JPS59159892A - Viscosity depressant for concentrated coal/water slurry - Google Patents

Abstract

PURPOSE:To provide a viscosity depressant which contains formalin condensates of sulfonate of polycyclic aromatic compd. and sulfonate of monocyclic aromatic compd. as essential ingredients and produces a concentrated coal/water slurry which can be transported by pumping. CONSTITUTION:A polycyclic aromatic compd. in which the aromatic nucleus may be substituted with hydrocarbon, hydroxyl or carboxyl group (e.g. naphthalene or anthracene) and/or monocyclic aromatic compd. in which the aromatic nucleus may be substituted with hydrocarbon, hydroxyl or carboxyl group (e.g. phenol or xylene) is sulfonated and the two compds. and blended in a molar ratio of 1:9-9:1. The mixture is condensed with formalin and is neutralized when necessary. The viscosity depressant contains the condensate (or salt thereof) as essential ingredient.

Description

[Detailed description of the invention] The present invention relates to a thinning agent for lime-water slurries.

More particularly, it relates to a thinning agent for dispersing pulverized coal in water to provide a highly concentrated lime-water slurry that can be pumped.

In recent years, due to the depletion of oil resources, the use of coal has been reconsidered.
Various ways of using it are being considered.

However, unlike petroleum, lime is a solid and cannot be transported by pump. Therefore, various methods of dispersing lime in powder form and dispersing it in water to make a water slurry have been investigated. On the other hand, lowering the coal concentration reduces transport efficiency and requires a dewatering process before combustion, which is expensive and difficult to transport. stomach.

Japanese Patent Publication No. 52-71506. In 1982-21636, lumps of phthalene sulfonic acid, these 71=, A/
Marine condensates have been described, but when these compounds are used alone, their viscosity-reducing effect is weak, and at high coal concentrations of 61% or higher, the viscosity increases rapidly and dilatancy occurs, making them impractical for practical use. Pumping becomes difficult. and stable.

This is a practical problem because stone sedimentation occurs and an l-do cake is formed.

The present inventors conducted extensive research on a thinning agent for stone-water slurry that makes highly concentrated coal-water slurry flowable and enables pump transportation. A thinning agent has been successfully developed which significantly reduces the viscosity and thus provides a coal-water slurry that can be pumped even at high coal concentrations.

As lime used in the coal-water slurry of the present invention (d
'Anthracite, blue coal, '1III nogastric coal, lignite, also 't
You can open the ones that have been cleaned and heated, but
It may be coal such as. In addition, the particle size of the stone jΔ in the water slurry may be any particle size as long as it is powder, but since the pulverized coal currently burned in thermal power plants is more than 200 particles per pass and 70% by mass. , this particle size is a guideline for the particle size of pulverized coal. However, the viscosity reducing agent of the present invention is determined by particle size and exhibits excellent effects no matter what particle size it is applied to coal powder.

Lime that has been thoroughly cleaned is made by removing inorganic substances such as ash and sulfur from coal. Examples of methods for cleaning coal include Oi], Agv'
, ] oITIpration method (referred to as Koshita OAm),
There are methods such as the coal selection method and the small armpit method. However, methods other than these W may also be used and are not particularly limited.

Regarding the 0A method, after grinding lime dry or wet, prepare a water slurry, and add an appropriate amount of oil with a surfactant added if necessary, or coat coal with the oil in advance and prepare a water slurry. By adjusting and stirring, the organic components of lime are selectively wetted by oil and water, making use of the difference in wettability of the organic components of lime and inorganic components to oil and water. . On the other hand, since the inorganic substance 1 has a weak affinity with oil, it is free in water, so if the aggregated lime is hydrolyzed, the inorganic substance can be removed at the same time. The coal concentration in the lime-water slurry in the OA method is usually 10 to 50% by weight.

The oil used in the OA method is crude oil or various fractions distilled from crude oil, such as kerosene, light oil, A heavy oil, B heavy oil, c
These include B oil, tar or shale oil, ethylene cracked residual oil, and various blended oils, oils commonly used as fuel, and mineral oils such as lubricating oils and cleaning oils. Water-insoluble oils such as benzene, toluene, xylene, and animal and vegetable oils are also used, but heavy oils such as C heavy oil and tar residue oil are particularly preferred because they are inexpensive. In general, an amount of 30% by weight or less is sufficient based on the coal in the stone extraction-water slurry to be prepared.

In addition, the flotation method is an existing selection method in which a very small amount of oil is added to the finely divided ash-water slurry and stirred to create foam.
Generate floss. In this method, like the OA method, the organic content of coal adheres to the froth oil film, but the inorganic substances are liberated in the water and can be separated from the organic content of coal.

