DE1542190A1 - Additives for minerals - Google Patents

Description

W.R. Grace & Co.

Cambridge, Mass. A »3t, Λ. Hamburg, July 10, 1969

Additives for minerals

The present invention relates to additives for improvement the grinding action bites] Grinding of minerals and preventing them from sticking or sticking together of minerals.

When processing minerals, a grinding process is usually required at some point in the process, to make the mineral into relatively small particles crush. The aim is to get the mineral to the desired particle size at a relatively high speed to marry. In general, a grinding aid is added to improve the grinding performance, as a result of which either the production speed increased or the fineness of the with the same production speed Product is increased without adversely affecting the properties of the millbase. When splitting the Particles during the grinding of minerals are exposed to fresh or nascent surfaces, which, likely by breaking ion bonds, have high energies. The surface forces of the ground Particles continue to have an effect long after the grinding process further and, if they are not reduced, lead to compaction or setting and / or worse FlieÖ- or pourability of the product, MLnoralpartchen,

f! C) ^c l 8 Γ? / I j 7 2

bad ^λγ " ^λ " · '' · ^u * *

which turn compacted due to vibrations, for example during transport in a hopper wagon, often form semi-solid Masses that can only be made flowable again by applying considerable mechanical forces. On the other hand, there is too much of a decrease or complete elimination of surface dispensing forces is undesirable, since the finely ground mineral then overshoots "; becomes liquid.

Under "Pestsetzen" the products. In the present Description the agglomeration or caking of Particles, for example, when storing or transporting understood as bulk goods. The sticking together of the parts is based on surface force, most of which are caused by Grinding the minerals arise. The "Pest Sets Index" .is a relative value that indicates numerically how it spawns or how heavy it is stored or transported as bulk material became · The "Fixing Index Ratio" is the ratio between the pestseta indices of the untreated and dar treated sample. With this ratio a comparison between different samples of the same mineral is possible. The plague index is determined in the following way: 100 g of mineral are poured into a 250 ml ErI enmeyer flask an adjustable shaker for 15 seconds. Then the piston is removed from the vibrator, clamped with a horizontally lying axis and rotated around its axis until the piston at the bottom of the 3 piston is too tight Cake compacted mineral collapses. The piston will rotated 180 ° about 100 times per minute. The Plague Index is the number of times the mineral cake collapses required 180 ° turns. So that means the larger the egg eggs required to destroy the cake, the higher the plague setting index,

η f) 9 H! 3 / J 3 7 2 '^

An additive has now been found, which one? as a grinding aid and as a fixative for minarals works *

With the invention, accordingly, assurances are made suggested ^ the one mineral and one intimate with it mixed compound of the general formula

R ²

EK (Λ)

in which R is an aryl radical or a substituted aryl radical, with the exception of a sulfonic acid-substituted hanthyl radical. R is a hydrogen atom or an alkyl radical and R ^ is Hydrogen atom or a hydroxy, allyl · · or aryi ^ est is, or the general formula

NR ⁵ (B)

π-ι

in the H N a substituted or not substituted

L J

ter pyrrole idyl, pyrrolyl, morpholine! - ,, morpholine or Plperidyl radical and R- * a hydrogen atom, an Al'.qrl-, Alkoxy or Kydroxyalkylrest is »or a general term» formula

in which Y is a pyridyl, piperidyl, pyrimidinyl or pyrazidinyl radical, η = 1 to 5 and R is a halogen atom, a hydroxy or alkyl radical, or - if η = 1 - is a hydrogen atom ,

or the reaction product of a compound of the formula (A) -, (B) or (C) with an aliphatic organic acid having 2 to 20 carbon atoms or an anhydride of such an acid.

0 0 9 8 13/1372 BAD WW

In these compounds, R is preferably an alkylphenyl or phenyl radical. The aryl radical can contain substituents such as halogens, for example chlorine and bromine, or alkyl, amino or hydroxyl groups. The alkyl groups R ² , R · ⁵ , R ^ and R ° are preferably lower alkyl radicals, ie with 1 to 6 carbons. The substituted pyrrolyl, pyrrolidyl, morpholino, morpholinyl and piperidyl radicals can be selected from the known radicals such as H- Methylmorpholino and 4- (2-aminoethoxy) äthylmorpholino exist.

