JPS60161730A - Dispersant and composition of antimony oxide - Google Patents

Abstract

PURPOSE:To provide a dispersant of antimony oxide capable of stably dispersing antimonoy oxide in a hydrophobic solvent at a high concn., constituted of an oil soluble phosphorus-containing anionic surfactant. CONSTITUTION:An antimony oxide dispersant comprises an oil soluble phosphorus-containing anionic surfactant and disperses antimony oxide in a hydrophobic solvent to enable the formation of a stable antimony oxide dispersed liquid composition. As the above mentioned phosphorus-containing anionic surfactant, phosphoric ester, alkali metal, alkaline earth metal of ammonium phosphonate and/or amine salt are pref. used. The stable antimony oxide dispersed liquid composition prepared by containing 0.05-30wt% of the above mentioned dispersant, 10-50wt% of antimonoy oxide such as Sb2O4 or Sb2O5 and the hydrophobic solvent such as a petroleum fraction is further diluted by the hydrophobic solvent so as to adjust the concn. of antimonoy oxide to 0.1-10wt% and this diluted composition is used in the fire retardant treatment of plastics of the deterioration inhibiting 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 separation liquid composition in which antimony oxide is stably dispersed in a hydrophobic solvent at a high concentration.

Antimony oxide is used as an additive in the production of plastics, III-combustion treatment laths for fibers, ceramics, etc.; as a raw material for glassy enamel, etc. In recent years, it has been discovered that deterioration of the catalytic action caused by metals such as nickel can be prevented by depositing antimony oxide (1) onto catalyst elements for fluid catalytic cracking of quality petroleum fractions (2). The method for depositing antimony oxide on the catalyst 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, converting it into inorganic antimony and depositing it on the catalyst. A method is used to deposit it.

However, this method requires the production of organic antimony compounds. Furthermore, in order to dissolve antimony in petroleum fractions, it is necessary to use an antimony compound with a fairly bulky organic group, and furthermore, it is said that organic groups have no effect on preventing deterioration of catalytic activity. There is a problem.

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 most effective to continuously add 10 to 200 ppHl of antimony oxide to the heavy petroleum fraction, which is the raw material, to the catalytic cracking reaction system. However, it is extremely difficult to effectively disperse solid antimony oxide into the raw material by continuously applying a certain amount of force.

The present inventors have conducted extensive research to solve the above problems, and as a result, have arrived at the present invention.

That is, the present invention provides a dispersant for antimony oxide in a hydrophobic solvent (first invention), which is characterized by comprising an oil-soluble phosphorus-containing anionic surfactant, and sb, o, and 5
antimony oxide selected from the group consisting of byOs, a hydrophobic solvent and 0.05 to 30% by weight of the composition
A stable anti-thin oxide dispersion composition (second invention) is characterized in that it contains a dispersant consisting of an oil-soluble phosphorus-containing anionic surfactant.

Regarding the oil-soluble phosphorus-containing anionic surfactant used in the present invention, oil-soluble refers to one that dissolves almost transparently in oils such as petroleum and fats and oils at room temperature or in a heated state.
Therefore, at temperatures lower than room temperature, the above-mentioned oils may not dissolve transparently, but may become cloudy, precipitate, or undergo phase separation.

Examples of oil-soluble phosphorus-containing anionic surfactants include those listed above.In this active agent, the salts include alkali metals (sodium, potassium, etc.), alkaline earth metals) IJ! , (calcium, magnesium, etc.), ammonium and amines (alkanolamines such as mono-, di- or triethanolamine, dimethylethanolamine, mono- or diisopropanolamine; lower alkylamines such as methylamine, ethylamine, etc.) and two of these. I can give my son salt. Preferred are amine salts and alkaline earth metal salts. As alkylene oxide (hereinafter abbreviated as AU), C2-→AO
For example, ethylene oxide (hereinafter abbreviated as EO) and/
Or propylene oxide (hereinafter abbreviated as PO) can be mentioned.

