JPS58125789A - Viscosity depressant for highly concentrated coal-water slurry - Google Patents

Abstract

PURPOSE:The titled viscosity depressant lowering the viscosity of coal-water slurry, improving the flow properties and stability of coal-water slurry, containing a crosslinked polyether compound (derivative) obtained by adding an alkylene oxide to a specific aldehyde condensate. CONSTITUTION:The desired viscosity depressant containing (A) a polyether compound (derivative) having a molecular weight of 1,000-100,000, preferably 10,000-100,000, obtained by adding an alkylene oxide containing >=95wt%, preferably 100wt% ethylene oxide unit to an aliphatic aldehyde condensate of an aromatic compound containing a phenolic hydroxyl group, or (B) a crosslinked polyether compound (derivative) having a molecular weight of 1,000-100,000, preferably 10,000-100,000, obtained by crosslinking the component A with a crosslinking agent such as polyfunctional isocyanate, polyfunctional epoxy compound, polyfunctional aldehyde, etc., as an active ingredient.

Description

[Detailed description of the invention] The present invention relates to a range adhesive for coal-water slurry.

More particularly, it relates to a thinning agent for dispersing pulverized coal in water to provide a highly concentrated charcoal-wood 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 oil, coal is a solid and cannot be transported by pump. For this reason, various methods are being considered for pulverizing coal and dispersing it in water to form a water slurry. However, with current technology, this method becomes difficult to pump as the coal thickens significantly as the coal concentration increases and loses its fluidity. - Reducing the degree of mangoku reduces transportation efficiency and requires a dehydration process before combustion, which is expensive and not a trivial idea.

The present inventors have previously succeeded in stably dispersing coal in oil using Boriethe/L's, and are currently applying for a patent.

Unexamined Japanese Patent Publication No. 54-52] (15, No. 54-52106, No. 5
4-53105. 54-58] 06, 54-58
58107. 54-581 (18.

54-5: (109, 54-657 (18, 54
-657 (19, 54-11) 5 (lfl, 55-1527899) However, these are for stably dispersing coal in oil and are not used for coal-water slurry.

The present inventors fluidized high-concentration phase coal-water nurary,
We have conducted intensive research into a thinning agent for coal-wood slurry that enables pumping. By adding a small amount of slag, the viscosity of the coal-wood slurry can be significantly reduced. - Succeeded in developing a viscosity reducing agent that provides water slurry.

By using the thinning agent of the present invention, coal can be fluidized with a small amount of water, which not only makes it possible to transport it by pump, but also allows it to be burned in a boiler as it is, eliminating the need for a dewatering process before combustion. can.

By using the thinning agent of the present invention, handling of lump coal becomes extremely simple, and its applications are greatly expanded.

The coals used in the coal-water slurry include anthracite, bituminous coal,
Any type of coal may be used, such as sub-bituminous coal, lignite, or cleaned versions thereof. Furthermore, the particle size of the coal 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 70% or more of 200 mesh bath, this particle size is suitable for pulverized coal. This is a guideline for the particle size. However, the thinning agent of the present invention is not affected by particle size, and exhibits an excellent rh effect even on coal powder with a particle size of For example, ash and sulfur have been removed. Examples of methods for cleaning coal include heavy liquid separation, Q
There are methods such as coal flotation method (hereinafter referred to as FOA method) and coal flotation method. 17 However, methods other than these may also be used and are not particularly limited.

Regarding the OA method, after dry or wet pulverization of coal, a water slurry is prepared and an appropriate amount of oil is added, or
After coating coal with oil in advance, a water slurry is prepared and stirred. The oil that wets the coal is used as a binder to cause agglomeration of organic coal components. On the other hand, inorganic substances have a weak affinity with oil and are liberated in water, so this method can remove inorganic substances at the same time by separating water from coagulated coal.
The coal concentration in the coal-water slurry of method A is usually 10 to 65
The oil used in the OA method is crude oil or various distillates obtained from crude oil, such as 1 oil, light oil, heshin oil, B heavy oil, C heavy oil, tar or rY)・
Or egg shin decomposition residual oil or various blended oils 4. Used as a lubricant, mineral oil, lubricating oil, cleaning oil, etc.Also benzene, /, 1 toluene, xylene, animal and vegetable oils (oils that are insoluble in water are also used)
Heavy oils such as heavy oil and tar residue oil 4C are particularly suitable for TIE because they are inexpensive. It is generally sufficient to use this oil in an amount of 30% by weight or more based on the coal in the coal-water slurry to be treated for mineral removal.

