DE1810571A1 - Process to prevent stone-forming deposits in aqueous systems - Google Patents

Description

üoh. A. Benckisisii GrobH * t »7 Ludwcsnaien / nhein 3 P ° ^s * fac" 1 81 057 1

Telephone * * 590 31 · Telephone code 0621 Telegraph 0464372 ζ jab d Wire address Benckiser Ludwigshafenrhsin

Pat / Dr.B / Pa - 6h2 - November 15, 1963

"Procedure for the prevention of 3 tons of forming deposits * in aqueous systems "

The present invention relates to a method for preventing stone-forming deposits in aqueous media 33 ^ s tem en. ■

To prevent stone-forming deposits in aqueous systems, polyphosphates in particular are used extensively today Dimensions used. Polyphosphates - are mainly used because they are already in sub-stoichiometric amounts, So-called vaccination quantities work and are relatively cheap. It is known, however, that the polyphosphates under Can hydrolyze under certain circumstances in aqueous solutions, whereby the consumption of polyphosphates is sometimes relatively high and the effect is often no longer satisfactory.

As complexing agents, which can be kept indefinitely in aqueous solution and which also form stone-forming substances in sub-stoichiometric amounts Prevent deposits from having in the. In recent years the aminoalkylenephosphonic acids have become increasingly stronger Gained importance. SiG are used because of their resistance to hydrolysis mainly used in aqueous systems. So can they added, for example, liquid cleaning solutions different storage conditions are available in these solutions durable for a long time. The phosphonic acids, however, have the greater part than the polyphosphates relatively expensive sir.d, due to that in and of itself expensive starting materials.

M 2 - '

008826/1733 bm> o «qjn«.

4.23a rovrqr äO £ 03

-Joh. A. Benckiser d-.tbH - G7 Ludwig! slhsfan / Flhein 3

Telephon ** 59031 > prefix 0621 Telegraph 0464872 ζ Jab d wire address Benckiser Ludwigshafenrheiri

- 642 -

It is also already known that 3 dextrins, which are produced by treating starch with acids and subsequent roasting, that is, heating the pretreated starch to temperatures of 150 to 20O ⁰ Cj, prevent the deposition of stone-forming deposits.

Surprisingly, it has now been found that stone-forming Deposits in aqueous systems are also prevented, when one receives modified starches which are obtained by treating starch with acids or by the action of oxidizing agents below the gelatinization temperature alone or in a mixture with aminoalkylenephosphonic acids in sub-stoichiornetri saw quantities (vaccination quantities), based on the hardeners.

It was not to be expected that the inventive modified Starches have a hard-stabilizing effect, as they are chemically different in comparison with the dextrins Products. Thus the modified starches of the invention are partially hydrolytically cleaved and partially oxidized starches, while the dextrins are only formed in the roasting process that follows hydrolysis, in which it nor to intra- and intermolecular condensations and polymerizations comes.

The concentration in which the modified starches according to the invention are added can be up to 500 mg / l of water, preferably 10 to 30 mg / 1 V / water.

The modified starches can be prepared according to known methods by adding starch swellings a certain amount of acid, such as hydrochloric acid, nitric acid, sulfuric acid, and.

QQ 98 2 * Original _{on BA 0}

Joh. A. Benckisor GmbH < 67 LucSwigsfrafen / Rhein 3

Telecall ** 590 31 · Tel prefix 0621 Telegraph 0464872 r jab d Wire address Benckiser Ludwigshafenrhein

- 642 -

Heated to half the gelatinization temperature until the desired Degree of degradation has been reached. Depending on the concentration of the acid added, this takes 4 to 9 hours. The concentration of the acids can for example be 1/10 n to Be 2n and higher. Then the aqueous suspension is neutralized, the starch is sucked off, washed out and dried in the air or in a drying cabinet at 40 to 45 ° C. But you can also use the starches with oxidizing agents, such as sodium hypochlorite according to the Ullmanns Encyclopedia of Industrial Chemistry I967, Volume 16, Page 343 treat the method described. The ones with sodium hypochlorite treated starches are easily soluble in water, which is advantageous for many purposes, especially when you want to produce concentrated solutions that are only adjusted to the required application concentration on site.

The modified starches can be obtained from different types of starch, such as potato starch or corn starch will.

The hardness-stabilizing effect of the modified starches is increased if they are mixed with aminoalkylenephosphonic acids in a weight ratio of modified starch to aminoalkylenephosphonic acid of 1: 1 to 50: 1, preferably 4: 1 to 20: 1 in amounts of up to 500 mg / l of water, preferably 10 to 30 mg / l of water. It a synergistic effect is achieved with such mixtures, which far exceeds the effect of the individual .Substanzen goes out. According to the invention, suitable aminoalkylenephosphonic acids, for example diethylenetriamine-penta- (methylenephosphonic acid), Ethylenediamine-tetra-Cmethylenephos-

0098 26/173 3

«Joh. A. BanckiscrCtr.bH * 67JUudwiTc _J £, | -j; ji- © rj / i ^: 'äih »®jrr3

Remote call ** 59 0 31 · Remote code 0621 Telegraph 0464872 ζ jab d _ 2i _ Wire letter Benckiser Ludwigshafenrhein

- 642 -.

