JPS59161486A - Coal and alcohol mixture - Google Patents

Abstract

PURPOSE:A mixture of powdery coal and alcohol that contains specific amounts of a nonionic surfactant and a hydroxide, respectively, thus being flowable, even after standing for a long period of time, and showing high flowability at low temperature suitable for transport through pipes. CONSTITUTION:The objective mixture of powdery coal and alcohol contains (A) 0.01-7wt% of a nonionic surfactant composed of an alkylene oxide adduct to a starting substance bearing active hydrogens and (B) 0.01-3wt% of a hydroxide of the formula: X(OH)n (X is alkali or alkaline earth metal, complex ion, ammonium; n is 1-3). As a comonent B, the one whose solubility is more than 0.01wt% in water at 20 deg.C is preferred.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a mixture mainly composed of powdered coal and alcohol, which has excellent flow characteristics even at low temperatures and is suitable for pipe transportation.

There are concerns about the supply of petroleum fuels. There is a need to diversify energy sources, and coal, which is estimated to have more reserves than oil, is being seen as an energy alternative to oil. Despite the fact that coal can be obtained extremely cheaply in the production areas. Because it is solid.

Unlike gases such as natural gas and liquids such as oil, it is impossible to transport them over long distances by pipeline.

Furthermore, handling during use is extremely inconvenient, leading to high energy costs at the consumption site.

In order to solve these difficulties, there is an idea to transport pulverized coal as a coal/water slurry by pipeline, but this would also involve transporting water, which cannot be used as an energy source. The effect of improving transportation costs is extremely small. In addition, in the so-called coal-oil mixed fuel, in which powdered coal is mixed with oil, the entire mixture is used as energy, but because oil becomes a viscous liquid or solid at low temperatures, long-distance transportation by pipeline has not yet been realized. It leaves many unresolved issues.

Coal/alcohol mixed fuel, which is made by dispersing powdered coal in alcohol, is an excellent mixture that can solve the above problems all at once. However, the powdered coal in the coal/alcohol mixture has a higher settling speed than the other slurry systems mentioned above, and tends to separate from the liquid force and deposit only solids on the bottom of the reactor.

When this slurry is in a fluid state, it can be handled with a relatively low viscosity, but once the slurry is in the device, it cannot be fluidized unless an abnormal force is applied due to the powdered coal deposited at the bottom of the container, and in extreme cases, particles There are times when comrades solidify and become unable to flow.

Due to these difficulties, coal-alcohol slurry has low viscosity and has excellent properties of maintaining fluidity even at low temperatures in winter, but it has not yet reached the stage of practical use.

The present inventors have discovered the above-mentioned excellent properties of the coal-alcohol mixture! As a result of intensive studies to facilitate stationary refluidization without causing damage, it was determined that a specific nonionic surfactant would be needed to prevent consolidation due to sedimentation of coal particles and reduce viscosity7. The present invention was achieved by discovering that the problem could be solved by using hydroxide in combination.

That is, 1 the present invention provides a mixture containing powdered coal and alcohol as main components, in which 0.01% of the nonionic surfactant is used.
~7% by weight and the general formula % (wherein, X represents an alkali gold stripe, alkaline earth metal, lead-based ion or NH, and n represents 1 to 3). The present invention relates to a mixture of coal and alcohol characterized by a mixture of 0.01 to 3% by weight.

As the nonionic surfactant that can be used in the present invention, polyethylene glycol type surfactants are preferably used.
53956.57-153957, the use of which is disclosed by alkylene oxide adducts of starting materials with one or more active water groups. Examples of such starting materials include alcohols such as ethyl alcohol, lauryl alcohol, cyclohexanol, benzyl alcohol, ethylene glycol, polyethylene glycol, butanediol, glycerin, triethanolamine, sorbitol, partially saponified polyvinyl acetate, starch, n- Hexyl alcohol, 3-n-hexene-1-
ol, 1so-octyl alcohol, lauryl alcohol, n-dodecane-2-ol.

Examples include cetyl alcohol, stearyl alcohol, lylunyl alcohol h1e12-n-octadecanediol, and sorbitol. Examples of carboxylic acids include acetic acid, shiulic acid, and heptalic acid.

Ethylenediaminetetraacetic acid, acrylic acid polymer, caproic acid, incaproic acid, caprylic acid, n-undecanoic acid,
Examples include 4-dodecenoic acid, stearic acid, oleic acid, sebacic acid, n-heptadecane-1°3,5)+1 carboxylic acid, and the like. Examples of phenols include phenol, alkylphenol, and naphthol. Furthermore, examples of amines include dimethylamine, laurylamine, aniline, and triethylenetetramine.