[l] Phosphate ester salt or phosphonate long chain alkyl phosphate ester salt, saturated or unsaturated higher alcohol (cetyl alcohol, stearyl alcohol, etc.) having a DJ element i of usually 6 to 20, preferably 12 to 18. , oleyl alcohol, etc.), e.g. oleyl alcohol phosphate monoester diammonium salt, Book 1 Polyoxyalkylene alkyl ether or polyoxyalkylene alkylaryl ether phosphate ester salt, before C RQ Saturated t or unsaturated alcohol with AO additives (the number of moles of additive is usually [~
8) or an alkyl group having 8 to 12 carbon atoms at least 11A1. Phosphate mono- or diester salts of AO additives (the number of moles added is usually 1-8) of alkylphenols or alkylnaphthols (nonylphenol, dodecylphenol, dinonylphenol, etc.) preferably having 1 to 2 alkylphenols or alkylnaphthols (nonylphenol, dodecylphenol, dinonylphenol, etc.), such as stearyl alcohol EO ('5 ) Diester monopotassium phosphate salt (represents monopotassium phosphoric acid diester monopotassium salt of E 0.5 mole adduct of stearyl alcohol. The same description will be used hereinafter).

Nonylphenol EU (5) phosphoric acid diester monoethanolamine salt, etc.]; Long chain alkyl phosphonate [Long chain alkyl group (usually 6 to 24 carbon atoms, preferably 12 carbon atoms)
Phosphorus-containing anionic surfactants such as phosphonates or monoester salts having ~2o alkyl groups (including alkenyl groups, such as cetyl groups, oleyl groups, etc.), such as oleylphosphonate diethylethanolamine salt, etc.) Preferred are long chain alkyl phosphate ester salts and polyoxyalkylene long chain alkyl phosphate ester salts.

Examples of hydrophobic organic solvents used in the present invention include petroleum fractions (gasoline, kerosene, light oil, heavy oil, etc.), II-halaffinic solvents (C6 to CI5 n-paraffins, e.g.
-hexane, 1]-heptane and 11 of C6-CI5
- a mixed 11-paraffinic solvent consisting of paraffin),
Isoparaffinic solvents (such as fluoropylentitramer),
Aromatic hydrocarbon solvents (toluene, xylene, naphthalene, methylnaphthalene, and mixtures of two or more phases of these, etc.), ketone solvents (methyl isobutyl ketone, tertiary butyl ketone, etc.), ester solvents (ethyl acetate, etc.) , butyl acetate, etc.), ether solvents (butyl ether, methyl butyl ether, etc.), alcohol M solvents (z-ethylhexanol, nonyl alcohol,
dodecyl alcohol, and a mixture of two of these. Among these, preferred are petroleum fractions, 11-paraffinic solvents, isoparaffinic solvents and aromatic hydrocarbon solvents.

Antimony rSb in the present invention, 0. (antimony tetroxide) and/or SL+20. Among (antimony pentoxide), preferred are sb and o.

The antimony oxide used in the present invention is usually in the form of a powder, and its particle size is, for example, 5 mm or less, preferably 1M or less.

The content of antimony oxide in the composition of the present invention is not particularly limited, and is based on the weight of the composition.
Usually O is 1% to 60%, preferably 5% to 10% to 50%. When the content of antimony oxide exceeds 60%, the viscosity of the composition becomes high and handling becomes difficult.

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 M of the dispersant is less than 0.005%, 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, resulting in an economically small group 1.

It is desirable that the JJI of the dispersant be varied depending on the amount of antimony oxide in the composition. and λ are usually 5 to 100%, preferably 20 to 5% in terms of the amount of antimony oxide.
It is 0%.

The content of the hydrophobic solvent is also not particularly limited, and is usually 20 to 99.8%, preferably 40 to 90%, based on the weight of the composition.