In addition, the flotation coal flotation method is an existing reselection method in which a very small amount of oil is added to the pulverized coal-water slurry and stirred to remove the coal.
Generate floss. This method is similar to the OA method, either the organic content of coal adheres to the oil film, or the inorganic substances are released [70%] in the water.
, is a method that can separate coal organic content.

The oils used in the flotation coal flotation method are turpine oil, tar, A heavy oil, C heavy oil, light oil, and 1 oil.It is common that several tens of weight percent or more of inorganic substances are removed from the coal by the method described in 1-1. be.

When using coal that has been cleaned in this way, the effect of the additive of the present invention is significantly superior to that of uncleaned coal, and a coal-water slurry that is several points higher can be obtained. When cleaned coal is used for awns, other benefits (such as suppressing boiler corrosion during coal combustion and reducing the burden on ash removal equipment and desulfurization equipment) are very large.

The thinner for coal-water slurry of the present invention (al) is a product obtained by adding alkylene oxide to an aliphatic aldehyde condensation product of an aromatic compound having a phenolic hydroxyl group, and necessarily contains ethylene oxide as the alkylene oxide, and its content is A polyether compound having a molecular weight of 1,000 to 100,000, preferably 10,000 to 100,000, or a tree of the polyether compound, which is greater than 95% by weight of all alkylene oxides to which is added, preferably all of the alkylene oxides are composed of ethylene oxide, and preferably has a molecular weight of 10,000 to 100,000. Derivatives obtained by various reactions of terminal hydroxyl groups, or (t)l Alkylene oxide derivatives added to aliphatic aldehyde condensates of aromatic compounds having phenolic hydroxyl groups, which always contain ethylene oxide and whose synthesis A polyether compound having a ratio greater than 95% by weight of all added alkylene oxides, preferably all of the alkylene oxides consisting of ethylene oxide, is a polyhydric isocyanate, a polyhydric epoxy, a polyhydric aldehyde, a polyhydric carboxylic acid or Molecules crosslinked with one or more crosslinking agents selected from polycarboxylic acid derivatives, peroxides, and formalin 1i1000
It contains as an essential component a crosslinked polyether compound of 10,000 to 100,000, preferably 10,000 to 100,000, or a derivative obtained by various reactions of the wood end hydroxyl groups of the crosslinked polyether compound.

Examples of aromatic compounds having a phenolic hydroxyl group include: 1) Phenols and substituted phenols such as phenol, cresol, xylenol, butylphenol, nonylphenol, aminophenol, and hydroxybenzoic acid; 2) Naphtho-p, methylnaphthol, and butylphenol; Naphtho-p and substituted naphthols such as naphthol and octylnaphthol 8) Polyhydric phenols such as catechol, resoμcine, and pyrogallol 4) Polyhydric naphthols such as naphresorcin and α-naphthohydroquinone 5) Bisphenol A1 bisphenol -yvs and other condensed phenols.

Examples of aliphatic aldehydes include formalin, acetaldehyde, and glyoxal, with formalin being common.

As the alkylene oxide, ethylene oxide, propylene oxide, butylene oxide, etc. are used, and these may be used alone or in combination of two or more types. In the case of two or more types, the arrangement is block polymerization type or random polymerization type. Although any of these may be used, the block polymerization type is common.

It is effective that the content of ethylene oxide is greater than 95% by weight of all the added alkylene oxides, and it is even more effective that all the added alkylene oxides are preferably composed of ethylene oxide.

