DE1567580C - Process for the production of remote metal skates - Google Patents

Description

new, metal silicate pigments. Other advantages and Purpose of the invention emerges from the following description. . . , ._: '_; ... .

The present invention enables manufacture of metal silicates by converting oxides or hydroxides into divalent, basic ones Metal as well as mixtures of various such metal oxides or hydroxides with reactive ones

The invention relates to a process for io a new economical process for production

Production of mono-part metal silicates with one of metal silicate pigments available and with it particle size, in the diameter range from 0.025 to
5 microns of silicon dioxide, its BET surface area
.'at least in the range from 50 to 130 m ² / g
can, which is characterized in that you have a 15
aqueous slurry forms which is at least 1 mole
a metal oxide or hydroxide of barium, lead,
. Magnesium, calcium and zinc or their mixture to 4 mol of finely divided, reactive, phylloi-

The silica contains the silanol groups in silica in any desired molar ratio

a concentration of at least 1 micromol / m ² of metal oxide to silicon dioxide at increased

flat surface and a BET surface temperature and sufficient working time to achieve the

"has from 40 to 130m ² / g or. to complete silanol groups in a reaction

Concentration of at least 20 micromoles / m ^{2 of} flat different metal oxides and hydroxides with different surface area and a BET surface area of 300 25 dene reaction times to allow the formation of the corresponding

up to 500 m ² / g has to lead the slurry to 100 to 175 ° C chenden metal silicate to the end. One

heated to the end of the reaction and the product slurry of calcium oxide and reactive

wins. "According to silicon dioxide, for example, reacts at room temperature

A phylloidal (sheet-like) silicon dioxide that. slowly, but can, by heating the reaction, contain a certain minimum amount of silanol group suspension for 1 hour to about 100 ° C in 1 hour, is fully implemented in German Patent 1,224,282. A response not suggested. In addition, zinc oxide and reactive substances are used in the slurry. The method according to the invention temperatures of 100 silicon dioxide on the other hand requires a continued up to 175 ° C applied, whereas in the German patent heating to about 100 ⁰ C of 8 hours duration; around tentschrift only a temperature of 90 ⁰ C is mentioned. 3g to complete the implementation. At atmospheric

The pressure obtained in the process according to the invention is that for the complete course of the reaction

ten, new reaction products are finely divided, required times usually between 1 and 8 hours,

pigment-like materials, which are predominantly produced by heating

Metal-silica composition are formed. possible under pressure. In the case of a reaction slurry

and with a grain size in the diameter range 40 mung of zinc oxide and reactive silicon

from 0.025 to 5 microns. These pigments, for example, can lead to a complete reaction

are usually white in color, but without, in boiling at a pressure of 8.4 to 9.8 atmospheres

depending on the starting materials, limited to this, less than 4 hours can be obtained. A rea-

to be. , 'tion slurry of lead oxide and reactive

These reaction products can be for one, Rather ₄₅ enabled silicon dioxide, the full environmental

It can be used for purposes such as paper and rubber compounds as fillers for setting at atmospheric pressure, conditioning agents for powdery substances, including common salt, chemical cleaning agents,
phosphorescent compounds, ceramic bodies, 50
Catalysts, ⁷ anti-caking agents and light stabilizers

for plastics, in paints and other protective coatings, as an extender for primary pigments, such as titanium dioxide, in paper, paints, caoutchouc or rubber compounds and plastics.

Due to the considerable, commercial need for finely divided, inorganic pigments, such as metal silicates, Many methods for the production of these substances have already been developed. So this pigment

2- requires to about 100 ⁰ C to 4stündiges heating can be completely implemented within one hour by cooking at 8.4 to 9.8 atm pressure.

Many finely divided, silicon dioxide-containing substances are unsuitable for use under the conditions according to the invention. The silica must be one finely divided, reactive silicon dioxide, like the product according to the Belgian patents 623 366 and 624155. These silicas Substances are obtained by adding strong mineral acids with calcined or uncalcined clay implements carefully controlled conditions.

