JPS60161729A - Dispersant and composition of antimony oxide - Google Patents

Abstract

PURPOSE:To provide a dispersant capable of stably dispersing antimony oxide in a hydrophobic org. solvent at a high concn., constituted of an oil soluble anionic surfactant such as sulfonate, sulfuric ester or carboxylate. CONSTITUTION:A dispersant for dispersing antimony oxide in a hydrophobic org. solvent consists of an oil soluble surfactant selected from sulfonate, sulfuric ester and carboxylate, and if necessary, a phosphorus-containing oil soluble surfactant and can form a stable antimony oxide dispersed liquid composition. As the above mentioned sulfonate, sulfosuccinic ester and/or alkylbenzene sulfonate are especially preferably used. The stable antimony oixde dispersed liquid composition formed by containing 0.05-30wt% of the above mentioned dispersant, 10- 50wt% of antimony oxide such as Sb2O4 or Sb2O5 and the hydrophobic solvent can be used in the fire retardant treatment of plastics or the deterioration inhibitting treatment of the fluidized catalytic cracking catalyst of a heavy oil fraction.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to antimony oxide dispersants and compositions. More specifically, the present invention relates to a dispersant and a dispersion composition capable of stably dispersing antimony oxide in a hydrophobic solvent at a high concentration.

Antimony oxide is used as a clutter treatment agent for plastics and fibers, as an additive in the production of glass and ceramics, and as a raw material for glassy enamel. It has recently been discovered that by depositing antimony oxide on catalysts for fluid catalytic cracking of heavy petroleum fractions, deterioration of the catalytic action by metals such as nickel can be prevented.

A method for depositing antimony oxide on a catalyst for fluid catalytic cracking is to dissolve an organic compound containing antimony in heavy petroleum fraction, which is the raw material for fluid catalytic cracking, and subject it to a catalytic cracking reaction at high temperature to convert it into inorganic antimony. A method has been adopted in which the catalyst is deposited on the catalyst.

However, this method requires the production of an organic antimony compound. Another problem is that in order to dissolve antimony in petroleum fractions, the antimony compound must have a fairly noble (bulky) organic group, and organic groups have no effect on preventing deterioration of catalyst activity. There is.

There is also a method in which antimony oxide itself is added to the catalytic cracking reaction system and deposited on the catalyst.

However, antimony oxide is completely insoluble in all petroleum fractions, so even if it is added as is, it will settle in the pipeline of the catalytic cracker and cannot be effectively sent into the reaction system.

In addition, in order to prevent deterioration of the activity of the cracking catalyst, it is necessary to add 10 to 2QO1 to the heavy petroleum fraction that is the raw material. It is most effective to continuously add +1 antimony oxide to the catalytic cracking reaction system, but it is extremely difficult to continuously add a certain amount of solid antimony oxide and disperse it effectively into the raw material. It is.

The present inventors have conducted intensive research to solve the above problems, and have arrived at the present invention.

That is, the present invention is characterized by comprising an oil-soluble anionic surfactant selected from the group consisting of sulfonates, sulfate ester salts, and carboxylates, and optionally an oil-soluble phosphorus-containing anionic surfactant. Dispersant of antimony oxide in hydrophobic solvent (first invention) and Sb+0+
and 5bzOs, a hydrophobic solvent, and an oil selected from the group consisting of sulfonates, sulfate ester salts, and carboxylates as a dispersant based on the weight of the composition. A stable antimony oxide dispersion composition (second invention) characterized by containing a dispersant consisting of a soluble anionic surfactant and, if necessary, an oil-soluble phosphorus-containing anionic surfactant.

In the oil-soluble anionic surfactant of the present invention and the oil-soluble phosphorus-containing anionic surfactant used as necessary, oil-soluble means that it is almost transparent to oils such as petroleum and fats and oils at room temperature or in a heated state. It refers to something that dissolves in the above-mentioned oils, and therefore, at temperatures lower than room temperature, the above-mentioned oils may become cloudy, precipitate, or phase-separated instead of being transparently dissolved.

Examples of the oil-soluble anionic surfactant selected from the group consisting of sulfonates, sulfate ester salts and carboxylates include those listed in f.