The additives of the formulas (B) and (C) are preferred because these classes of compounds have particularly good properties as anti-sticking agents and at the same time improve the grinding performance.

As examples of the additives which can be used according to the invention the following compounds can be mentioned in particular: aniline, p-toluidine, m-phenylenediasnine, dimethalaniline, Diphenylamine, 2, ^, 6-tribromaniline, N-phenylhydroxylamine, ß-phenylethylamine, morpholene, pyridine, Piperidine, pyrrole, pyrroline, pyrrolidine, pyridazine, pyrimidine, N-methylmorpholn, dimethylpyridine, dimethylethylpyrrole and piperazine.

The additives can be used together with the mineral in the Mill are ground to improve the grinding effect and to achieve other beneficial results, such as the settling of the product stored as bulk goods or the formation of foam in some mineral processing operations to prevent. It has been found that the additives to the ground minerals also provide the necessary Flow properties during transport in conveyor systems, especially in compressed air systems.

009813/1372

The term "mineral" in the present Description naturally occurring inorganic minerals such as phosphate mineral, some of which are processed Minerals such as fortified iron ore and mineral oil blends understood as cement clinker or ceramic masses. Other suitable minerals are Berylliurnoiiyd, limestone, Plaster of paris, clays and bauxite. Particularly good results are achieved with cement and cement-forming substances * in particular Portland cement. Portland cement is a class of hydraulic cements which is used in the consist essentially of two calcium silicates and a smaller proportion of calcium aluminate · These cements are produced by an intimate mixture of fine-grained lime material (limestone) and clay material (Clay) heated to melt, resulting in a clinker. The clinker is then plastered with about $ 5 or one grind another form of calcium sulfate to the desired one A. To maintain binding properties in the finished cement. The new proposed with the present invention Additives are preferably added to the clinker, to improve the grinding action and a subsequent one To prevent the finished cement from setting.

The additives according to the invention are either in used dry or in liquid form. In order to be able to meter the additive precisely into the mineral stream, it is best used in liquid form »additives, which are not very water-soluble can be emulsified with a suitable wetting agent such as Sodium dodecylbenzenesulfonate can be brought into liquid form. The additive can either be before Grinding added or introduced into the grinder at the same time as the mineral. If the additive only to prevent the seizure and to flow

0098 13/1372

is used, it can be used at any for this purpose a suitable place to be added to the processing procedure

The additive according to the invention can be used as the only grinding aid or in a mixture with one or more other grinding aids or with other known additives such as the setting retarders or accelerators used in cement! be used.

The additive can be used with good effect in a wide range of concentrations. The preferred one Range is about 0.001 to 1 wt. # And in particular about 0.005 to about 0.1 wt. ^, Based on the mineral weight, d.ho weight of additional dry matter on weight of mineral dry matter (hereinafter referred to as TS on TS). In a particularly preferred embodiment, based on the mineral weight, about 0.05 wt all percentages on Gevr. #). The higher ones Amounts of additive become proportionate when grinding large surface area and the amount of additive is only required by the Surface size and the desired flowability of the product are limited.

The following Table 1 shows the effectiveness of the additives as grinding aids. The values reported were obtained by grinding of cement clinker and gypsum in a Type 1 Laboratoriumsmünle at 99 ⁰ C with 11 ^ 7 MUhlemiradrehungen.

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Table I. Surface size Additive Amount of additive according to Blaine, cm ² / g {% TS on TS) ? 44l Blank sample - 3505 aniline 0.01 3660 aniline 0.05 3480 Morpholine 0.01 3500 N-methylmorphol in 0.01 3570 p-toluidine 0.01 3542 Pyrrolidine 0.01 3515 Pyrrolidine 0.05 3499 Piperidine 0.01 3550 Diphenylarain 0.01

The following table 2 shows the setting indices for Cement, which together with additives according to the invention was married.

