JPS6055089A - Dispersion stabilizer for aqueous slurry of petroleum coke - Google Patents

Abstract

PURPOSE:To provide the titled dispersion stabilizer contg. a specified polyether compd. (deriv.) and an amine compd. or amide compd. as effective ingredients, which produces an aqueous slurry of petroleum coke having excellent quiescent stability and a high fluidity. CONSTITUTION:The stabilizer contains as effective ingredients (A) polyether compd. (deriv.) having an MW of 5,000-200,000 which is obtained by adding ethylene oxide-contg. alkylene oxide to a polyamine compd. (e.g. ethylenediamine) and in which the total weight of polyoxyethylene chain segments account for 40-95wt% of the total MW, (B) at least one nitrogen-contg. compd. selected from among amine compd. and amide compd. (e.g. octylamine or stearamide) and preferably (C) at least one of aliphatic alcohol, sorbitan ester of fatty acid and silicone compd.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a dispersion stabilizer for an aqueous slurry of petroleum coke powder. More specifically, the present invention relates to a dispersion stabilizer for dispersing petroleum coke powder in water and stabilizing the dispersion to a state where it can be transported in twin pipes.

Due to the inevitable rise in crude oil prices and the diversification of crude oil supply destinations, the proportion of 'IJi' oil in Japan's imported crude oil tends to increase. On the other hand, with the remarkable development of the petrochemical industry, the demand for light buying whistles as part of the drug industry continues to increase. For these reasons, heavy fractions in crude oil have become excessive, and this trend is expected to increase in the future. Therefore, in fields such as the petrochemical industry and the energy industry, there is an urgent need for technological development for the effective use of heavy fractions.

Against this background, attention is currently being paid to the use of petroleum coke obtained by dry distillation or separation of heavy fractions as a liquid fuel.

As one of the attempts to make petroleum coke into a slurry, a method is known in which petroleum coke is dispersed in oil such as heavy oil.

Since the fuel made by dispersing petroleum coke in oil requires the use of oil, recently a technology has been developed to make water slurry in which petroleum coke is dispersed in water, which allows petroleum coke to be handled as a fluid without using oil. being researched.

Petroleum coke-water slurry is made by dispersing petroleum coke's enemy powder in water to form a slurry. This method allows petroleum coke to be handled as a fluid just like oil, making operations such as transportation and storage easier. It becomes easier.

Directly TL petroleum coke/water slurry! In order to burn it, it is necessary to reduce the water content as much as possible and increase the concentration of petroleum coke, but since petroleum coke is hydrophobic, it causes agglomeration in water and loses fluidity when heated. There are many cases where this happens, and it becomes a big deal when it comes to practical application.

When a surfactant, which is a dispersant, is added to the petroleum coke/water slurry, the surfactant is adsorbed at the interface between the petroleum coke and water, loosening the petroleum coke particles into pieces, and causing the petroleum coke particles to interact with each other. It is expected to create a good dispersion state due to the effect of preventing agglomeration.

However, surfactants such as general alkylbenzenesulfone #R salts, petroleum sulfonates, and quaternary ammonium salts have insufficient fluidity and lack practicality. Also, an alkylphenolamine oxide adduct has been proposed for the same purpose (% opening 57-131285
Some of these compounds are effective, but if the coke concentration in the slurry is about 60 wt%, it has fluidity, but if it exceeds that, the fluidity becomes extremely poor.
It is difficult to produce a slurry with a high concentration of 0 wt% or more.

The present inventors have arrived at the present invention as a result of intensive research to improve the drawbacks of such petroleum coke/water slurry.

