) .3H ₂ O is included.

) 50 mg of K ₄ (Fe (CN) ₆ ) OH ₂ O, which is in the 4.30

100 "conversion product of ₀

ZnCl ₂ with

150 "K ₄ (Fe (CN) ₆ ) OH ₂ ⁰ 0

₂₀₀ η is included. ₀

The molar ratio in all three cases of zinc milk was 1: ^u l. '-

> 5.

- 11 -

0 ö ¥ | 82V ff

ϊϊ

Mm 2U seigea. äa§ mis finer tr & grig§R suspension .v.aa li the h & sfrsts AatibsetewipKuns achieved weräM Man, - wur4 «a fei

i) ilia dusted stone corn wijsäe with the iföfc ^ r example 1

2) 2 «-entstiLut» teiäj OsIa wuräsa

by * KAiiiiinhex & eyanof © yrat (TI 5 toä Zinkttedtftt and geioisehts § © dlsg on atm Sälg a Zinkmiioh ent stand

was separated into two identical branches # 11 ©, To 4 © is a Tßil wmrcl © @ in§ wSteii® solution from Kniiiam

(II) "ad su. Atm: other & -Te £ i © ins ¥ oa ^ inkacetat given." The two files were cut separately, then combined again .

se »shares nuraen.iBBaer so t> emesaen» dafi dag 3 Ji entiei-t ,; _: Ay ».- di.e ^^ fi MisBhsageR -wMrdep wietier Fornlcörpar made, welehe at 9 ^ ° C 48 hours« · ^

at & Qlxiessen <ä ertpÖBimert; became. The results are standardized in 1 _{,; r} _.

- .Vi

BAD ORIÖINaC

Tabel

O-sample means salt with 3 % water and no added anti-baking agent.

Additional aig / kg / salt O-sample

10 mg K ₂ ZrLj (Pe (CN) ₆ J ₂ .7 H ₃ O

25 mg dry mixed

50 mg

100 mg

150 mg

200 mg

PO sample 10 mg of zinc milk by adding 25 mg of aqueous potassium

50 mg hexacyanoferrate (IIJ-100 mg and zinc acetate solution 150 mg create 200 mg on the salt

O-sample

10 mg of zinc milk by adding

25 mg of each component

50 mg to two parts of salt and

100 mg then mix up

Let 150 mg of the salt arise 200 mg

009882/176

SAD ORKSiNAL

Shatter pressures kg / cm , 59 28 , 55 10 , 56 10 , 73 11 , 38 9 , 16 ίο. .35 9. , 15
i., ^ r '-, ■ 28, .63 "'" '* 6, , 39 7, .25 6, .86. 5. 08 5. 69 4, 63 ...... 33, 27 5. 07 4, 82 3, 76 1, 76 1,

Claims (1)

S chut ζ claims; 1. Additive to reduce or * prevent caking of sodium chloride or mixtures of substances containing sodium chloride with the use of Aikalihexacyahoferrat, characterized in that One solution or colloidal solution, suspension per kg of salt or »emulsion of the additive, consisting of 0.5 * 10 "" ^ moles to 1.0.10 " ^S moles, preferably 0.2. ΙΟ "* ⁵ to 1.0, 10 ^- ^ moles of alkali hexacyanoferrate (II) and 1.5 * 10" to 1.0 * lo "moles, preferably 1.5 * 10 * ^ to 1.0 * ΙΟ * " ² moles of zinc compounds calculated on zinc, used in a ratio of 1: 0.8 to 1: 1.4 as additional packs, 2, additional means to reduce or "prevent the to" saffimenbäckens vött natrium chloride according to claim 1, thereby marked »that a soluble zinc salt or * a zinc compound in Korfifeinätien with Aikäiihöic & dyianö <* If necessary with the addition of a dissolving agent, a colloid-soluble conversion product is used or * a Ümsetaüngsprodukt inr6üsp; ensiphs * or 7915645 3. A method for reducing or preventing the caking of sodium chloride using the additive according to claims 1-2, characterized in that the sodium chloride or sodium chloride-containing substance mixture with a solution or
Colloid solution, suspension or emulsion of the additive is sprayed, ground or mixed. 4. A method for reducing or preventing the caking of sodium chloride according to claims 1-3. » characterized in that potassium hexacyanoferrate (II) and water-soluble zinc salts in a molar ratio
From 1 i 0.8 to 1: 1.4 can be used as an additive * GERMAN SOLVAY PLANTS
Company with limited liability MMI2 / 17 ··