Polyether compounds may be produced by first condensing an aromatic compound having a phenolic hydroxyl group using an aliphatic aldehyde and then adding an alkylene oxide, or by first condensing an aromatic compound having a phenolic hydroxyl group with an alkylene oxide. Although it is also possible to add an alkylene oxide to and then condense using an aliphatic aldehyde, the former is common.

However, the production method is not limited to a specific one, and any production method can be used as long as the desired viscosity reducing agent can be obtained. The degree of condensation with aliphatic aldehydes is 1.5
It is preferably from 2.0 to 50, more preferably from 2.0 to 30.

The polyether compound obtained is effective if the content of ethylene oxide is greater than 95% by weight of all added alkylene oxides, preferably one in which all the added alkylene oxides are composed of ethylene oxide, and the molecular weight is 1000%. A range of from 10,000 to 100,000, preferably from 10,000 to 100,000 is effective.

A crosslinked polyether compound is obtained by crosslinking a polyether compound with a crosslinking agent.

As a crosslinking agent for a polyether compound, polyvalent isocyanate, polyvalent engineered polymer, polyvalent aldehyde, 13-peroxide (radical generating catalyst), and formalin can be used. Specifically, as a polyvalent isocyanate compound, hexamethylene is used. diisocyanate, tolylene diisocyanate, xylene diisocyanate, 5 naphthylene diisocyanate), 4,4' diphenylmethane diisocyanate, and polyvalent epoxy compounds include diglycidyl bisphenol A and diglycidyl ethylene glycol. , diglycidyltetraoxyethylene glycol, etc. 'Polycarboxylic acid derivatives include carboxylic acids having two active hydrogen atoms, such as oxalic acid, malonic acid, phthalic acid, maleic acid, glutaric acid, adipic acid, azelaic acid, cepatic acid, Carphonic acids with 3 active hydrogens, such as dodecanionic acid, dimer alcohol, 0-7 enylene diacetic acid, etc. Carphonic acids with 4 active hydrogens, such as hemimellitic acid, trimellitic acid, etc., such as butanetetracarboxylic acid, pyromellitic acid , engineered ethylene diamine tetraacetic acid@, etc., carboxylic acids having 5 or more active water bladders, such as acrylic polymers, acrylic acid copolymers, methacrylic acid polymers, methacrylic acid copolymers,
Maleic anhydride polymers, maleic anhydride copolymers, partially saponified products of polymers and copolymers of acrylic esters and methacrylic esters, anhydrides of the above acids, and acid halides can be used.

As peroxides (radical generating catalysts), hydrogen peroxide, penzoyl haloquine, CAa-based benzoyl di-tertiary butyl haloquine, cumene oxide, dicumyl peroxide, etc. are optionally used. Cross-linking by reacting formalin under acidic conditions is also effective. When cross-linking is performed using a polyvalent incyanate compound or a polyhydric acid compound, the proportion of the cross-linking agent used is arbitrary, but in general is 0.0 based on the terminal hydroxyl group equivalent of polyether.
5 to 5 equivalents, preferably 0.1 to 3 equivalents are used.

The crosslinking conditions include mixing the polyether compound and the crosslinking agent and heating the mixture at 40 to 15.0°C, preferably at 50 to 12°C while stirring.
Heating is carried out in the range of 0''C, if necessary, when crosslinking is carried out using acid or L-form which is usually used for crosslinking,
The proportion of the crosslinking agent used is arbitrary, or it is generally
0.05 to 5 based on the terminal hydroxyl group equivalent of the ether
Equivalence rod: Use 0.1 to 8 equivalents. When using polyvalent carboxylic acid as the crosslinking condition, the polyether compound and the crosslinking agent are mixed in the presence or absence of an inert solvent. , reduced as necessary from 60'C to 250°C
The purpose can be easily achieved by carrying out the dehydration by heating, preferably at a temperature in the range of 80 to 220°C. In this case, in order to facilitate the reaction, an esterification catalyst (t7) can usually be used.