Phonic acid) , 1 , 2 Propylenedianine-tetra-'CinethyienphosphonGäure).,. 1, ^ - Propylenedlainine-tetra- (r.ethylenephosphonic acid) .. triethylene _t tetraraine-hexa- (iTiethylenphosphonsaur ^ e) ₃ Änino-tri- (r.iethylonphosphonsäure) _: 1 , 2 Cyclohsxandiaoin-tetra- (niethylenphosphon - acid) , 1-arninomethyl-cyclopentylamine (2) -tetra- (methylenephosphonic acid) and others.

The vaccination effect of the starches modified according to the invention sorie the synergistic effect of the combination of modified Strong with Aninoalkylonphosphonsäuren is based of the examples summarized in the following tables. are shown.

To determine the vaccination effect, a .determined amount (mg) of the substance or substance to be tested was dissolved in a 1000 ml-3schoi: · glass by boiling it in 1 1 '..' water of approx. 15 dli and after cooling, 12 g of sodium hydroxide were added. The beaker was' with a; ^1st Watch glass covered and. left to stand at room temperature. It was then checked whether a _: .i glass rod or at the junction of the 3ochergla: jes crystals had deposited.

-D-

00982 (5/1733 BADORIQiNAL

! Hill '■' ■■■

. A. Benclkiser Grnl ^ H ■ 67 Luclwi ^ & h & fen / Fihein 3

. P.O. Box 181057 1

Telecall ** 59 031 · Tel prefix 0621 Telegraph 0464872 ζ Jab d _ c _ Wire address Benckiser Ludwigshafenrhein

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Table 1
Irnpf'.rirkurig the modified starches

Amount days

4 6

g g

_fflg 2 4 6 8 10 12 U

Strength A:

Potato starch 7 at 40-45 C 20 --------

rait 1n KCl treated pQ 000000-

Strength 3:.

Potato starch 8 ⁿ at 40-4-5 C 12.5 0 ----- -

treated with 2n HCl ■ 20 - 0 0 0 0 0 _T -

Thickness C: _h

Potato starch 7 at 40-45 C 12.5 -------

rait 2n ENT ₃ treated 20 0 0 0 0 ---

Thickness D:,

Corn starch 7 at 40-45 C 12.5 0 0 ------

treated with 2n HCl 20 0 0 0 0 0 - -

Strength E: '

Potato starch rait KaOCl 12.5 0000 ---

treated (5 % active chlorine 20 000 000-on dry matter)

Strength F:

Potato starch rait NaOCl 12.5 0 0 0 - - - .-

treated (7.5 % active chlorine 20 0000000 on dry matter)

Thickness G:

Potato starch rait NaOCl 12.5 000 ----

treated (10; o active chlorine 20 0000000 on dry matter)

Thickness H:

Corn starch treated with KaOCl 12.5 0 0 0 - - - -

(5 fo active chlorine on dry matter) 20 0000000

+ Thickness J 12.5 -------

20 0000 --- ·

+ Strength K- .12.5 -------

20 0 0 0 0- 0 - -

+ Thickness L 12.5 - ------

20 00000--

'Untreated potato starch j50 -------

Untreated corn starch J> 0 -------

0 = no coating on the glass rod and the wall of the beaker class

- 6 -009826/1733

'up «" v ^la '' ^Λ

üoh. A.Benckicnv CJrnbH 57 l.-

P.O. Box

- 5 -

Remote call ** 59 0 31 · Remote code 0621 Telegraph 046-4872 ζ jab d Wire address Benckiser Ludwigshafenrhein

~ 642 -

+ The starches J, K and L are commercially available modified starches:

Starch J: corn starch below the gelatinization temperature, oxidatively degraded;

Starch K; Corn starch below the gelatinization temperature acidic degraded;

Starch L: Potato starch degraded under acidic conditions below the gelatinization temperature.

Tabel

Inoculation effect of aminoalkylenephosphonic acids

substance lot 1 Days
2 ^ 4 5 Diethylenetriamine penta-
(methylenohosphonic acid)
= DATPMP 2.5 mg 0 0 - - Ethylenediamine tetra
(methylenephosphonic acid)
= ÄDTMP 2.5 mg 0 - - _. - 1,3 propylenediarnine tetra
(ethylene phosphonic acid)
= PDTMP 2.5 mg - - - Amino-tri- (methylene- phosphonic acid.) d. ₉ ρ mg

= .no coating on the glass rod and the wall of the Bochergiasos,

0Q9826 / 1733

^{P.O. Box} 1 61057 1

Telephon ** 59031 · Tel prefix 0621 Telegraph 0464372 ζ jab d _ , γ Wired address Benckiser Ludvvigshafenrhein