Table II

Additive Additive amount Pestsetz · index

{$ TS on TS)

Blank sample 0.05 12.6 aniline 0.01 10.0 Morpholine 0.05 11.3 Morpholine 0.01 2.0 N-methylmorpholine 0.01 11.3 p-toluidine 0.05 12.3 p-toluidine 0.01 4.0 Pyrrolidine 0.05 8.0 Pyrrolidine 0.01 1.0 Piperidine 0.05 9.0 Diphenylamine 7.3

00 98 13/137 2

In a particularly preferred Ausführung3f orm is used as an additive or a morpholine Morpholinylderivat "Besides, good results were obtained with different degrees of awareness Hein morpholine. A particularly preferred material for compounds of the morpholine type is a by-product obtained in the continuous industrial production of heterocyclic amines. This by-product contains a mixture of aliphatic and heterocyclic mono- and diamines. The dominant group, however, is the morpholinyl ring.

The following table 3 shows typical analysis values for a by-product, which consists mainly of a mixture of 4- (2-aminoethoxy) 8thylmorpholine, 2- (4-morpholyl-sthoxy) ethanol and bis-2- (4-morpholinyl) ethyl ether.

Table III

Titratable amine, meq / g 7 * 52

Primary amine, raXq / g 1.66

Tertiary amine, mftq / g 4.57

Total nitrogen, meq / g 7.93

Total acetylatable, meq / g 7 * 02

Specific gravity, 20/20 ° C 1.07β

Water content, w / w ^ 0.08

The following table 4 shows the grinding effect and the setting index when using the additive Table 3 · The values were obtained by grinding cement clinker type 1 and gypsum in a laboratory grinder 99 ° C obtained with 7411 mill rotations.

009813.7,1372

Table IV Fixing index Amount of additive
(J * TS to TS) surface size
after Blaine, em ² / g 12.6
1.0 0.05 3441
3605

From this table it can be seen that even if a very small amount of the additive is used, there is an improvement the grinding effect by about 164 units and a substantial reduction in the Pestsetz index is achieved.

The new additive according to Table 3 was also used for grinding phosphate mineral. Here, the phosphate mineral with 0.03% of this additive was ground 3752 revolutions mill at 93 ⁰ C in a laboratory mill. 61% of the grinded product passed through a Tyler 200 sieve (sieve opening 0.074 mm), while only 54 # went through a Tyler 200 sieve (sieve opening 0.074 mm) in the case of a comparative sample, which had been milled without additive.

Except for the amine compounds described above per se can also use their reaction products with aliphatic organic acids having 2 to 20 carbon atoms as Mineral additive to be used «These products are used produced by adding an acid, preferably glacial acetic acid, the pH value is lowered no further than about 7. In a preferred embodiment, the pH lowered to around 8. The acetylated amine acetate is obtained «if the acid anhydride is added to the amine instead of the acid ·

009813/1372

The following table 5 shows the use of the with Conversion of the amine according to Table 3 n * lt acetic acid (pH 8) obtained reaction product when grinding cement clinker. Cement clinker type 1 and gypsum 4 were used Grind 4095 revolutions in a laboratory mill heated to 93 ° C

Table V Fixing
index Air entrapment
according to ASTM CI85 Amount of additive
(JS TS to TS) Surface size
according to Blaine cnsr / g 6th
0 10.0
10.3 Blank sample
0.058 3590
3850

From Table 5 it can be seen that the Hahlwlrkung and the Fixing properties are improved and no air is trapped "

As already mentioned, the invention also relates on mixtures of additives. A particularly preferred one Mixture is made of dea AmIn according to Table 3 * triethanolamine and acetic acid. A preferred triethanolamine material is that used in the manufacture of ethanolamines residue product obtained. The exact composition this residual product fluctuates within certain limits; so the residue product in addition to triethanolamine mono- and / or contain diethanolamine · Such a residue product has, for example, before neutralization the following analysis values

0 0 9 813/1372 bad original

Table VI

Triethanolamine 45 to 55 % by volume

Equivalent weight 129 to 139

Tertiary amine 6.2 to 7.0 meq / g

Water max. 0.5 wt. #

Density 1.14 kg / liter

In the following table 7 the grinding effect is shown, when using the reaction product of acetic acid with a mixture of equal parts by weight of the amines according to Table 3 and Table 6 is achieved. The mixture had a pH of 8. Cement clinker was used for the tests Type 1 and plaster of paris at 1O5 ° C in a laboratory chair marry.