That is, the present invention (aJ boriadenone compound) in which an alkylene oxide containing ethylene oxide as an essential component is added, and the total amount of heavy violet in the polyoxyethylene chain portion is 4% of the total molecular weight.
0 to 95% heavy duty and further molecular weight of 5,000 to 20
000 or a derivative thereof,
and (bJ Contains one or more nitrogen-containing compounds selected from adenone compounds or and compounds as an essential component, and further contains (03 aliphatic alcohol, sorbitan fatty acid ester, and silicone compound) as an essential component. This is a dispersion stabilizer for an aqueous slurry of petroleum coke powder, which contains 1Wi or 211 or more selected from the group consisting of:

Examples of the boriayne compound used as the raw material for the polyether compound or its derivative, which is obtained by adding an alkylene oxide containing ethylene oxide as an essential component to the borianne compound used as the dispersion stabilizer (aJ acid component) of the present invention, include ethylene diamine, butylene cyphon, and diethylene triamine. Examples include polyalkylene polyamines such as ion, triethylene tetrane, and tetraethylene pentamine, and polyethylene ions.

A polyether compound can be easily obtained by adding an alkylene oxide containing ethylene oxide as an essential component to a boria compound by a conventional method.

Among these, block or partially block adducts of ethylene oxide and propylene oxide are particularly preferred, and the order of addition may be in any order, but propylene oxide (hereinafter abbreviated as po) is added first. (Hereinafter abbreviated as EO.) When tP is added, good dispersion stability is shown.

The molecular weight of the polyether compound or its derivative is s, o
o o ~ 200,000 and preferable tL< is 10.000
~1 rJ O,00Q more preferably 30.0 mouths 0
~a o, o o o is @ enclosed. Further, the total overlap of the go chain portions is 40 to 95% of the total molecular weight, preferably 80 to 95% of the total molecular weight.

Derivatives of the polyether compound of the present invention include 4il oxides, phosphoric oxides,
Examples include carboxyalkylated products, fatty acid esterified products, and products in which part of the nitrogen atoms are cationized. Among these, fatty acid esters and cationized products are particularly preferred.

In the case of fatty acid esterification, the fatty acid used preferably has 7 to 25 carbon atoms, but the number of double bonds, branching, etc. have no effect on performance. Examples of the cationized product include compounds obtained by cationizing a polyether compound with sulfuric acid, alkyl genide, etc., and cationized products neutralized with acetic acid, alkylbenzenesulfonic acid, etc.

As component (I) of the present invention, one or more i1-containing purple compounds selected from azene compounds and amide compounds are used. Among these electrocontaining wood compounds, azene compounds include primary amines such as octylalune, laurylamine, beef tallow azene, secondary amines such as diethylamine, distearylazene, morpholine, etc., tertiary ammoniums such as dimethylstearylazene, dimethyl 2 Urylamine, aromatic amines such as aniline, dibenzylamine, toluidine, etc., and borianne compounds such as polyalkylene polyamines, alkyl (or alknyl) polyalkylene polyamines, polyethylene esters, etc., examples include ethylene diacene, triethylene tetrane, etc. ,
Laurylpropylene diamine, stearyl triethylene nato, stearyl tetraethylene pentamine, stearyl pentaethylene hexane? There is Min. Ein salts produced by neutralizing these amine compounds with acidic compounds and quaternary ammonium salts quaternized by known methods are also effective. For example, amine salts include acetates, tR salts, sulfates, etc. of the above amine compounds, and 4R ammonium salts include compounds obtained by cationizing the above azene compounds with alkyl hassides, dimethyl sulfate, etc. using known methods. An example is lauryltrimethylammonium(chloro)'% xf
Examples include 7lyltrimethylammonium chloride.

In addition, the amide compound is a reaction product of carboxylic acid and ammonia or the above-mentioned amine compound, and examples thereof include stearic acid adenate, ethylene diacrylate monoacid, triethylenetetraine stearate cyanoacide, etc. can be mentioned.

Also used as necessary in the dispersion stabilizer of the present invention (0)
Among the components, aliphatic alcohol has 6 to 1 carbon atoms
2 aliphatic alcohols are used, such as octyl alcohol, 2-ethylhexyl alcohol, 2-uryl alcohol, etc. ? Rubitan fatty acid esters include sorbitan monolaurate, sorbitan monopalzate, sorbitan monooleate, sorbitan monostearate, and the like. Similarly, among the components (0), silicone compounds include polydimethylsiloxane,
Examples include dimethyl silicone oil and fluorosilicone oil.