The described in the above patents,

art ζ. B. through chemical reactions in the vapor-reactive, silicon dioxide-containing substances are phase, chemical precipitation methods, sublimation-fine, discrete particles phylloidal (leaf or niken and high-temperature solid phase melt reactant-shaped) form, which generates a large ratio of ions . Have or are thin due to high cost or width to thickness. These methods can be used to determine analytically inferior quality products if they contain reactive silicon, at best classified as not completely satisfactory 65 dioxyde-containing substances up to about 85% SiO ₂ , but due to the need for such other oxides in an amount not exceeding 15 % before pigments, these production methods have been used, despite lying and at least 5% bound water of their defects. are present. The reactive, silicon dioxide

Like substances are further characterized by the fact that _ Example

their total surface up to 90% due to the measurable ■

Porosity is formed in the elementary particles. 47 g of reactive silicon

The BET surface area (surface, determined according to dioxide, obtained according to Example A of the Belgian Brunauer, Emmet and Teller) of this phyl- 5 patent specification 623 366 in 1275 g of water with 178 g of loidal, reactive, silicon dioxide-like substances Ba (OH) ₂ · 8 H ₂ O on ,. heated to 100 ° C, this is maintained by the materials.dieaus uncalcined kaolin temperature for 2 hours, cools the reaction -. clay are obtained, generally in the range of \ mixture from, the product wins by filtering and 40 to 130 m ² / g and dries from calcined kaolin clay. The product is a white, fine 'powder'. "Obtained in the range from 300 to 500 m ² / g. For the io that 1 mole of BaO combined with 1 mole of SiO ₂ contains. And.;" - Determination of the BET surface area compare "BET a BET surface area of 6.1 m ² / g 'without measurable ^ Pp-; 5 multilayer absorption theory", Journal of the rosity. .... /. ; · ._ .. ";:; ί: '>> ??:: Α ^ ΐ-ΐ:

American Chemical Society, Vol. 60, p. 309 (1938). '... Example ' 2 ■ '■ "^ S ^ - ^' ίτ:

Structurally, the reactive, silicon-di-. -. ··.,. * _^: .. ■ '■' ■. '^ - C ^^: -. ^^'

Oxide-like substances are further characterized in that 15 "The procedure of Example 1 is carried out with the exception of; it repeats the silicon, hydrogen and oxygen atoms, changing the reaction time to 4 hours; an orderly laminar arrangement The resulting product is similar to that of Example 1, which means that the individual particles have a porosity of the phylloidal shape and their - 14% and a BET -Surface of 6.1 mVg.'ii. ^ I ^ vr ^ surface reactive silanol groups (SiOH) 2 ° - _R .. J, ■ '"' y '^ ir ^^^ t -' ^ '

at a concentration of at least 1.0 micromoles / _. ^eis P ..... '- · - ;;.; :: · ■. · ■

m ^{2 of} their flat surface or particle-forming The procedure of Example 1 is carried out under "

Surface. · Dung of 59.3 g of reactive silicon dioxide and

It is assumed that the possibility of 165.7 g of lead oxide, slurried, in 1275 g of water, -this phylloidal, reactive, silicon dioxide- repeats itself with the modification that the reacting substances with oxides and hydroxides two-time 4 hours is stretched. As a product of valuable, basic metals to finely divided metal, there is a white, fine powder that converts 1 mol of PbO with silicates according to the invention, of which 1 mol of SiO ₂ combined and a BET surface area of these reactive silanol groups of 14, 6 m ² / g, which could add up to 9% porosity. ... 30 declines. .

For the purposes of the invention, the compounds are. Eg i 4 '

gen CaO, MgO, ZnO, Ba (OH) ₂ and PbO as well as na-.,. .:.

naturally occurring mixtures of different, the-. ,. , 78 g of the belser according to Example B are slurried Oxides, e.g. burned dolomite, suitable: gischen patent specification '623 366 product obtained in ·,' ·.