The oils used in the n-free selection method are Kuhi°neol, tar, A heavy oil, O heavy oil, light oil, and kerosene LD+.

The above method generally removes several tens of weight percent or more of inorganic material from coal.

In this way, if clean (burned) coal is used, compared to uncleaned coal, the present invention's Attachment 7
The effect of ``is very good, and it is possible to obtain a coal-water slurry with several points higher concentration. In addition to the effect of using FC using cleaned lime, there is also the effect of reducing boiling rot during soot burning.
- suppressed 1 and sent to ash removal equipment, desulfurization equipment q) negative phase, 7
5=The benefits such as reduction are very large.

Next, the viscosity-reducing temperature 1 used in the coal-water slurry of the present invention is as follows.
is a thinning agent for highly concentrated de-stone-water slurry used to lower the viscosity of coal-water slurry and improve its fluidity and stability, and the aromatic nucleus is R (hydrogen group, [a] Sulfonic acids of polycyclic aromatic compounds and monocyclic aromatic arsenic compounds, which may be substituted with hydroxyl or carboxyl groups; (Sulfonic acid of arsenic compound and monocyclic aromatic compound (sulfonic acid of arsenic compound, or formalin condensation product of sulfonic acid of polycyclic aromatic compound and monocyclic aromatic r arsenic compound, It is a thinning agent for coal-water slurry characterized by containing or a salt thereof as an essential component.

More specifically, the polycyclic aromatic compound of the present invention's viscosity reducing agent includes an r compound having a naphthalene ring, an anthracene ring, or a phenanthrene ring.

, these polycyclic aromatic compounds or their sulfonic acids (component A) fd, such as naphthalene, anthracene,
Examples include phenanthrene, butylnaphthalene, butylnaphthalene, propylnaphthalene, methylanthracene, naphthol, methylnaphthol, naphthoic acid, lignin, and their sulfones.

Monocyclic aromatic compounds or their sulfonic acids (component B), such as henzene, phenol, cresol, butylphenol, nonylphenol, salicylic acid, female aromatic acid, toluene, xylene, ethylbenzene, etc., and their sulfonic acids are It will be done.

That is, the thinner according to the present invention can be any combination of polycyclic aromatic compound and monocyclic aromatic compound that are capable of sulfone ft reaction and condensation reaction with formalin.

The thinner according to the present invention is a polycyclic aromatic compound alone, a monocyclic aromatic arsenate alone, or both a polycyclic aromatic arsenate and an r@cyclic aromatic compound. After sulfonation using a conventional method and condensation reaction with formalin,
It can be produced by neutralizing it to form a salt if necessary.

However, it is not limited to a specific method,
Any method can be employed as long as the desired compound can be obtained.

In this case, the average degree of condensation is preferably 1.5 to 20, more preferably 2 to l○. When the average degree of condensation is outside this range, the viscosity-reducing effect of the stone removal-water slurry is weak. Furthermore, the composition ratio of component A and component B to be subjected to the reaction is (component A)/(component B) = l/9 to 9/l, preferably 3/7.
~8/2.

When the composition ratio is outside this range, the viscosity-reducing effect of the present invention is weak, and it is difficult to increase the concentration of the coal-water slurry.

Salts include (d1) alkali metal salts such as sodium and potassium, alkaline earth metal salts such as calcium, ammonium salts, and amine salts.

The additive 7Il]♀ of the thinner of the present invention is 0.501 to 5.0% by weight, preferably 0.03% by weight, based on the lime-water slurry.
~2.0% by vehicle weight, and an excellent effect is exhibited with this amount of 7J. The fluidity limit of a lime-water slurry varies depending on the type and particle size of the lime, and generally, if a thinner is not added, fluidity disappears when the coal concentration is around 50% by mass.
If the viscosity reducing agent of the present invention is added, the viscosity is significantly reduced, so that the coal has fluidity even when the coal concentration is 61% by weight or more, especially 70% by weight or more. Even more clean (b
Stone/! 7 concentration increases by several more points, typically 3-1'O points.

The thinning agent of the present invention can also be used in combination with other surfactants.

Method for producing lime-water slurry and adding thinner (
Regarding C, there is a method in which coal is dry-pulverized in advance and then a viscosity reducing agent is mixed with VC in an aqueous solution.

A method of adding a thinner after making a coal-water slurry, or adding lime, water, and a thinner to the mill.

Various methods can be used, such as a method of mixing stone removal while crushing it, and a method of mixing using cleaned lime instead of lime in each method.