These anionic activators contain alkali metals (sodium, potassium, etc.), alkaline earth metals (calcium, magnesium, etc.).

Ammonium, amines (alkanolamines such as mono-, di- or triethanolamines).

Dimethylethanolamine, isopropanolamine, etc.; lower alkylamines such as methylamine, ethylamine, etc.) and salts of two or more thereof. Preferred are amine salts, alkali metal salts and alkaline earth metal salts.

[1] Sulfonate (a) Sulfosuccinate ester salt Dialkyl sulfosuccinate ester salt (the number of carbon atoms in the alkyl group is 6 to 20, preferably 8 to 18.
For example, n-octyl group, 2-ethylhexyl group, n-
Decylno; “!”-dodecyl group, etc.) For example, C2-
Ethylhexyl sulfosuccinate sodium acid,
Di-n-octyl sulfosuccinate calcium salt, etc.

(b) Alkylbenzene sulfonate An alkylbenzene sulfonate having one and/or more branched or straight-chain noalkyl groups, usually having 8 to 20 carbon atoms and preferably 12 to 18 carbon atoms, such as thorium dodecylbenzene sulfonate; 3°(c)Alkanesulfonate such as calcium dodecylbenzenesulfonate Alkanesulfonate having an alkyl group usually having 8 to 20 carbon atoms, such as calcium tetradecylsulfonate.

(d) α-olefin sulfonate Sulfonic acid sodium salt of α-olefin usually having 15 to 18 carbon atoms.

(e) Lignosulfonate (sodium salt).

Calcium salts, etc., petroleum sulfonates (calcium salts, etc.), etc. [11] Sulfate ester salts (a) Alkyl sulfate salts Straight chain and/or branched saturated and/or carbon atoms having usually 6 to 20 carbon atoms, preferably 12 to 18 carbon atoms. Sulfate ester salts of unsaturated alcohols, such as cetyl alcohol sulfate calcium salt, stearyl alcohol sulfate sodium salt, oxo alcohol (C11 to C17, side chain ratio 50% or more) sulfate jetanolamine salt, etc. .

(b) Polyoxyalkylene alkyl sulfate salt AO adduct of linear and/or branched saturated and/or unsaturated alcohol having usually 6 to 20 carbon atoms, preferably 12 to 18 carbon atoms (the number of moles added is usually 1 to 10 Preferably 1~
6) sulfate ester salts, such as cetyl alcohol E,
O+4+ sulfate ester triethanolamine salt, stearyl alcohol E(]31 sulfate ester calcium salt, etc. (In the above and below, AO indicates alkylene oxide, EO indicates ethylene oxide, PO indicates propylene oxide. Also, 0 indicates the number of moles added. AO having 2 to 4 carbon atoms is usually used).

Ao of alkylphenol or alkylnaphthol having at least one alkyl group having 8 to 12 carbon atoms.
1 adduct (the number of moles of the adduct is usually 1 to 10, preferably 1 to 10)
6) Sulfate ester salts, such as dinonylphenol EO
[4) Saturated and/or unsaturated fatty acid monoglyceride sulfate salt having 10 to 20 carbon atoms, such as coconut oil monoglyceride sulfate ester sodium salt.

(E) Sulfated parts, highly sulfated parts Sulfated fatty acid enosters, sulfated fatty acid funnel oil, sulfated sodium salts of olenic acid, etc. (f) Sulfated olefins Sulfated sodium salts of α-olefins having 12 to 18 carbon atoms, etc.

(g) Higher fatty acid alkylolamide sulfate salts Saturated and/or unsaturated fatty acid alkylolamide sulfate salts having 10 to 20 carbon atoms, such as beef tallow fatty acid monoethanolamide sulfate jetanolamine salts. ' [+11] Carboxylate salts of saturated and unsaturated fatty acids and hydroxyl group-containing fatty acids having usually 6 to 20 carbon atoms, preferably 12 to 18 carbon atoms;
For example, lauric acid triethanolamine salt, oleic acid calcium salt, etc.

Among the above anionic surfactants, preferred are sulfosuccinic acid ester salts, alkylbenzene sulfonates and carboxylic acid salts, and particularly preferred are sulfosuccinic acid esters and alkylbenzene sulfonates.