- 642 -

Table 3

Impairment of mixtures of modified starches and Aminoalkylenphosphonscrareii

substance

Amount of days

im 2 4 6 8 10 12 14 16 18 20

Thickness A (Tr.belle 1) 10.0 0000000000

ADTMP 2.5

Starch C (Table 1) 10.0 OOO00000--

DATPIiP 2.5 υυυυυυυυ--

Thickness D (table 1) 10.0 0000000 ---

PDTMP 2.5

Starch E (Table 1) 8.0,000,000,000

DaTPwP 2.0 0000000 ---

Thickness P (table 1) 10.0 00000000--

Amino-tr i- (never ethylene- 2,5 υυυυυυυυ--

phophonic acid)

Thickness G (Table 1) 10.0 η η r \ r, η

ÄDTMP 2,5 UULUU -----

oooooooooo

KSS ^K < ^{Tabclle 1} > ¹ ^ ooo o. O o. Ooooo

Thickness L (table 1) 11.25 0 000 000 000

DÄTPMP 1.25

0 = no coating on the glass rod and the wall of the beaker,

009826/1733

■ Joh. Λ. Benckiser Crtniri-S '67! L

181.057

_O
- O -

Remote call ** 59 0 31 · Remote preselection 0S21 Telex 0464872 ζ jab d wire address Benckiser Ludwigshafenrhein

- 642 -

The products listed in the tables above of course also with your own pl-i-v; ert d-it wassers a good stabilizing effect on * it was however in the alkaline area worked * to the beneficial Stabilizing effect of the products according to the invention to show in such a milieu as is the case with very many Cleaning operations is required.

The products according to the invention can in particular be added to acidic or alkaline cleaning solutions. The use of the products is particularly advantageous, for example in automatically operating bottle washers or when cleaning tanks and containers. -Here especially occurs when rinsing with water, i.e. in the stage of Cleaning process in which only traces of the cleaning agent are present, which are diluted with a lot of ".-" water and. be washed out, easily a stone deposit. This stone separation is done with small amounts (inoculation amounts) of the products according to the invention, the ir: the rinsing solution are present, prevented. In cases where it is necessary, a small amount of additional dosage can be added to the product Stone separation is carried out in particularly endangered zones.

Suitable cleaners can, for example, include the following Own settlement:

example 1

40 'p acidic monophosphoric acid alkyl esters with C ^ to C ,, 10 p of the erfindur.gsge.-r.aSen combination of modified starch and A: r.inoalkyl.enphosphonic acid, 1 O> S antifoam and rust V / water.

009826/1733

BATH ORIGINAL

Joh. A. BenckissrOmlcH * 67 L

1 81 Q B

Telephone * * 59 0 31 · Telephone code 0621 Telegraph 0464872 ζ jab d - ^ - Wire address Benckiser Ludwigshafenrhein

~ 642 -

0.3 % of this mixture is added to 1% sodium hydroxide solution. The detergent solution can be used to rinse the bottle.

Example 2

50 % 67% gluconic acid solution, 20 γ> a starch treated with NaOCl and the Res.t V / water.

0.2% of this mixture is introduced into 1-cell sodium hydroxide solution and the solution can be used to rinse the bottle.

Beispi el J>

35% sodium silicate, 3% of a treated starch with hydrochloric acid, 20 fo soda, caustic soda I7 fi, fa 5 wetting agent, 10 # and 10 fo Natriurnsulfat Trinatriumrnonophosphat.

Some solutions of the mixture can be used to clean the milk can can be used.

- 10 -

009826/1733

Claims (5)

Jioh. A. Benckieer CJmbH «67 LudwigsCiafen / Rhein 3 Fernruf ** 59 031 · Phone code 0621 Telegraph 0464872 ζ Jab d wire address Benckiser Ludwigshafenrhein -10- - Patent claims 1. A method for preventing stone-forming deposits in aqueous systems, characterized in that one by treatment with acids or by the action of oxy- ■ agents below the gelatinization temperature modified starch obtained alone or in a mixture with aminoalkylenephosphonic acids in substoichiometric amounts Quantities (inoculation quantities) based on the hardness components of the water. 2. The method according to claim 1, characterized in that the modified starch in amounts of 2 to 500 mg / 1 water, preferably 10 to 30 mg / l of water is used. 3. The method according to claiml, characterized in that there is a mixture of modified starch and aminoalkylenephosphonic acid in a weight ratio of modified starch to aminoalkylenephosphonic acid of 1: 1 to 50: 1, preferably from 4: 1 to 20: 1, in amounts of up to 500 mg / l of water, preferably 10 to 30 mg / l of water. 4. The method according to claim 1 and 3 _9, characterized in that one aminoalkylenephosphonic acids, preferably diethylenetriamine-penta- (methylenephosphonic acid), ethylenediamine-tetra- (methylenephosphonic acid), 1,3 propylenediamine-tetra (methylenephosphonic acid), amino-tri- (methylenephosphonic acid) ) starts. 5. The method according to claim 1 to 4, characterized in that modified starch alone or in a mixture with Aminoalkylenephosphonic acids together with cleaning solutions begins. 009826/1733