Table VII surface size
according to Blaine.ca / g Fixing
index Additive tightness
{% TS on TS) Mill
Revolutions 4270
4330
4400
4300 55
6th
7th Blank sample
0.012
0.018
0.025 7558
7343
6587

Another additional mixture, which is particularly suitable for the purposes of the invention, consists of 60 % of the additional mixture, the mill values of which are given in Table 7, 20 % of urea and 20% of water. Table 8 shows the mill values that when using a mixture of this type, cement clinker type 1 and gypsum are then ground in a laboratory mill

009813/1372

5092 revolutions at 1Q5 ° C and a concentration of Additive of 0.0 * l · # (TS to TS) were obtained.

Table VIII

Surface size

according to blaine, oravg index

Blank 3250 38.0

with additive 3599 1 * 5

This additive has the further advantage that it does not become too viscous at low temperatures »

The above description has primarily focused on the use of the additives according to the invention for grinding Cement clinker and phosphate mineral are described, however the additives are also with equally good results suitable for grinding other minerals.

009813/1372

Claims (5)

Claim 1 · Use a compound of the general formal R ² R? (A) in which R is an aryl radical or a substituted aryl radical, with the exception of a sulfonic acid-substituted naphthyl radical, R is hydrogen or an alkyl radical and R ^ is Is a hydrogen atom or a hydroxy, alkyl or aryl radical, or of the general formula R ⁴ NR ⁵ (B) I J I ₄ ι in which R N is a substituted or not subeti-IJ tuated pyrrolidyl, pyrrolyl, morpholinyl, morpholine or piperidyl radical and R- * is a hydrogen atom or is an alkyl, alkoxy or hydroxyalkyl radical, or of the general formula in the (C) in which Y is a pyridyl, piperidyl, pyrimidinyl or Pyrazidinylreat, η = 1 to 5 and R is a halogen atom, a hydroxy or alkyl radical, or - if η = 1 - a hydrogen atom, or of the reaction product of a compound of the general formulas (A), (B) or (C) with an aliphatic organic acid having 2 to 20 carbon atoms or an anhydride of such an acid BAD ORIQINAi. 009813/1372 -. as an additive to prevent feet setting or Caking together of minerals, in particular phosphate mineral, cement and cement-forming substances. 2. Use of an additive according to claim 1 in an amount based on the mineral weight of 0.001 to 1 weight £, preferably 0.005 to 0.1 Gevr, #. 3. Use of a compound of the general formula (Λ), in which R is an aryl or alkaryl radical and preferably a phenyl or alkylphenyl radical, as an additive according to claims 1 and 2. 4. Use of the implementation product of a connection general formula (A), (B) or (C) with acetic acid or acetic anhydride as an additive according to claims 1 and 2, 5. Composition consisting of an intimate mixture of a mineral (according to the definition above) with a Compound of the general formula in which R is an aryl radical or a substituted aryl radical, except for a sulfanic acid-substituted naphthyl radical ^ R is a hydrogen atom or an alkyl radical and Br is a hydrogen atom or a hydroxy, alkyl or aryl radical, or of the general formula R ⁴ NR ⁵ (B) IJ 0 0 9 8 13/1372 Γ * I in the RN a substituted or unsubstituted IJ tuated pyrrolidyl, pyrrolyl, morpholinyl, morpholines or piperidyl radical and R is a hydrogen at ora or a Is alkyl, alkoxy or hydroxyalkyl radical, or of the general formula in which Y is a pyridyl, piperidyl, pyrimidinyl or Pyrazidinyl radical, η * = 1 to 5 and R a halogen atom, a hydroxy or alkyl radical, or - if η = 1 - a Is hydrogen atom, or the reaction product of one Compound of the general formulas (A), (B) or (C) with an aliphatic organic acid with 2 to 20 carbon atoms or an anhydride of such Acid· coll: wy 009813/1372