The products according to the invention are characterized by 35 1275 g of water with 147 g of Ba (OH) ₂ -8 H ₂ O, heated further by the fact that they are finely divided powder pigment. to 100 ⁰ C, this temperature maintains 2 hours, ■ represent nature, where at least 60 to. Cool the reaction mixture then off, the product _v 1ÖO ° / _O wins the BET surface of each particle of one. by filtering and drying. The product is a flat surface formed with any white, fine powder containing 1 mole of BaO with 2 MoI _- SiO ₂ . Residual surface is due to pores. The combined 40 and having a BET surface area of 17 m ² / g BET surface areas of the products are comprises of the training that goes back to 18 ° / ₀ in porosity .: J; . raw materials and are between 40 and ... .._,. .

500 m ² / g. The particle size of the products varies tfeispieio. . now diameters of 0.025 and 5 microns. The procedure of Example 4 is repeated with the morphology of the products depending on the change in phylloi, that the reaction time to the silicon dioxide-like reactants is from 4 hours. expands. As a product falls a fine one, and resembles its morphology. The chemical additive - white powder, which contains 1 mol of BaO with 2 mol of SiO ₂ composition of the products depends on the agreement and has a BET surface area of on average residual metal oxide content, generally up to about 22 m ² / g , the. 21.5% is due to porosity. 15% arLAl ₂ O ₃ , of the phylloidal silicon dioxide and 5 ° - -

the metal reaction '·· ■ -';; ~ B eis ρ ie 1 6 ■ -. ""'.'"*

participant. As predominant compositions ". ', ... · ■. _-

in the method according to the invention '/ In the procedure of Example 4, 94 g of metal silicates are obtained. "X-ray diffraction tests: reactive silicon dioxide and 131 g of PbO. · Investigations have shown that these products are new 55 slurried in 1275 g of water. The products are products and are normally crystalline; a white, fine powder is obtained, the 1 mole of PbO with: the magnesium silicate product, on the other hand, appears to contain 2 moles of SiO combined and a BET surface area amorphous ^.: '"; ^l . '·'. .. of 21.2 m ^s / g, which is 14% due to porosity - "

The degree of crystallinity. and the crystal size that goes. ■; .. ΐ · ;; Ι; Λ ■., - :.:; ί- ^ β-φΙ-μΆΚ: / .: reaction products depend to a certain extent 6o -Example 7 - ^ SS ^ SH .: "

on the reaction time and purity of the reactive - ^-:; - '' ■ '': ■ '■ - -' - ' ';;'¥:-i.'L ^ i4 · -

capable of phylloidal silicon dioxide. The procedure of Example 4 is carried out using. the .Abeine reaction has occurred or not, can be repeated by changing the reaction time to a comparison of the BET surface area of the products is extended to 4 hours. The product obtained is a white powder, 6g of fine powder from a dry mixture of the reactants, which contains 1 mol of PbO _{solidify with 2 mol of SiO 2} and has an average BET surface area. The following examples serve to further explain / g has an average of 11.5% on tion of the invention. Porosity decreases.

Example 8

The procedures of Examples 1 to 7 are followed by replacing the reactive silica equimolar amounts dos reactive, phylloidal Repeated silica obtained according to Example A of Belgian patent 624155. In in each case a white, fine powder is obtained.

■ Example.9

* Man'schlämmt 195 g of the filtered according to Example B of the Bel • cal Patent 623,366 the obtained reactive Siliciumdioxydes in 21 water, adding 105 g of MgO added, "the reaction mixture heated to 10O ⁰ C, kept at this temperature 2 hours upright, The product is a white, fine powder which contains 1 mol of MgO combined with 1 mol of SiO ₂ and has a BET surface area of 425.8 m ² / g, 32% of which is due to porosity .

