JPS59166591A - Solid fuel-aqueous slurry composition - Google Patents

Abstract

PURPOSE:A solid fuel-aqueous slurry composition, containing a specific amount of a mixture of a water-soluble aromatic polymer with a water-soluble aliphatic polymer at a specific ratio, and capable of dispersing a solid fuel powder, e.g. coal (carbonized coke)or petroleum coke, stably and in a high concentration in water. CONSTITUTION:A solid fuel-aqueous slurry composition obtained by adding 0.01-5wt% total of (A) a water-soluble aromatic polymer, e.g. salt of naphthalenesulfonic acid-formamide condensate, having usually 500-50,000 MW weight and (B) a water-soluble aliphatic polymer, e.g. salt of a copolymer of a 2-30C aliphatic alpha-olefin and maleic anhydride, at (1:9)-(9:1) weight ratio as an additive to a slurry composition consisting of 50-80wt% solid fuel powder and water.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a solid fuel-water slurry composition for stably dispersing solid fuel powder such as carbonized coke or petroleum coke in water at a high concentration.

Because solid fuels, represented by coal, have a solid shape, they have long yielded the kingship of fuel to petroleum, but in the wake of the oil shock, solid fuels were reconsidered, and coal-oil mixed fuels (COU) were used. As typified by the above, many attempts have been made to treat solid fuel as a fluid rather than mixing solid fuel powder with a medium.

However, in the case of coal-oil mixed fuel, it is impossible to avoid the disadvantage that about half of the fuel is oil, and there is a desire to develop another slurry fuel.

In recent years, slurry, a fluid in which solid fuel is dispersed at a high concentration using water as a medium, has become suitable for transportation by pipeline or oil tanker, and has also been used as an alternative fuel for oil in various boilers and for gasification. Attempts are being made to use it as a raw material. In the case of this slurry, since the medium is water, it is preferable that the slurry has the following properties.

That is, it must have a high solids concentration, a low viscosity, and excellent long-term stability without causing agglomeration or sedimentation of the solid powder. It is also desired that the slurry be able to maintain stability even when mechanical shearing force is applied.

By the way, conventionally, in order to modify the properties of coal-water slurry, rust inhibitors and antioxidants have been added to the slurry.

It is already known to add various additives such as dispersants. However, among these known additives, very few have been found that give very good results on solids concentration or viscosity and also satisfy both this property and the stability of the slurry. for example.

U.S. Patent No. 2.346.151, Japanese Patent Publication No. 1983-
Phosphoric acid esters, various amines, reaction products of alkylene oxides with alkylphenols, naphthols, and other acidic phosphates, and polycarboxylic acids such as polymethacrylic acid disclosed in Japanese Patent Application Laid-Open No. 54-16511, etc. Additives such as salt have poor viscosity lowering properties and are difficult to obtain highly concentrated slurries.

In addition, the sulfonate of an oxyethylene adduct of an alkyl- or alkenyl-substituted phenol proposed in JP-A-56-20090 has a viscosity-lowering function compared to the above-mentioned additives, and it also has a somewhat less stable slurry stability. However, there is still room for improvement in these properties, and the disadvantage is that when mechanical shearing force is applied to the slurry obtained, its stability is extremely reduced, so it is still too early to put it into practical use. I couldn't find anything that satisfied me.

The present invention provides an industrially useful solid fuel-water slurry composition that has an improved low viscosity compared to the one proposed above, and also has excellent static stability and stability against shearing forces. The object of the present invention is to provide a solid fuel-water slurry composition containing a water-soluble aromatic polymer and a water-soluble aliphatic polymer as additives.

That is, when the above additive is used, it is possible to prepare a highly concentrated slurry due to its excellent viscosity lowering function, and it is possible to easily obtain a highly concentrated solid fuel-water slurry composition containing 50 to 80% by weight of solid fuel powder. In addition, this composition has excellent static stability with suppressed oral aggregation and sedimentation, and has high shear force stability without compaction even when subjected to mechanical shear force. It will also be excellent.

If such a composition with excellent shear force stability is manufactured overseas, transported by long-distance pipeline or long-term ship, and then consumed in Japan, This is very advantageous because the composition can maintain sufficient stability against mechanical shearing forces.

As described above, the solid fuel-water slurry composition of the present invention has advantages such as being easy and economical to transport by pipeline or other means, and being easy to supply to a combustion device.

