JPH0443958B2 - - Google Patents

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 suitable for pipeline transportation. Since the oil crisis, the proportion of heavy distillates in Japan's imported crude oil has tended to increase due to the rise in crude oil prices and the need to diversify crude oil supply destinations. On the other hand, with the remarkable development of the petrochemical industry, the demand for light distillates as raw materials continues to increase. For these reasons, heavy fractions in crude oil are becoming 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 cracking 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. However, since the fuel made by dispersing petroleum coke in oil requires the use of oil, recently research has been conducted into a water slurry technology in which petroleum coke is dispersed in water, which allows petroleum coke to be handled as a fluid without using oil. There is. Petroleum coke water slurry is made by dispersing petroleum coke fine 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. In order to directly burn petroleum coke/water slurry, it is necessary to reduce the water content as much as possible and increase the concentration of petroleum coke. However, since petroleum coke is hydrophobic, it causes coagulation in water and increases the concentration. Fluidity is often lost, and when put into practical use,
This will be a big challenge. When a surfactant, which is a dispersant, is added to the petroleum coke/water slurry, the surfactant adsorbs to the interface between petroleum coke and water, loosening the petroleum coke particles into pieces, and causing the petroleum coke particles to coagulate with each other. It is expected to create a good dispersion state due to the effect of preventing However, surfactants such as general alkylbenzene sulfonates, petroleum sulfonates, and quaternary ammonium salts have insufficient fluidity and lack practicality. Also, alkylphenolamine oxide adducts have been proposed for the same purpose (Japanese Patent Application Laid-Open No.
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, and if the coke concentration in the slurry is about 60 wt%, It is difficult to produce a slurry with such a high concentration. 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 provides (a) an alkylene oxide that essentially contains ethylene oxide is added to a polyamine compound, and the total weight of the polyoxyethylene chain portion is 40 to 95% by weight of the total molecular weight, and the molecular weight is 5,000 to 200,000. Contains as essential components one or more nitrogen-containing compounds selected from polyether compounds or derivatives thereof, and (b) kamine compounds or amide compounds, and further contains (c) aliphatic alcohol and sorbitan fatty acid as necessary. This is a dispersion stabilizer for an aqueous slurry of petroleum coke powder, characterized by containing one or more selected from the group consisting of esters and silicone compounds. Examples of polyamine compounds used as raw materials for polyether compounds or derivatives thereof, which are obtained by adding alkylene oxide containing ethylene oxide to the polyamine compound used as component (a) of the dispersion stabilizer of the present invention, include ethylene diamine, propylene diamine, diethylene triamine, and triethylene. Examples include polyalkylene polyamines such as tetramine and tetraethylenepentamine, and polyethyleneimine. A polyether compound can be easily obtained by adding an alkylene oxide which essentially contains ethylene oxide to a polyamine compound by a conventional method. Among these, block or partially block-like adducts of ethylene oxide and propylene oxide are particularly preferred, and the order of addition may be in any order, but propylene oxide (hereinafter referred to as
Abbreviated as PO. ) is added first and then ethylene oxide (hereinafter abbreviated as EO) is added, showing good dispersion stability. The molecular weight of the polyether compound or its derivative is
The range is 5,000 to 200,000, preferably 10,000 to 100,000, and more preferably 30,000 to 80,000. Also
The total weight of the EO chain portions is 40-95% by weight of the total molecular weight, preferably 80-95%. Examples of the derivatives of the polyether compound of the present invention include sulfates, phosphoric oxides, carboxyalkylated products, fatty acid esterified products of the terminal hydroxyl group of the polyether compound, and those obtained by cationizing a part of the nitrogen atom of the polyether compound. 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 23 carbon atoms,
The number of double bonds, branching, etc. have no effect on performance.
Examples of cationized products include compounds obtained by cationizing a polyether compound with dialkyl sulfuric acid, alkyl halide, etc., and cationized products neutralized with acetic acid, alkylbenzenesulfonic acid, etc. Component (b) of the present invention is one or two nitrogen-containing compounds selected from amine compounds and amide compounds.
More than one species is used. Among these nitrogen-containing compounds,
Amine compounds include primary amines such as octylamine, laurylamine, tallow amine, secondary amines such as diethylamine, distearylamine, morpholine, etc., tertiary amines such as dimethylstearylamine, dimethyllaurylamine, aromatic amines such as aniline, dibenzyl, etc. Amine, toluidine, etc. and polyamine compounds include polyalkylene polyamine, alkyl (or alkenyl) polyalkylene polyamine, polyethylene imine, etc. Examples include ethylene diamine,
These include triethylenetetramine, laurylpropylene diamine, stearyltriethylenetoteramine, stearyltetraethylenebentamine, and stearylpentaethylenehexamine. Also effective are amine salts produced by neutralizing these amine compounds with acidic compounds and quaternary ammonium salts quaternized by known methods. For example, amine salts include acetates, hydrochlorides, sulfates, etc. of the above-mentioned amine compounds, and quaternary ammonium salts include compounds obtained by cationizing the above-mentioned amine compounds with alkyl halides, dimethyl sulfate, etc. using known methods. Examples include lauryltrimethylammonium chloride and stearyltrimethylammonium chloride. Further, the amide compound is a reaction product of carboxylic acid and ammonia or the above-mentioned amine compound, and examples thereof include stearic acid amide, ethylenediamine lauric acid monoamide, triethylenetetramine stearic acid diamide, and the like. In addition, among the components (c) used as necessary in the dispersion stabilizer of the present invention, the aliphatic alcohol specifically has a carbon number of 6 to 12.