The dispersion stabilizer of the present invention has a
Mouth 1~s, o ILJlit%, preferably 0.05~
Petroleum coke particles can be dispersed in water by adding 2.0jL'Ik%.

Both component (b) and component (0) in the dispersion stabilizer of the present invention are relative to component (1), a polyether compound or its derivative! O3 [lid % or less, preferably 15 to 5 heavy electric %,
It may be added to the petroleum coke slurry together with component (a), or may be added separately to the petroleum coke slurry.

The mixing order of petroleum coke, dispersant, and water may be in any order, but it may be prepared by adding the dispersant to water by MWI, adding petroleum coke or petroleum coke imitation powder, and using a suitable mixing device or crushing device. Of course, a method may be adopted in which petroleum coke, a dispersant, and water are added at the same time, and the dispersant is added again after crushing.

The petroleum coke particles to be used may have an appropriate particle size from the viewpoint of combustion and crushing cost.
~90% bus is used as a guideline.

The R-dynamics of a petroleum coke-water slurry generally varies depending on the type and particle size of the petroleum coke powder, but when no dispersion stabilizer is added, the viscosity increases rapidly when the petroleum coke chain degree exceeds sO Dendo%. I'll come. On the other hand, when a predetermined amount of the dispersion stabilizer of the present invention is added, petroleum gas particles are dispersed, fluidity is significantly improved, and a highly concentrated slurry can be obtained. - It is possible to create a slurry with excellent storage stability that does not form cakes. If the concentration of petroleum coke constituting the petroleum coke-water slurry is too low, the transportation efficiency will be poor, and the dewatering process will be costly, making it meaningless. Also, if it is too large, the viscosity will become too high, so the w1 of petroleum coke varies depending on the viscosity, but generally 60
-85%, preferably 50-7aliz%.

The dispersion stabilizer of the present invention has as an essential component a polyether compound or a 700 conductor obtained by adding an alkylene oxide to a boriaine compound, and one or more of an i1-containing compound selected from an atom compound or an adendo compound. By using two or more acids in combination, or by using OJ acid components selected from aliphatic alcohols, sorbitan fatty acid esters, or silicone compounds (by varying the OJ acid component as necessary, excellent effects can be achieved with a relatively small amount of additives, Furthermore, it has revolutionary performance that is not affected by particle size distribution, preparation conditions, etc.

This is because the (bt, (0) component, which has a lower molecular weight than the (aJ component), forms an a layer into the pores of 1 meter on the surface of the petroleum coke and makes the pores hydrophobic, thereby preventing water necessary for dispersion from penetrating. This is thought to be due to the fact that dispersion stability is dramatically improved compared to the hindrance (a) component alone.

The dispersion stabilizer of the present invention can be used in combination with other anionic surfactants or nonionic surfactants. For example, fatty acids such as oleic acid, phosphoric acid esters such as triptylphosunate, or aluminium stearate are added to petroleum coke using a naphthalene sulfonic acid formalin condensate or sodium lignin sulfonate, and the dispersion stabilizer of the present invention. By adding metal soap or the like, a stable slurry with less air bubbles can be made.

The petroleum coke-water slurry to which the dispersion stabilizer of the present invention has been added is a liquid that is immiscible with water as a dispersion medium in order to separate and recover the petroleum coke from the slurry at the end of its use as a means of transportation. A method of granulating petroleum coke powder by adding hydrocarbon oil, etc., and separating and recovering it from water is attracting attention. For this purpose, hydrocarbon water and oil are sometimes added when preparing petroleum coke-water slurry in advance, but the dispersion stabilizer of the present invention has a dispersion effect even in systems where such hydrocarbon oil coexists. Shows excellent performance without loss of performance.

The aqueous slurry of petroleum coke powder obtained by adding the dispersion stabilizer of the present invention has good fluidity with little increase in viscosity even at high concentrations, and has good dispersion without forming hard cakes even during long-term storage. Bike line transportation to maintain stability,
Tank storage, boiler) - Direct combustion is possible. In addition, the water slurry of petroleum coke obtained using the dispersion stabilizer of the present invention has fewer bubbles during production, has less increase in volume of the slurry, and can prevent thickening due to air bubbles, resulting in good properties. can.