The water-soluble aromatic polymer in this invention includes:

Salts of naphthalene sulfonic acid formaldehyde condensates which may have an alkyl substituent having 1 to 22 carbon atoms, styrene and maleic anhydride or acrylic acid or methacrylic acid which may have an alkyl 1σ substituent having 1 to 3 carbon atoms. Salt of copolymer with carbon number 1. There are salts of a copolymer of styrene sulfonic acid and a vinyl compound, which may have up to 3 alkyl substituents, a compound represented by the following general formula f+), and a formaldehyde condensate thereof.

Its molecular weight is 500-50,000, preferably 10
00-311000.

6- Kyl group or alkenyl group, AO is an oxyalkylene group having 2 to 4 carbon atoms, and at least 6 of the total oxyalkylene groups
0% by weight is an oxyethylene group, and m is 5 to 300.
n is ] or 2. ) As the water-soluble aliphatic polymer in this invention.

Aliphatic α-olefins having 2 to 30 carbon atoms and anhydrous maethylene, propylene, butene-1, isobutylene, butadiene, hexene-1, diisobutylene, dodecene-1% hexadecene-1, and the like are used. Homopolymers of acrylic acid and methacrylic acid are also used.

These compounds are usually used in the form of ammonium salts, alkali metal salts or lower amine salts.

Examples of alkali metal salts include lithium, sodium, or potassium salts, and examples of lower amine salts include alkylamine salts such as methylamine, dimethylamine, trimethylamine, ethylamine, propylamine, and butylamine, and amines having a monoethalcanol group. There is salt.

In this invention, the above-mentioned water-soluble aromatic compound 1 is used as an additive.
It is necessary to select one or more types from among the compounds, select one or more types from among the water-soluble aliphatic polymers, and use both in combination. The ratio of water-soluble aromatic polymer to water-soluble aliphatic polymer is 1,
The quantitative ratio is from /9 to 7/3, preferably from 1 to 7/3. It is thought that this is because by using an aromatic polymer and an aliphatic polymer in combination as in the present invention, the adsorption of each onto the solid fuel particles becomes stronger. Such additives may include known additives such as gelling agents, rust preventives, and preservatives, and alkaline substances, if necessary.

The amount of additive added to the solid fuel-water slurry composition is:
Although it varies depending on the slurry characteristics, that is, the particle size and concentration of the solid fuel powder, or the type of the active ingredient itself, the active ingredient is generally 0.001 to 5% by weight in one composition, particularly preferably O. , OM amount%. As the amount added increases, the viscosity-lowering effect increases, and good results are obtained in terms of stability. but,
If the amount exceeds a certain amount, no further effect can be expected, which is economically disadvantageous.

The method of adding the additive is arbitrary, and an appropriate method may be selected depending on whether the solid fuel powder is obtained by dry pulverization or wet pulverization. For example, in the dry grinding method,
It is preferable to add and mix the additive of the present invention in advance into the water in which the pulverized powder is to be dispersed, and then add and mix the pulverized powder thereto. On the other hand, in the wet pulverization method, it may be added in advance to the water used for wet pulverization, or wet powder may be added in advance to the water used for wet pulverization. homogenizer,
It is best to mix using a stirrer such as a line mixer.

When this invention is applied to coal, the type of coal may be sub-bituminous coal, blue coal, anthracite coal, etc., and is not particularly limited. Further, the solid fuel is pulverized by a dry method or a wet method to obtain a powder for water slurry, but the particle size of this powder is not particularly specified. However, care must be taken to avoid problems such as wear and blockage during pipeline transportation and burner combustion.

Generally, it is preferable that the 200 mesh pass is 50% by weight or more, and more preferably 70% by weight or more.

Next, examples of the present invention will be described and explained more specifically.

The water-soluble aromatic polymers (&
1 to A4) and the water-soluble aliphatic polymer (Ban 5 to Ya 8) were used alone and both were used in combination (Ban 910- to &Js). The properties were compared.

The following test example + VC Therefore, a solid fuel-water slurry composition was actually prepared, and the influence of 9'jiA on the viscosity (25°C), static stability, and shear force of this composition, 6
Table 2 shows the industrial analysis values of petroleum coke obtained from industrial bituminous coal and heavy oil from the Middle East. Table 2 As for the properties of the solid fuel-water slurry composition, viscosity, static stability, and stability against shearing force were measured.