Examples of aliphatic alcohols used include octyl alcohol, 2-ethylhexyl alcohol, and lauryl alcohol. Examples of the sorbitan fatty acid ester include sorbitan monolaurate, sorbitan monopalmitate, sorbitan monooleate, sorbitan monostearate, and the like. Similarly, silicone compounds of component (c) include polydimethylsiloxane, dimethylsilicone oil, fluorosilicone oil, and the like. The dispersion stabilizer of the present invention can disperse petroleum coke particles in water by adding it in an amount of 0.01 to 5.0% by weight, preferably 0.05 to 2.0% by weight, based on the water slurry. Both components (b) and (c) in the dispersion stabilizer of the present invention are 30% by weight or less, preferably 15 to 5% by weight, based on the polyether compound or its derivative as component (a), and It may be added together with the coal coke slurry, or it may be added separately to the petroleum coke slurry. The mixing order of petroleum coke, dispersant, and water may be in any order, but the dispersant may be dissolved in water, petroleum coke or petroleum coke fine powder may be added thereto, and the mixture may be prepared 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 used can have an appropriate particle size from the viewpoint of combustion and crushing cost, but 200
A 60-90% pass is used as a guideline. The fluidity of a petroleum coke-water slurry generally varies depending on the type and particle size of the petroleum coke powder, but if no dispersion stabilizer is added, the viscosity will increase rapidly when the petroleum coke concentration exceeds 30% by weight. It's coming. On the other hand, when a predetermined amount of the dispersion stabilizer of the present invention is added, petroleum coke particles are dispersed, fluidity is significantly improved, and a highly concentrated slurry can be obtained.At the same time, if left for a long time, it will settle and form a hard cake. A slurry with excellent storage stability that does not form can be obtained. 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,
Since the viscosity becomes too high, the content is generally 30 to 85% by weight, preferably 50 to 78% by weight, although it varies depending on the type and viscosity of petroleum coke. The dispersion stabilizer of the present invention has as an essential component a polyether compound obtained by adding alkylene oxide to a polyamine compound or a derivative thereof, and uses this in combination with one or more nitrogen-containing compounds selected from amine compounds or amide compounds. Furthermore, if necessary, component (c) selected from aliphatic alcohols, sorbitan fatty acid esters, or silicone compounds can be used in combination to achieve excellent effects with a relatively small amount of addition, and to improve particle size distribution, preparation conditions, etc. It has revolutionary performance that is unaffected. This is because components (b) and (c), which have lower molecular weights than component (a), adsorb to the pores on the petroleum coke surface and make the pores hydrophobic, allowing the water necessary for dispersion to enter. This is thought to be due to the fact that the dispersion stability is dramatically improved compared to component (a) alone. The dispersion stabilizer of the present invention can be used in combination with other anionic surfactants or nonionic surfactants. For example, naphthalene sulfonic acid formalin condensate or sodium lignin sulfonate, petroleum coke using the dispersion stabilizer of the present invention, fatty acids such as oleic acid, phosphate esters such as tributyl phosphate, or metal soaps such as aluminum stearate. By adding such substances, a stable slurry with less air bubbles can be obtained. Petroleum coke added with the dispersion stabilizer of the present invention
In order to separate and recover the petroleum coke from the water slurry after its use as a means of transport, a third liquid such as hydrocarbon oil that is immiscible with water as a dispersion medium is added to the water slurry to form petroleum coke powder. A method of granulating, separating and recovering from water is attracting attention. For this purpose, petroleum coke-
Although hydrocarbon oil is sometimes added when preparing an aqueous slurry, the dispersion stabilizer of the present invention exhibits excellent performance without losing its dispersion effect even in systems where such hydrocarbon oil coexists. 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 stability without forming hard cakes even after long-term storage. Pipeline transportation, tank storage, and direct boiler combustion are possible. In addition, the petroleum coke water slurry obtained using the dispersion stabilizer of the present invention has fewer bubbles during production, and the volume of the slurry is less increased.
Further, thickening due to air bubbles can be prevented and good properties can be obtained. 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 2 No. 4 compound 1.85 g, Table 3 No. 1 compound 0.19 g
0.19 g of Table 4 No. 3 compound is dispersed in 109 g of water, and 397.8 g of the petroleum coke shown in Table 1, which has been crushed to a 200 mesh 80% pass, is added little by little at room temperature. After the entire amount was added, the mixture was stirred for 5 minutes at 5000 rpm using a homo mixer (manufactured by Tokushu Kikako) to prepare a petroleum coke-water slurry. The viscosity was measured at 25°C and was 360 centipoise, indicating good fluidity. Under the same conditions, the petroleum coke shown in Table 1, the polyether compound or its derivative (a component) shown in Table 2, and the petroleum coke shown in Table 3
The results are shown in Tables 5 and 6, including other Examples and Comparative Examples in which various combinations of component (b) and component (c) shown in Table 4 were used. Low viscosity indicates good fluidity. (2) Evaluation of the stability of water slurry The stability of the slurry is determined by allowing the slurry to stand for 30 and 60 days after production, and then gently inserting a stainless steel rod with a diameter of 5 mm (weight 50 g) into the slurry and observing its sedimentation state. Observed. The slurry prepared in (1) had good stability and showed almost no compaction even after 60 days. The results, including other Examples and Comparative Examples, are shown in Tables 5 and 6.