Reduced viscosity of the present invention 7! The reason why i+1 exhibits an excellent effect is that after it is strongly adsorbed to the particle surface due to its special NQ structure, it prevents particle agglomeration due to acid 1j: factors and stabilizes it as a -order particle, improving fluidity. It seems that the use of cleaned lime such as 'ice ash will further increase its effectiveness.The reason is that 115U ash is highly hydrophilic, has fine particles, and has a large surface area. This is because the reduced irradiation agent of the present invention acts effectively on the coal surface, which has improved organic properties by being removed, and thereby it is possible to measure the concentration of stones.

The uninvented thinning agent has excellent ability to stably disperse coal in water, and for long-term use, for example, it does not cause water separation even after being left in the water for a month, and can form a homogeneous lime-water slurry. keeping.

Thus, the thinner of the present invention is preferably 0.01 to 5.0% by weight, preferably 0.03 to 2.0% by weight, based on the coal-water slurry.
By simply adding 0% by weight, the viscosity of the lime-water slurry can be significantly reduced, and a lime-water slurry that can be pumped at a low concentration can be produced.

A major example is shown below. The percentage in the case of firearms depends on the small amount.

Meitellia Example 1 Add 20
Add powdered lime at room temperature with stirring to adjust the slurry to a predetermined concentration (7) lime-7 up to 80% pass. The viscosity of this slurry is measured at 25°C and the fluidity is observed. Add this slurry to 500
After putting it in a πl cylinder to a lightness of 18o++ and leaving it for one month, the lime concentration in the upper wI (Icy from the top) and lower layer (lCM from the bottom) was determined by the γ law.

The test results are shown in Table 2. As shown in Table 2, when the thinner of the present invention is added, the viscosity is 1100-2800 cP even at a coal concentration of 74-77%, and the fluidity is extremely good.

In addition, even after the slurry was allowed to stand for one month, there was almost no sedimentation of the coal, and it was very stable. On the other hand, when a general anionic surfactant of 0 is added or no thinning agent is added, the viscosity is 20.0 at a coal concentration of 50%.
0002 or more, and there is no flow at all.

East Leprosy Example 2 A clean coal-water slurry of a predetermined concentration is prepared in the same manner as in the East Leprosy Example 1 using clean heated coal. The grain size of the grain is 80% higher than that of the 2007 grain. The viscosity of this slurry was kept constant with oil at 25° C., and the fluidity was also observed. After allowing this slurry to stand still for one month, Example 1
In the same way as above, the agricultural rate of coal in the upper and lower layers is determined by I.

Table 1 shows the uninvented viscosity reducing agent 4 used in the test. The trial tightening results are shown in Table 3.

As shown in Table 3, when the uninvented viscosity reducing agent is added to the clean fossil water slurry, the viscosity is 1200-2900c, P even when the lime concentration is 78-80%, and the viscosity is low and the fluidity is good. Further, the slurry is extremely stable with almost no primary sedimentation even after it has been allowed to stand for one month.

On the other hand, when a general anionic surfactant is added or no thinning agent is added, the viscosity becomes 20.000 cP or more at a pellet concentration of 50%, and it does not flow at all.

Claims (1)

[Scope of Claims] (1) A thinning agent for highly concentrated coal-water slurry used to reduce the viscosity of coal-water slurry and improve fluidity and stability, the aromatic nucleus being a hydrocarbon. sulfonic acids of polycyclic aromatic compounds and sulfonic acids of monocyclic aromatic compounds, which may be substituted with groups, hydroxyl groups, or carboxy/V groups; 1. A thinning agent for coal-water slurry, characterized in that it contains a polymarine condensate of a sulfonic acid of a group compound and a monocyclic aromatic compound, or a salt thereof as essential components. (2) The composition ratio of the polycyclic aromatic compound or its sulfonic acid (component A) and the immediate ring aromatic compound or its sulfonic acid (component B). Molar ratio (A component)/(B component) = 1/9 to 9/1
, preferably 327 to 8/2.
The thinner for coal-water slurry described in section 1). (3) The average degree of condensation of the formalin condensate is preferably 1.5 to 20. The thinning agent for coal-water slurry according to claim (1) or (2), which preferably has a molecular weight of 2 to 10. +41 Thinning for coal-water slurry according to any one of claims (1) to (3) for use in coal-water slurry having a lime concentration of 61% or more, preferably 70% or more agent. (5) The thinning agent for stone removal-water slurry according to any one of claims (1) to (4), wherein the stone tip is clean rIZ coal.