If the content of the hydrophobic solvent is less than 20%, the viscosity becomes high and handling becomes difficult.

In addition, a small amount (weight i+ of the composition) may be added to the dispersion composition as necessary.
Based on this, it is usually 0 to 10% better.

In some cases, preferable results can be obtained by containing water in an amount of 0 to 6%.

In addition, hydrophilic solvents such as monovalent lower alcohols (methanol, ethanol, propatool, phthanol, etc.), polyhydric alcohols (ethylene glycol, diethylene glycol, propanediol, glycerin, pentaerythritol, etc.) are used to stabilize the dispersion of the dispersion composition. , ammonia, amines (for example, lower amines (methylamine, ethylamine, etc.), alkanolamines (monoethanolamine, jetanolamine, triethanolamine, impropaturamine, etc.), etc., are included in the composition. In some cases, satisfactory results may be obtained, in which case the content is usually between O and O, based on the weight of the composition.
10%, preferably 0-6%.

The method for preparing 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 hydrogen peroxide, subchloric acid, and its salts are used. A dispersion containing sb, o4 and/or 5b2o is obtained by adding an aqueous solution of an oxidizing agent or the like and heating to perform an oxidation reaction. If an excess of oxidizing agent is used to remove water from the dispersion obtained in step 2, it is desirable to decompose the oxidizing agent by an appropriate method after the oxidation reaction is complete.) The solid obtained is dried and ground. By adding the above-mentioned hydrophobic solvent and dispersant to the antimony oxide mixed in a 1:1 ratio as in step 2 and stirring and mixing, a dispersion composition according to 1 can be obtained.

As a method for stirring and mixing, it is preferable to use a special machine such as a speed mill or a roll mill that has a pulverizing function, or 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 higher than 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.

The properties of the composition of the present invention include antimony oxide containing 11i-
1. It can vary depending on the type of solvent and the type and amount of dispersant. 2. It is usually a white to yellow or light brown opaque liquid with a low content of antimony oxide (・The liquid is semi-transparent with a burl-like luster). It becomes a transparent liquid.

In the composition of the present invention, the dispersed antimony oxide particles are 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.

In addition, the stability of the dispersion composition is also good; in general, the dispersion state will not be destroyed even at high temperatures from 0°C to 100°C or higher, and the dispersed particles will not settle even when left at room temperature for a long time. It is almost never seen. Furthermore, when diluting by adding a hydrophobic solvent such as a petroleum fraction, the dilution can be done to any desired ratio (for example, so that the content of antimony oxide is usually 0.1 to 10% by weight) without affecting the dispersion state. I can do two things.

The composition of the present invention is extremely useful as an additive for preventing deterioration of the activity of a catalyst for fluid catalytic cracking of heavy petroleum fractions because it exhibits the effects described in item 1 above. 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, clog part of the filter installed in the piping, or clog 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.

Although attempts to disperse antimony oxide in water or hydrophilic organic solvents have already been made and have been put to practical use, there have been very few attempts to disperse antimony oxide in hydrophobic organic solvents.

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, it was found that antimony trioxide further oxidized is suitable, and although attempts have already been made to use cationic surfactants as dispersants, oil-soluble phosphorus-containing agents such as those used in the present invention have been used as dispersants. It has been found that ionic surfactants exhibit much better dispersion stability.

The present invention will be further explained below with reference to Examples, but the present invention is not limited by these Examples.

Example 1 JP-A-52-Z772F772℃ and JP-A-52-52
? 4-J? ? 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 (Sb20.) 1800 P and water 4
8002 was heated to reflux in a lOJ Kolben with chilled bones. Add this to 30% hydrogen peroxide for 1,400 yen! 9 was added dropwise, and after the completion of the addition, aging was carried out for 2 hours. The aqueous suspension of antimony oxide (referred to as antimony pentoxide) obtained by cooling this was a white to pale yellowish white colloidal liquid.