The number of moles of alkylene/oxide added is preferably an integer of 5 or more, more preferably an integer of 10 to 100, and it is better for the ethylene oxide group to be partially or completely bonded to the terminal, and not to be added randomly. Not enough effect. In the molecule, at least one type selected from ethylene oxide group, propylene oxide group, and butylene oxide group is an ethylene oxide group, and it may be used alone or in combination of two or more types.

In the final polyether compound of the sword/karu, the ethylene oxide content is in the range of 30% by weight or more, more preferably 40% by weight or more. In this case, if the ethylene oxide content is less than 30% by weight, the hydrophobicity of the polyether compound becomes strong and the stability effect becomes small. The molecular weight is preferably 1,000 to 100,000°, more preferably 3,
If the molecular weight is less than 1,000, the stability effect tends to be poor, and if it exceeds 100,000, the solubility in alcohol tends to be low.

Examples of hydroxides used in the present invention include hydroxides of alkali metals such as sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, etc., and hydroxides of alkaline earth metals include hydroxide. Examples include calcium oxide and barium hydroxide.

Examples of the complex compound include hexaammine cobalt hydroxide and hexaammine chromium hydroxide, and examples of the ammonia hydroxide include ammonium hydroxide.

The above-mentioned hydroxide is one example, and the present invention is not limited thereto. The hydroxide used in the present invention preferably has a solubility in water of 0.01% by weight at 20°C.
Above, more preferably 1 weight or more, and if it is less than O, Oi type weight, the effect as a viscosity reducing agent is surprisingly small, and the hydroxide water bath liquid is preferably alkaline, and more preferably In an aqueous solution at 20° C. and a concentration of 1% by weight, l'H is 7.5 or more, and if the pH is less than 7.5, the effect as a viscosity reducing agent tends to decrease. The amount of the above-mentioned nonionic surfactant in the aqueous dispersion is 0.01 to 7% by weight based on the total amount of the mixture of coal and alcohol.

Preferably, the proportion is in the range of 0.5 to 3% by weight.

If the amount added is less than 0.01% by weight, a sufficient stability effect cannot be obtained, and if the amount added exceeds 7% by weight, economic efficiency is lost.

The amount of hydroxide is in the range of 0.01 to 3% by weight, preferably 0.1 to 1% by weight, based on the total amount of the mixture of coal and alcohol. The percentage is 0.01% by weight.
If it is less than 3% by weight, a sufficient viscosity-lowering effect cannot be obtained, and if it exceeds 3% by weight, economical efficiency is lost.

The particle size of powdered coal is usually adjusted to 1 arm or less.

The preferred coal concentration to maintain optimal fluidity of powdered coal is relative to the total amount of coal and alcohol.

It ranges from 30 to 80% by weight. From a cost standpoint, the higher the coal concentration is, the better it is, but if the concentration is too high, the power required to transport it through pipes will be too high, and economic efficiency will be lost.

1 In the present invention, it is possible to increase the concentration by utilizing the viscosity reduction caused by hydroxide, so the total amount of coal and alcohol is 5%, which is a practically important coal concentration range.
It can be 0 to 70% by weight.

The type of alcohol does not need to be particularly limited as long as it coagulates at low temperatures and maintains a relatively low viscosity even at low temperatures, but alcohols that satisfy the low-temperature physical properties mentioned above include carbon. Numbers 1 to 4 are practical. Furthermore, considering the production cost of alcohol, the production cost of alcohol with one carbon number, that is, methanol, is much cheaper than other alcohols, and methanol has the most important position among the alcohol groups used in the present invention. .

The additive of the present invention may be added at the time of mixing coal and alcohol or added to the mixed liquid, and either method can achieve the effects of the present invention.

The coal used in the present invention may be anthracite S-bituminous coal, sub-bituminous coal, or lignite, and may be used alone or in combination.

The solid-liquid mixture of the present invention can contain water in an amount of 30% by weight or less based on the total amount, but if it is too large, it is economically and physically disadvantageous. Although coal itself naturally has a considerable amount of attached water, it is preferable that the total amount of water used in adjusting additives is in the range of 5 to 10% by weight.