- - ■

Example 10

The procedure of Example 9 is repeated with the modification that the reaction time is extended to 4 hours. The product obtained is a white, fine powder which contains 1 mol of MgO _{reacted with 1 mol of SiO 2} and a. Has a BET surface area of 433.6 m ² / g, 36% of which is due to porosity.

Example 11

In the procedure of Example 9, 237 g of the reactive silicon dioxide and 63 g of MgO are used. The product obtained is a white, fine powder which contains 1 mol of MgO with 2 mol of SiO _? contains combined and has a BET surface area of 344.3 m ² / g, 18% of which is due to porosity. ...

Example 12

The procedure of Example 11 is carried out with the ab-. Change repeats that the reaction time is extended to 4 hours. A similar product is obtained, but its BET surface area is increased to 364.3 m ² / g.

Example 13

Slurry 207 g of the obtained according to Example C of beigischen Patent 623,266, reactive Siliciumdioxydes in 21 water, is added 105.6 g of ZnO, the reaction slurry heated to 10O ⁰ C and keeping it for 8 hours this temperature, the reaction mixture filtered, wins the precipitate and dries. As a white product precipitated, fine powder of, ent united 1 mole of ZnO with 2 moles of SiO ₂ holds ^v and a BET surface area of 54.7 m ² / g has, going back to 9% porosity.

■ · .--; ._ ... - B e i s ρ i e I 14

Slurry 134 g of the siliciumdioxydartigen product 'of' Example B Belgian Patent ■ - ■ 623 366 in 400 ml of water, are added 108.5 grams of lime, the reaction mixture is heated to 1OQ ⁰ C and keeps it for 1 hour at this temperature, the product is recovered by filtering and drying. The product obtained is a white, fine powder which contains 1 mol of CaO combined with 1 mol of SiO ₂ .

Example 15

The procedure of Example 14 is repeated using 54.25 g of lime. The product obtained is a white, fine powder which contains 1 mol of CaO combined with 2 mol of SiO ₂ .

B e i s ρ i e1 16

16.3 kg of the product from Example A of Belgian patent specification 623 366 are slurried in 127.0 kg of water, 6.4 kg of dolomite lime (an equimolar mixture of CaO and MgO) is added and the reaction mixture is heated. to 10O ⁰ C, kept at this temperature 4 hours upright, the product is isolated by filtration and dried. The product obtained is a white, fine powder which, when combined, contains a total of 1 mol of CaO · MgO combined with 2 mol of SiO ₂ and has a BET surface area of 194.2 m ² / g, with no measurable porosity being present. ■ ■ ■ · --- ■ .-> ■ '.

In the present example, a natural mixture of calcium and magnesium oxides is used; an artificial mixture - delivers the same results. "· ■ · ■ ''■■;■" - ■ "■■■■ · ■■ ' ■.: -'.:. :: '■■ ?. ν: -: '''

At spieK17 · '.-' "''. '" ·. "' ''

The procedures of Examples 9 to 16 are repeated, replacing the silicon dioxide-like material with an equimolar amount of the product from Example C of Belgian patent 624155 (in which the kaolin clay is ^{calcined at 80O 0} C for 2 hours). In each case a white, fine powder is obtained which corresponds to the products of Examples 9 to 16. . .. ■■ .. ■

Example 18. ',.' ",;.;

177 g of the silicon dioxide-like material (obtained as in Example C of Belgian patent 624155 with calcining kaolin clay at 80O ⁰ C for 2 hours) are slurried with agitation in 1333 mol of water in a 3-1 beaker provided with a stirrer 51 g of added MgO which Geraisch heated to 10O ⁰ C, kept at this temperature 4 hours upright, the product was filtered off and dried. The product obtained is 212.7 g of a white, fine powder which contains 1 mol of MgO combined with 2 mol of SiO ₂ and has a BET surface area of 452.5 m ² / g. .