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

Thus obtained antimony pentoxide 602, xylene solvent (Marukubi Sekiyu 5WA-310) 1109, oleyl alcohol phosphate ester diethylethanolamine salt (molar ratio of oleyl alcohol and phosphoric anhydride is 2.5:
1) 20P and water ICI' were placed in a 500-heater and forcefully stirred with a homomixer at 8000 rpm for 10 minutes. The P solution obtained by removing a small amount of undispersed matter remaining in the furnace was used as the dispersion composition of the present invention. This composition was in the form of a pale yellow-white colloid and contained 17.6 wt % of antimony. The second dispersion composition exhibited good dispersion stability and almost no sediment was observed even after being left at room temperature for one month. Moreover, it could be diluted with petroleum fractions such as xylene and light oil at any ratio, and the dispersion stability of the diluted product was also good.

Example 2 Antimony pentoxide (powder) 100P obtained in Example 1
, xylene 60g, oleyl alcohol phosphate ester triethanolamine salt 402 500 = 7! The antimony pentoxide dispersion obtained by placing the mixture in a beaker and stirring vigorously for 30 minutes using a homomixer (12,000 ml) was used as the dispersion composition of the present invention. The second composition has a viscosity of 2J? 1cps
(25°C) showed good dispersion stability in slurry form.

Example 3 Antimony pentoxide aqueous suspension 2007 obtained in Example 1
xylene containing 10% naphthalene in solvent r to
ii', Instearyl alcohol EO (5) Phosphate diester potassium salt 207 and diethylene glycol log were added and heated at 95°C to 140°C by xylene-water azeotrope, removing only water from the distilled liquid from the system. The antimony pentoxide dispersion obtained in this manner was used as the dispersion composition of the present invention.The second composition showed good dispersion stability.

Example 4 The antimony pentoxide aqueous suspension obtained in Example 1 was partially dehydrated to have an evaporation residue of 50%. Kerosene 113P and oleyl alcohol phosphate ester diethylethanolamine salt were added to 133P of hyantimony pentaacid paste and oleyl alcohol phosphate ester diethylethanolamine salt. (The molar ratio of oleyl alcohol and phosphoric anhydride is 2.5:1) Add 20P and mix well with a homomixer.1.Liquid at 95℃~
A dispersion of diantimony pentoxide obtained by removing water distilled out from the system at 120° C. was used as a dispersion composition of the present invention. This composition was in the form of a pale yellowish white colloid with a specific gravity of 1.15 (25°C) and contained 22% antimony. The second composition also showed good dispersion stability.

Example 5 Commercially available antimony pentoxide (11 concentrates A POXX
-8) 60, kerosene 1039, water 17P and cetyl alcohol phosphate ester diethylethanolamine salt 20
A dispersion composition of the present invention was prepared by adding 50011Ie Kolben Q and heating and refluxing at 95° C. with stirring until the solid matter disappeared. This composition showed good dispersion stability and petroleum distillate dilutability.

Claims (1)

[Scope of Claims] 1. A dispersant for antimony oxide in a hydrophobic solvent, comprising an oil-soluble phosphorus-containing anionic surfactant. 2, Sb, 0. and a dispersant consisting of antimony oxide selected from the group consisting of sb, o, a hydrophobic solvent, and an oil-soluble phosphorus-containing anionic surfactant in an amount of 005 to 30% based on the weight of the composition. A stable antimony oxide dispersion composition characterized by: 3. The composition according to claim 2, wherein the phosphorus-containing anionic surfactant is an alkali metal, alkaline earth metal, ammonium and/or amine salt of a phosphoric acid ester or a phosphonic acid. 4 The content of antimony oxide is based on the weight of the composition (・
Claim 2 or 3 which is 10 to 50%
Compositions as described in Section. 5. The composition according to claim 2 or 3, wherein the composition is diluted with a hydrophobic solvent. 6. The composition according to claim 5, which is diluted so that the content of antimony oxide is 0.1-10% by weight.