In addition, when using polyhydric carboxylic acid halide, BoIJ
In order to facilitate dehydrohalogenation, the ether compound and the crosslinking agent are mixed in the presence or absence of an inert solvent, and an inert gas is passed therethrough to facilitate dehydrohalogenation, or a known agent that can easily capture the generated hydrogen halide is used. Using -1o'C-
The purpose can be easily achieved by reacting at 150°C, preferably in the range of 0°C to 120°C. When crosslinking using peroxide, the proportion of peroxide (radical generating catalyst) used is: 0.0 for polyethers
Any amount can be used in the range from 5% to 10% by weight, preferably from 0.1% to 5% by weight.

For example, Journal
of Applied Polymer 5cie
nce Vol. 7, pp. 461-468 (19631, etc.), and these known techniques can be applied as they are for crosslinking, which is referred to as uninventive. Generally, a predetermined amount of peroxide is added to polyethers in the presence of a solvent. The reaction can be carried out in the absence of a binder at a temperature of 50 to 250°C, preferably 70 to 180°C, and if necessary, the solvent can be distilled off to obtain the target substance.

In the case of crosslinking using formalin, known techniques can be used, but it is generally carried out as follows.

That is, 0.1 to 10 equivalents, preferably 0.5 to 5 equivalents of nelmarine are used, and 0.05 to 0.005 equivalents of acidic catalyst are added to 60 to 10 equivalents per one equivalent of the polyether compound.
The temperature was raised to 0C, stirred for 1 to 3 hours, and then heated to 100
The reaction is completed by raising the temperature to ~180°C.

The crosslinked polyether compound obtained by crosslinking the polyether compound in this way has a molecular weight of 1000 to 100,000,
Preferably, 10,000 to 100,000 is effective.

For example, you can list the following: 1) Esterified products that react with organic acids or inorganic acids.

2) Anti-Li with halogenated hydrogen and phosphorus halide:
-C' 1a replaced with water MM or halogen/.

; 3) Produced by a solubilization reaction: alcohol or carbo]
・However.

・1,) Small acid group and upper Neuson ratio and σ] anti-1+i
;, 1st generation 1゜l, 1 house 1. B1 The invention is [・example [this is limited≠], so (, 1t).

The reason why the thinner of the present invention exhibits an excellent effect is that after it is strongly adsorbed to the particle surface due to its special W4 structure, the numerous ether bonds utilize the surrounding water, and this water acts like a lubricating oil. It is thought that the lime particles are stabilized as primary particles and their fluidity is improved. At the same time, a significant decrease in viscosity occurs.

In addition, if you use clean coal such as deashing, the effect will further increase due to 1152 ash,
This is because the thinner of the present invention effectively acts on the coal surface, which has improved organicity by removing ash, which is highly hydrophilic and has fine particles with a large surface area. −σ)! ;You can measure your progress.

The present invention〇) Thinning agent is used in winter 11 for coal-water souffle.
6, 0. (1N-5.0% by weight, preferably 0.0%
3-2.0 jkfkt% addition" 4-6 and M Yon-
q-guJ is also effective. The fluidity limit of a coal-water slurry varies depending on the type and particle size of the slurry, but in general, if a thinner is not added, the coal concentration will be around 50% and the fluidity will be low. , if the present invention's thinner is added, the activity will be significantly reduced, so coal!r& is 61% by weight.
It has fluidity even when F1 is more than 70% by weight. If even cleaner coal is used, the coal concentration will increase by several points, typically 8 to 10 points.

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

Methods for making coal-water slurry and adding a thinner include methods in which the coal is dry-pulverized in advance and then mixed into an aqueous solution of the thinner, or after the coal-water slurry is made. 20- How to add a thinner, add coal, water and a thinner to the mill,
〈Crush and mix from IC;! , how to do it, that's the first thing tl
``Then, instead of coal, use cree〕-f.
Any method of mixing using coal, etc.
F+・Can be implemented.