The viscosity (25° C.) of the composition was measured using a B-type viscometer, and the static stability was examined using the following method. That is, the diameter is 51. A stainless steel cylinder with a height of 20 el+ was provided with stoppered outlets at positions 6 and 125+ from the bottom, and the unobtained composition was poured into the cylinder up to 18 es+ from the bottom and allowed to stand at room temperature for one week. I placed it. Next, the cylinder bottom is divided into an upper layer above 125 mm, a middle layer between 6 and 12 countries, and a lower layer below 6 mm, and the solid content of each layer is left in a dryer at 105° C. for 1 hour. It was measured with

f, Stability due to shear force was determined by the following method. That is, the obtained composition was put into a 1-inch beaker with a diameter of 1051% and a height of 15 mm up to the 5-nout line, an impeller with a blade diameter of 2α was set at the 400 mm position, and stirred at 2 nm rpm for 24 hours. After the stirring was stopped, the impeller was removed and left as it was for 14 days. Next, tilt the beaker to pour out the composition, and if all of it flows out, it will remain at the bottom, but if it can be easily re-fluidized with a glass rod, etc., a hard sediment will form at the bottom and be easily removed with a spatula, etc. Cases in which this is not possible are indicated by ◎, ○, or ×, respectively.

In the case of ◎ or 0, it was determined that a composition strong against shearing force was obtained.

Test Example 1 Dry crushing of American bituminous coal yields 2nO mesh pass of 70
% coal powder was obtained. The moisture content of this powder is 2% by weight.
(including attached water). Next, take 142.9 JF of an aqueous solution in which predetermined amounts of each of the additives of the above examples and Hisame examples were dissolved in a beaker of 3 (10 mm) using a homomixer M type manufactured by Tokushu Kika Kogyo ■. ~500rp
357.19 of the above coal powder while stirring slowly at m.
was gradually added, and after the addition was finished, the rotation speed of the homomixer was increased to 5.000 rpm VC and stirred for 10 minutes to obtain a coal-water slurry composition with a solid content of 70% by weight. The following Table 3 shows sample shop 9~ as additives of this invention.
5. These are the results of Test Example 1 when Sample Flats 1 to 8 were used as additives for comparison.

15- Test Example 2 In a ball mill with a capacity of 5 mm (ball filling rate: 30% by volume), 36°F of coarsely crushed petroleum coke in order of particle size was taken, and 140 t of an aqueous solution in which each of the above additives was dissolved was added. By grinding for 30 minutes, a petroleum coke-water slurry composition having a solid content of 72% by weight and having a particle size of 200 mesh particles of 1 petroleum coke powder of 78% by weight was obtained. Table 4 shows samples A9~ as additives of this invention.
These are the results when samples f1 to f8 were used as additives for comparison.

17-700- -18- As is clear from the above test results, by using the additive of the present invention, it is possible to achieve high concentration and low viscosity, and also to improve static stability and shear force stability. It can be seen that a homogeneous solid fuel-water slurry composition is obtained.

Patent applicant: NOF Corporation -1・9-

Claims (1)

[Scope of Claims] 1. In a solid fuel-water slurry composition consisting of 50 to 80% by weight of solid fuel powder and water, a water-soluble aromatic polymer and a water-soluble aliphatic heavy metal substance are mixed as additives in a ratio of 1:9. ~9:l
A solid fuel-water slurry composition containing a total amount of 001 to 5% by weight. 2. Water-soluble aromatic polymers include salts of naphthalene sulfonic acid formaldehyde condensates which may have an alkyl substituent having 1 to 22 carbon atoms, styrene and anhydride which may have an alkyl substituent having 1 to 3 carbon atoms. A claim that is a salt of a copolymer of maleic acid, acrylic acid, or methacrylic acid, or a salt of a copolymer of styrene sulfonic acid, which may have an alkyl substituent having 1 to 3 carbon atoms, and a vinyl compound. The solid fuel-water slurry composition according to item 1. 3 The water-soluble aliphatic polymer is aliphatic α having 2 to 30 carbon atoms.
- The solid fuel-water slurry composition according to claim 1, which is a salt of a copolymer of olefin and maleic anhydride, acrylic acid, or methacrylic acid. 4. The solid fuel-water slurry composition according to claim 1, wherein the solid fuel powder is coal carbonized coke or petroleum coke powder.