The dispersant of the present invention may consist of the oil-soluble anionic surfactant and, if necessary, an oil-soluble phosphorus-containing anionic surfactant.

As the oil-soluble phosphorus-containing anionic surfactant, any suitable one may be used.

[11 Phosphate ester salt or phosphonate long chain alkyl phosphate ester salt, [Saturated or unsaturated higher alcohol having usually 6 to 20 carbon atoms, preferably 12 to 18 carbon atoms (cetyl alcohol, stearyl alcohol, oleyl alcohol, etc.) phosphoric acid mono or/and diester salts, such as oleyl alcohol phosphoric acid monoester diammonium salts]; polyoxyalkylene alkyl ethers or polyoxyalkylene alkylaryl ether phosphoric acid diester salts, [of the saturated or unsaturated alcohols AO adduct (number of moles added is usually 1 to 8)
Or A O addition of an alkylphenol or alkylnaphthol (nonylphenol, dodecylphenol, dinonylphenol, etc.) having at least one, preferably one or two, alkyl groups having 8 to 12 carbon atoms? 1 (the number of moles added is usually 1 to 8) of phosphoric acid mono- or diester salts, such as stearyl alcohol EO [51 phosphoric acid diester monopotassium salt (stearyl alcohol E
The 5 molar adduct monopotassium phosphoric acid diester salt is shown. The same description will be used below), nonylphenol EO (
5) Phosphoric acid diester monoethanolamine salt];
Long-chain alkyl phosphonate [phosphonate or monophosphonate having a long-chain alkyl group (alkyl group (including alkenyl group) having usually 6 to 24 carbon atoms, preferably 12 to 20 carbon atoms, such as cetyl group, oleyl group, etc.) Ester salts such as oleylphosphonic acid diethylethanolamine salt, etc.

Among the phosphorus-containing anionic surfactants, preferred are long-chain alkyl phosphate ester salts and polyoxyalkylene long-chain alkyl phosphate ester salts.

The ratio of oil-soluble anionic surfactant to phosphorus-containing anionic surfactant can vary within a wide range, for example 100:
1-1:99 preferably 100:'0-20:
It is 80.

Examples of the hydrophobic organic solvent in the present invention include petroleum fractions (gasoline, kerosene, diesel fuel oil, etc.).

n-paraffinic solvents (α to C+5 n-paraffins such as n-hexane, n-hebutane and C6 to C+s
mixed n-paraffinic solvent consisting of n-paraffins)
, isoparaffinic solvents (propylene tetramer, etc.)
, aromatic hydrocarbon solvents (toluene, xylene, naphthalene.

methylnaphthalene and mixtures of two or more of these), ketone solvents (methyl isobutyl ketone, ditertiary butyl ketone, etc.), ester solvents (ethyl acetate, butyl acetate, etc.), ether solvents (dibutyl
-methyl, methyl butyl ether, etc.), alcoholic solvents (2-ethylhexanol, nonyl alcohol, dodecyl alcohol, etc.), and mixtures of two or more of these.

Among these, preferred are petroleum fractions, n-paraffinic solvents, isoparaffinic solvents and aromatic hydrocarbon solvents.

Among antimony oxides (Sb+Ot (antimony tetroxide) and/or 5bzO5 (antimony pentoxide)) in the present invention, 5bzOs is preferred.

The antimony oxide used in the present invention is usually in powder form, and the powder diameter is, for example, 5M or less, preferably 1 mm or more.

The content J11 of antimony oxide in the composition of the present invention is not particularly limited, and is usually 0.1% to 60%, preferably 10% to 50%, based on the weight of the composition. When the content of antimony oxide exceeds 60%, the viscosity of the composition becomes .6, making it difficult to handle.

The content of the dispersant is also not particularly limited, and is usually 0.05% to 30%, preferably 2% based on the weight of the composition.
~20%. If the content of the dispersant is less than 0.05%, it is difficult to obtain a stable dispersion composition, and if it exceeds 30%, there is no effect of further improving the stability of the dispersion composition, which is economically disadvantageous.

It is desirable to vary the amount of dispersant depending on the amount of antimony oxide in the composition. For example, usually 5 to 100%, preferably 20 to 50% based on the amount of antimony oxide.
It is.