【table】

【table】

【table】

【table】

【table】

【table】

【table】

Claims (1)

[Claims] 1 a Adding an alkylene oxide that essentially contains ethylene oxide to a polyamine compound,
and a nitrogen-containing polyether compound or a derivative thereof, in which the total weight of the polyoxyethylene chain portion is 40 to 95% by weight of the total molecular weight, and the molecular weight is 5,000 to 200,000, and (b) an amine compound or an amide compound. A dispersion stabilizer for petroleum coke water slurry, characterized by containing one or more compounds as an active ingredient. 2. The dispersion stabilizer for an aqueous slurry of petroleum coke according to claim 1, wherein the polyether compound is a block-like or partially block-like adduct of ethylene oxide and an alkylene oxide other than ethylene oxide. 3. The dispersion stabilizer for petroleum coke water slurry according to claim 1 or 2, wherein the alkylene oxides in the polyether compound are ethylene oxide and propylene oxide. 4. The dispersion stabilizer for petroleum coke water slurry according to any one of claims 1 to 3, wherein the polyamine compound is a polyalkylene polyamine or polyethylene imine. 5. 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. 6 a Adding an alkylene oxide that essentially contains ethylene oxide to a polyamine compound,
and the total weight of the polyoxyethylene chain portions is 40 to 95% by weight of the total molecular weight, and the molecular weight is 5,000 to 200,000. b. A nitrogen-containing compound selected from kamine compounds or amide compounds. 1. A dispersion stabilizer for an aqueous slurry of petroleum coke, characterized in that it contains one or more kinds of aqueous slurries of petroleum coke, and c. one or more kinds of aliphatic alcohols, sorbitan fatty acid esters, or silicone compounds.