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

Example 1 (1) Preparation and fluidity of water slurry Table 244 Compound 1.851. Table 5 Mu1 compound 0.197
1 and 2 44B compound 0.19jl to 10? 21) Petroleum coke 597.8 II shown in Table 1 crushed to 80% bath was added to this mixture.
Add little by little at room temperature. After adding the entire amount, mix with a homomixer (manufactured by % Shuki Kako) at 5000 rpm for 5 minutes.
A petroleum coke-water slurry was prepared by stirring for a minute.

The viscosity was measured at 25C and was 560 centipoise, indicating good fluidity.

Under similar conditions, petroleum coke shown in Table 1, polyether compound or its crocodile conductor (a component) shown in Table 2, (kl) component shown in Table 5, and (0) component shown in Table 4 were tied together. The results are shown in Tables 5 and 6, including other examples and comparisons. Low viscosity indicates good fluidity.

(2) Evaluation of stability of water slurry The stability of slurry was evaluated at sO days and 60 days after producing the slurry.
After cooling the device for several days, a stainless steel rod with a diameter of 5 g (weight 501
) was gently placed in the slurry and its settling state was observed w4. The slurry prepared in (1) has good stability and 60
There was little consolidation even after a day had passed. The results, including other Examples and Comparative Examples, are shown in Tables 5 and 6.

Table-1 Table 5(b) Composition Table 4 (oJ component'J Terakairo UGO-55089 (11) Table 5.6 (
Note) Pregnancy 1 See Table 2 Hexagram 2 vs.) '9 Ibase petroleum coke blue 6 See Table 5 Nutrition 4 Do 2 Ibase petroleum coke bone 5 See Table 4 Dishes 6 Do 2 Ibase petroleum coke Kan 7 Versus Dry Pace petroleum coke dinner 80: Good fluidity Δ: Paste-like and slightly fluid.

X: No fluidity 萱90: Good stability (no consolidation of petroleum coke Δ: somewhat good (slight consolidation of petroleum coke) ×: poor (
Petroleum Coke Consolidation Hole) Applicant’s Representative Kaoru Furuya

Claims (1)

[Scope of Claims] t a) An alkylene oxide containing ethylene oxide as an essential component is added to a boriaine compound, and the total weight of the polyoxyethylene chain portion is 40 to 40% of the total molecular weight?
5% by weight, and further has a molecular weight of 5,000 to 200,
A dispersion stabilizer for a water slurry of petroleum coke, which contains as an active ingredient one or more nitrogen-containing compounds selected from a polyether compound or a derivative thereof, and b) a fin compound or an and compound as an active ingredient. . 2 The polyether compound is a block-like or partially block-like adduct of ethylene oxide and an alkylene oxide other than ethylene oxide.Claim N1
A dispersion stabilizer for petroleum coke water slurry as described in . & The streak stabilizer for water slurry of petroleum coke as set forth in Claim 1 4. The streak stabilizer for water slurry of petroleum coke according to any one of claims 1 to 3, wherein the boriaine compound is polyalkyleneboriane or polyethylene ion. & According to any one of claims 1 to 4, the derivative of the polyether compound is a compound obtained by reacting a polyether compound with a fatty acid or a compound obtained by cationizing the nitrogen atom of the polyether compound. Dispersion stabilizer for water slurry of petroleum coke as described. 4&) An alkylene oxide containing ethylene oxide as an essential component is added to a boriaine compound, and the total weight of the polyoxyethylene chain portion is 40 to 95% of the total molecular weight, and the molecular weight is s, ooo to 200,00.
b) one or more nitrogen-containing compounds selected from nitrogen compounds or amide compounds; and one or two aliphatic alcohols, sorbitan fatty acid esters, or silicone compounds. A dispersion stabilizer for petroleum coke water slurry, characterized by containing the above as active ingredients and stagnation.