The content of the hydrophobic solvent is also not particularly limited, and is usually 20 to 998%, preferably 40 to 90%, based on the weight of the composition.

When the hydrophobic solvent content is 20%, the viscosity is high and handling becomes difficult.

Preferable results may be obtained by including.

In order to stabilize the dispersion of the dispersion composition, hydrophilic solvents such as monohydric lower alcohols (methanol, ethanol,
propatool, butanol, etc.), polyhydric alcohols (ethylene glycol, diethylene glycol, propanediol, glycerin, pentaerythritol, etc.), ammonia, amines, such as lower amines (methylamine, ethylamine, etc.), alkanolamines (monoethanolamine, Favorable results may also be obtained by including triethanolamine, isopropanolamine, etc.) in the composition. In that case, the content is usually 0 to 10%, preferably 0, based on the weight of the composition.
~6%.

The method for producing the composition of the present invention is not particularly limited. For example, antimony trioxide, which is a common oxide of antimony, is suspended in water and then mixed with hydrogen peroxide solution 9, hypochlorous acid and its salts, etc. A dispersion containing 5b201 and/or 5b20i is obtained by adding an aqueous solution of an oxidizing agent and heating to perform an oxidation reaction. If excess oxidizing agent is used to remove moisture from the dispersion obtained in this way, it is desirable to decompose the oxidizing agent by an appropriate method after the oxidation reaction is completed. Dry and grind the solid. The desired dispersion composition can be obtained by adding the above hydrophobic solvent and dispersant to the antimony oxide thus obtained and stirring and mixing.

A speed mill is used as a method for stirring and mixing the above.

A device that has a grinding function such as a roll mill.

A preferred method is to use a special machine such as a homomixer that has a turbulent flow function due to high-speed rotation.

In some cases, a slurry product obtained by reacting antimony trioxide and an oxidizing agent using water as a solvent may be heated to a temperature above the boiling point of water by adding a solvent and a dispersant with a boiling point higher than that of water. A stable dispersion composition can also be obtained by removing water from the system using a suitable method.

- The properties of the composition of the present invention include the content of antimony oxide,
It can be varied depending on the type of solvent and the type and amount of dispersant, but it is usually a white to yellow or light brown opaque liquid, and those with a low content of antimony oxide are translucent with a pearly luster. It becomes liquid.

In the composition of the present invention, the dispersed antimony oxide powder is very fine.

For example, even when observed using a microscope with a magnification of 1000 times, the size cannot be confirmed in many cases, and it is assumed that the size reaches 1 μm or less. The stability of the dispersion composition is also good, and the dispersion state is generally not destroyed even at high temperatures from 0°C to 100°C or higher, and the dispersed particles do not settle even when left at room temperature for a long time.・I can hardly see anything. Furthermore, when diluting by adding a hydrophobic solvent such as a petroleum distillate, it is possible to adjust the dilution to any desired ratio (for example, the content of antimony oxide is usually 0) without affecting the dispersion state.
．． (1 to 10% by weight).

Because of the above-mentioned effects, the composite acid of the present invention is very useful as an additive for preventing deterioration of the activity of catalysts for fluid catalytic cracking of heavy petroleum fractions. In other words, when used as an additive to prevent deterioration of catalyst activity, it is added to the heavy petroleum fraction, which is the raw material for fluid catalytic cracking, and introduced into the cracking reactor; If the dispersion state cannot be maintained when the oil is used, antimony oxide may settle in the piping of the reactor, the part of the filter installed in the piping may become clogged, or the tip of the nozzle that feeds the raw oil into the reaction equipment. However, with the composition of the present invention, such troubles do not occur.

Attempts to disperse antimony oxide in water or a hydrophilic organic solvent have already been made and put into practical use, but there are very few attempts to disperse it in a hydrophobic organic solvent.

In the present invention, research has shown that it is extremely difficult to disperse antimony oxide in a hydrophobic solvent using antimony trioxide, which is generally widely used, even with the help of any dispersant. Based on the results of It has been found that the anionic surfactant exhibits much better dispersion stability.