As mentioned above, in the present invention, by using a nonionic surfactant and a hydroxide in combination with a mixture whose main components are powdered coal and alcohol, it is possible to prevent compaction due to sedimentation of coal particles and to achieve an extremely high level of stability even in highly concentrated mixtures. Able to maintain low viscosity.

Hereinafter, the present invention will be explained in detail with reference to Examples and Comparative Examples.

Example 1 Powdered bituminous coal (particle size lIrIm or less, passed through 200 mesh 45% by weight, water content [6% by weight)] 2809% oxyethylene oxypropylene block copolymer (m in Table 2)
l) 1 part by weight and 2.5 f of sodium hydroxide (12.5 parts of water
Add to a mixture of 205 tons of methanol and 205 tons of methanol, and add to the mixture of
Stir for 5 minutes.

After filling a 300 yen measuring cylinder with 300 yen of this, vibration (low tag type, xascpm, o, 5G) was applied to 1
A consolidation acceleration test was conducted by adding additional time (equivalent to 30 days or more for the static stability test). After standing still, the consolidation height was measured by the method of rod penetration test (middle 1) described below, but no consolidation layer was observed.

A sample was prepared in the same manner, and the viscosity (medium 2) was measured using the method described below: VcJ, and found to be 60 Cp. This solid/liquid mixed fuel, mainly composed of a mixture of coal and alcohol, was suitable for pipeline transportation and was stable enough to withstand long-term storage.

(* 1) After the graduated cylinder that has completed the T41 penetration test and consolidation acceleration test is left standing,
A lid body with a glass rod guide hole was installed so that the guide hole was centered at the top of the cylinder.

Through the guide hole, a glass rod with a smooth tip (total weight of 40 f) having a diameter of 6 m was allowed to naturally fall vertically from the liquid surface. The space between the tip of the rod and the bottom of the cylinder when the rod is stopped is called a compaction layer, and the smaller the formation of this compaction layer, the better the static stability is.

(Medium 2) Viscosity measurement Measured using a double cylindrical viscometer (Rotor MVn, manufactured by Yasushi Kasha) at a liquid temperature of 20° C. and a shear rate of 20 SeC.

Example 2 The same method as in Example 1 was carried out, except that the ratio of coal/additive/alcohol, the type of additive, and the addition lid were changed.

A solid/liquid mixed fuel consisting mainly of a mixture of coal and alcohol was prepared. The viscosity and static stability of these products are shown in Table 1 along with the results of Example 1.

Comparative Example 1 Powdered bituminous coal (particle size 1 mm or less, 45% by weight passed through 200 mesh 5, water content 6% by weight) 2809 and 2 methanol
Add 20f and 50°rpm with 4 screw type blades.
, stir for 5 minutes. After filling this 1300-meter graduated cylinder with 300mA', vibration (rotor tube type, 135cp)
m, 0. sG)w was added for 1 hour to perform a consolidation acceleration test. When the consolidation height t was measured in the rod penetration test (after placing the rod in middle school 1), the formation of a consolidation layer was observed.

When the sample was prepared in the same way and the viscosity (rate 2) was measured, it was 3
It was 80 C'P.

This solid/liquid mixed fuel, which is mainly composed of a mixture of coal and alcohol, is compacted and has a high viscosity.

Not suitable for high concentration.

Comparative Example 2 Using the same method as Comparative Example 1, changing the ratio of 1 coal/added water/alcohol, using only nonionic surfactant, and using only hydroxide, respectively, compared to Comparative Example 1. The results are also listed in VC Table 1. The properties of the coal used in the Examples and Comparative Examples are shown in Table 3.

As shown in Table 1, by using a nonionic surfactant and hydroxide together, the solid/liquid mixed fuel produced by the IC of the present invention can be transported by pipeline at a high concentration regardless of the type of coal or alcohol VC. It was found to have suitable flow properties and long-term storage stability.

Table 2 (middle 3) E (J is ethyleneoxy)-, PO represents propylene oxide, and BO represents butylene oxide.

Claims (1)

[Scope of Claims] (Li) A nonionic surfactant consisting of an alkylene oxide adduct of the starting material having one or more active hydrogens Jk: 0.01 ~7% by weight and general formula % formula %) (wherein, X is an alkali metal, represents a lead-based ion or NH4, and n represents 1 to 3). A mixture of coal and alcohol characterized by a mixture of .01 to 3% by weight. , (2) The mixture according to claim 1, wherein the hydroxide has a solubility in water of 0.01 weight or more at 20°C. (3) The mixture according to claim 1, wherein the hydroxide is alkaline in aqueous solution.