B e i s ρ i e 1 19

1135 g of the reactive silicon dioxide obtained according to Example C of Belgian patent specification 623 366 and 586 g of zinc oxide are slurried in enough water to obtain a slurry with a solids content of 15%, and the reaction mixture is boiled for 1 hour at 172 ° C and 8.4atü. ¹ pressure, the product filtered off and dried. The product is a white, fine powder which contains 1 mol of zinc oxide combined with 2 mol of SiO and a BET surface area of 47.9 m ² / g. _N ....; ... V ^;

For example, the procedure of Example 19 is repeated with the modification that the reaction time is extended to -4 hours. A white,. fine powder which contains 1 mol of zinc oxide combined with 2 mol of SiO ₂ and has a BET surface area of 51.5 m ² / g. -

At game 21

497 g of the reactive obtained according to Example C of Belgian patent 623 366 are slurried Silica and 692 g of PbO in enough water. to create a slurry with a solid

55

^To obtain a substance content of 15%, the reaction mixture boils V? Hour at 175 ° C and 9.1 atmospheric pressure, the product is filtered off and dried. The product obtained is a white, fine powder which contains 1 mol of PbO combined with 2 mol of SiO ₂ and has a BET surface area of 8.2 m ² / g.

Example 22

The procedure of Example 21 is repeated with the modification that the reaction time is extended to 2 hours. The product obtained is a white, fine powder which contains 1 mol of PbO combined with 2 mol of SiO ₂ and has a BET surface area of 8.1 m ^a / g.

B e i s ρ i e 1 23

675 g of the reactive silicon dioxide obtained according to Example C of Belgian patent specification 623 366 and 1300 g of Ba (OH) ₂ · 8H ₂ O are slurried in enough water to obtain a slurry with a solids content of 15%, and the reaction mixture is boiled 2 hours at 172 ° C. and 8.4 atmospheres pressure, the product is filtered off and dried. The product obtained is a white, fine powder which contains 1 mol of BaO combined with 2 mol of SiO ₂ and has a BET surface area of 47.9 m ² / g.

Example 24

Was slurried in 1125 g of the in accordance with Example C of Belgian Patent 623,366 the obtained reactive Siliciumdioxydes and 296 g of MgO in enough water to produce a slurry having a solids content of 15% ^to obtain the reaction mixture boiled for 2 hours at 172 ⁰ C and 8, 4 atmospheric pressure, the product filtered off and dried. The product obtained is a white, fine powder which contains 1 mol of MgO combined with 2 mol of SiO ₂ .

Claims (5)

Patent claims: 1. A process for the production of finely divided metal silicates with a particle size in the diameter range from 0.025 to 5 microns from silicon dioxide, the BET surface area of ^{which can be at least in the range from 50 to 130m 2} / g, characterized in that an aqueous slurry is formed which contains at least 1 mol of a metal oxide or hydroxide of barium, lead, magnesium, calcium and zinc or their mixtures per 4 mol of finely divided, reactive, phylloidal silicon dioxide, which contains silanol groups in a concentration of at least 1 micromol / m ^{2 of} flat surface and a BET -Surface of 40 to 130 m ² / g or silanol groups in a concentration of at least 20 micromol / m ² flat surface and has a BET surface area of 300 to 500 ^{m 2} / g, the slurry to 100 to 175 ⁰ C up to The reaction process is heated and the product wins. 2. The method according to claim 1, characterized in that one of a 1 mol of the metal oxide or hydroxide on 1 to 2 moles of silica-containing slurry. 3. The method according to claim 1, characterized in that that a mixture of calcium and magnesium oxide is used in the proportions contained in the burned dolomite. 4. Process according to claims 1 to 3, characterized in that the slurry heated to 100 ° C. 5. Process according to claims 1 to 4, characterized in that the slurry boils at a pressure of about 8.4 to 9.8 atmospheres. . 009 585/360