The thinner of the present invention also has the effect of safely dispersing coal into water immediately and for a long period of time, e.g.
If left undisturbed for 7 months, water separation will occur, and the water slurry will remain in the water slurry.

As described above, the thinner of the present invention preferably has a weight ratio of 0.01 to 5.0%, preferably <Ke008 to
By simply adding zO in a heavy weight percent, the viscosity of the 4i coal-water slurry can be significantly reduced, and a gypsum-water slurry with a high concentration of 1 can be easily transported.

Examples are shown below. The percentages in the examples are based on City 1) 4.

Example 1 A predetermined amount of an aqueous solution containing a thinner shown in Table 1 (2)
00 Mesonyu Add coal crushed to 80% lotus while stirring the chamber with a crystal, F4F Joonoma Ii! :S7
/N Adjust slurry. The viscosity +V' of this slurry is 2
Measure with FI T-: and observe fluidity. Add 500 ml of this slurry to the cellar and let it stand for 1 month.
Measure the coal concentration in the first layer (1 part to l C11) and the lower layer (11 from the bottom). The test results are shown in Table 2 (,
: Not. As shown in Table 2, when the viscosity reducing agent of the present invention is added, the viscosity decreases to 1000 even for coal made from 74% to 77%.
~2800 cp, and has extremely good fluidity. Furthermore, the slurry remains extremely stable with almost no sedimentation even after it has been allowed to stand for one month. On the other hand, when a general anionotropic activator is added or no thinner is added (well, the viscosity is 20.000 cp at coal m#50%).
10 (Kona O1 doesn't flow at all.)

Example 2 Cleaned coal was used in the same manner as in Example 1. "Clean coal at a constant concentration - Adjust water slurry 4. - Coal particle size is 200 me fsh 8 ()% Hass σ)" 〇) The viscosity of this slurry was measured at 251 mm, and the fluidity was also observed. 〇) After the slurry was left to stand for one month, Measure coal concentration.

The viscosity reducing agent C of the present invention used in the test is as shown in Table 1. The test results are shown in Tables 3 and 8 [As shown, when the thinner of the present invention is added to the cleaned coal-water slurry, the viscosity decreases to 1000-2 even when the coal level is 78-80%.
400 cp, and has extremely good fluidity. In addition, the slurry is extremely stable with almost no coal settling even after it has been allowed to stand for one month. - When a thinning agent other than the one invented by the strength wood is added, or when no thinning agent is added, the viscosity becomes 20.00 (more than 1 cp) at a coal concentration of 50%, and it does not flow at all.

(Margin below) 651

Claims (1)

[Claims] A thinning agent for highly concentrated coal-water slurry used to reduce the viscosity of coal-water slurry and improve fluidity and stability, comprising: [al] an aromatic compound having a phenolic hydroxyl group; An alkylene oxide added to an aliphatic aldehyde condensate of a compound, which necessarily contains ethylene oxide as the alkylene oxide, the content of which is greater than 95% by weight of the total added alkylene oxide, preferably all of the alkylene oxide is derived from ethylene oxide. Consisting of +
11,000 to 100,000, preferably 10,000 to 100,000 polyether compounds, derivatives obtained by various reactions of the wood end hydroxyl groups of the polyether compounds, or aliphatic aldehyde condensates of aromatic compounds having phenolic hydroxyl groups. A polyether compound in which an alkylene oxide is added to the alkylene oxide, which necessarily contains ethylene oxide, the content of which is greater than 95% by weight of the total added alkylene oxide, and preferably all of the alkylene oxide is composed of ethylene oxide. , multififii v shea *-1-, +
i Crosslinked with one or more crosslinking agents selected from epoxy, polyvalent aldehyde, polyvalent μ-boxylic acid or polyvalent carboxylic acid derivative, peroxide, and formalin + flIO (100,000 to 100,000, preferably] 10,000 to 100,000 to A thinning agent for coal-water slurry, characterized in that it contains as an essential component a crosslinked polyether compound of 100,000 or a derivative obtained by reacting various types of hydroxyl groups at the ends of the crosslinked polyether compound.