The present invention will now be further explained using practical examples, but the present invention is not limited to these examples.

Example 1 JP-A-52-21-28 and JP-A-52-4?
4-'? '? Antimony pentoxide was produced by oxidizing antimony trioxide with hydrogen peroxide according to the method for producing antimony pentoxide described in the publication.

Antimony trioxide (SbzO3) lsoog and water 48
009 was heated to reflux in a 108 Kolben with chilled bones.

After dropping 1400 fj of 30% hydrogen peroxide solution,
Time aging was performed. The aqueous suspension of antimony oxide (referred to as antimony pentoxide) obtained by cooling this is white ~
It was a pale yellowish white colloidal liquid.

The antimony pentoxide powder obtained by drying and pulverizing this colloidal liquid at 120°C for 2 hours was a white to slightly yellowish white powder and contained 672% of antimony.

100 g of antimony pentoxide (powder) thus obtained, xylene solvent 3359 containing 10% naphthalene, water 155' and sodium dioctyl sulfosuccinate 3
Put 5g into a 1g beaker and mix with a homomixer at 10,000 rpm.
After stirring, 15 g of monoethanolamine was added and the mixture was forcefully stirred for an additional 15 minutes. The antimony pentoxide dispersion obtained by removing a small amount of undispersed matter remaining by centrifugation was used as the dispersion composition of the present invention.

This composition was a colloid with a pale yellow color and contained 135% antimony, and almost no sediment was observed even when it was left at room temperature for one month. It could be diluted in petroleum solvents such as xylene and light oil at any ratio, and the dispersion stability of the diluted product was also good.

Example 2゜30 g of antimony pentoxide powder obtained in Example 1,
60 g of kerosene and 10 g of calcium dodecylbenzenesulfonate were vigorously stirred for 10 minutes at 10,000 rpm in a homomixer. The antimony pentoxide dispersion obtained by removing a small amount of undispersed matter remaining by centrifugation was used as the dispersion composition of the present invention.

This composition had good dispersion stability and good dilubility with 9 petroleum distillate oils.

330 g of kerosene, 35 g of sodium dioctyl sulfosuccinate, and 25 g of oil alcohol phosphate ester triethanolamine salt (the molar ratio of oleyl alcohol and phosphoric anhydride is 2.5:1) were mixed by stirring well, and mixed using a colloid mill (TK manufactured by Tokushu Kiko KK). Mycolloider) was passed five times. The antimony pentoxide dispersion obtained by removing a small amount of undispersed matter remaining by centrifugation was used as the dispersion composition of the present invention. This composition showed good dispersion stability.

Example 4 6 og of antimony pentoxide aqueous suspension obtained in Example 1
175g of xylene 12g of sodium diophthylsulfosuccinate in a 5oome colben, 95°C to 14
An antimony pentoxide dispersion obtained by removing only water from the water-xylene azeotroped at 0°C was used as the dispersion composition of the present invention.

This composition is a light brown colloid with 10% antimony.
．． Contained 0%. Moreover, both dispersion stability and petroleum distillate dilutability were good.

Claims (1)

[Claims] 1. A dispersant of antimony oxide in an oil-soluble hydrophobic organic solvent selected from the group consisting of sulfonates, sulfuric acid ester salts, and carphonic acid salts. 2, antimony oxide selected from the group consisting of Sb+04 and 5bzO+, 0.05-30% sulfonic hydrochloric acid based on the weight of the composition as a hydrophobic solvent and dispersant;
A stable oxidation agent characterized by containing an oil-soluble anionic surfactant selected from the group consisting of sulfuric acid ester salts and carboxylic hydrochloric acid, and optionally a dispersant consisting of an oil-soluble phosphorus-containing anionic surfactant. Antimony dispersion composition. 3. The composition according to claim 2, wherein the oil-soluble sulfonate is a sulfosuccinate salt and/or an alkylbenzene sulfonate salt. 4. The composition according to claim 2 or 3, wherein the content of antimony oxide is 10 to 50% based on the weight of the composition. 5. The composition is diluted with a hydrophobic solvent. 6. The composition according to any one of claims 2 to 4, wherein the composition is diluted so that the content of antimony oxide is 0.1 to 10^. Composition of.