JPS5817196A - Additive for agglomeration of powder coal in coal/water slurry - Google Patents

Abstract

PURPOSE:The titled additive for agglomeration of powder coal having a large agglomeration effect and recovering the powder coal at a high rate, which comprises a specified polyether, a crosslinked product thereof, a condensate thereof, etc. CONSTITUTION:As an additive for agglomeration of powder coal, at least one polyester compd. selected from a polyether of MW1,000-600,000 or a deriv. thereof, a polyether of MW1,000-600,000 obtd. by adding an alkylene oxide with an alcohol having at least three active hydrogen atoms, etc. or an org. compd. having at least one phenolic OH group and at least two active hydrogen atoms, a compd. obtd. by crosslinking a polyether of MW1,000-600,000 by using a polyvalent isocyanate, polyvalent carboxylic acid, a peroxide, etc., a polyester/ formalin condensate of MW1,000-600,000 prepd. from a starting material consisting of an arom. compd., etc. is used. Said additive is added in an amt. of about 20% or less based on the coal contained in coal/water slurry, together with an oil such as C fuel oil or tar.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an additive for pulverized coal flocculation that can significantly increase the flocculation effect and significantly improve the pulverized coal recovery rate in a method for flocculating and recovering pulverized coal from an aqueous slurry using oil. .

In recent years, due to the depletion of petroleum energy, the use of coal has been reaffirmed, and various ways of using it are being considered. Among them, research and development related to Sufu 9-Pc has been actively conducted, such as methods for improving handling by turning coal into pulverized coal and creating a water slurry mixed with water, and methods for crushing coal in water to create a water slurry for deashing. be.

Coal-water slurry requires that the coal be recovered from water and dehydrated prior to combustion, and no economical and efficient method for recovering and dehydrating the coal has currently been found, so coal-water slurry technology has not seen widespread adoption. Table.

For example, in JP-A-53-F00FLO, the operation of adding and mixing emulsified oil to coal-water slurry is repeated two or more times.
In order to improve the recovery rate and create emulsified oil, surface active agents (cationic detergents, nonionic detergents, fatty soaps,
Sodium O1~(3111 alkylbenzene sulfonate, sodium 0#~C□, alkyl sulfate,
However, as stated in the above publication, when these emulsified oils are used, the coal powder is not coagulated sufficiently, and the effect of the emulsified oil is inferior. Because of this, the problem was that complex operations had to be rethought and implemented, and there were major problems in practical application.

Under such circumstances, the present inventors have discovered an additive that can significantly increase the coagulation of pulverized coal and significantly improve the recovery rate of pulverized coal by simply adding it to coal slurry together with oil and mixing it without performing complicated table operations. This is the book that led to the present invention as a result of extensive research.

That is, in recovering powdered coal from coal-water slurry using oil: 1) Molecular weight of 1,000 to 600,000, preferably 3,000
~300,000 polyethers or polyether derivatives.

2) Using any one or more of alcohols, amines, carboxylic acids, and derivatives thereof having at least 3 or more, preferably 5 or more active hydrogens in the molecule as a starting material, alkylene oxide is added thereto, and its molecular weight is determined. 1
,000 to 600,000, preferably 7,000 to 300,000.

3) Adding an alkylene oxide to an organic compound having one or more, preferably two or more, phenolic OH groups and having two or more, preferably three or more total active hydrogens as a starting material, A polyether having a molecular weight of 1,000 to 600,000, preferably 000 to 300,000.

4) Molecular weight 1,000 to 600,000, preferably 2,000
0 to 20,000 polyether compound as polyvalent isoV anate,
A compound crosslinked using at least one selected from polyvalent epoxy and polyvalent aldehyde compounds.

5) Molecular weight 1,000 to 60,000, preferably 2,000
~20,000 polyether compounds are reacted with one polyvalent carboxylic acid or a polyvalent carboxylic acid halide to create intramolecular or intermolecular crosslinking.

6) Molecular weight from 1.000 using an aromatic compound as a stimulant
A compound obtained by condensing 600,000, preferably 20,000 to 20,000 polyether compounds using formalin.

7) Molecular weight 1. OOO~600,000, preferably 2,000
A compound obtained by crosslinking 0 to 20,000 polyether compounds in the presence of a peroxide (radical generating catalyst).

8) Impregnating at least an ethylene oxide group and a propylene oxide group in the molecule, the content of ethylene oxide is 3 to 80 wt., preferably 10 to 50 wt.;
and a polyether compound whose molecular weight is from 1,000 to 600,000, preferably from 0,000 to 300,000.

9) Molecular weight 1,000 to 600,000, preferably 2,000
~300,000 sulfonated diosulfuric acid esters or phosphoric acid esters of aI21, or their counter ions, at least one compound as an essential component. This is an additive for powdered coal flocculation (hereinafter referred to as an additive), which is characterized by being added.

The coal used in the stone-water slurry includes various types of coal, such as smokeless coal, bituminous coal, subbituminous coal, lignite, etc., regardless of type or origin, and regardless of chemical composition or moisture content. , anything can be used. Such coal is dry-pulverized or coarsely crushed in a gas (air, nitrogen, combustion exhaust gas, etc.) in an ordinary mill, or crushed or coarsely crushed in ice to form a water slurry. Although the coal concentration in the coal-water slurry is not particularly critical, it is usually about 10 to 65%, and the grain size of powdered coal is generally smaller than about 10111. Concentration can be.

This applies to all types of coal-water slurry that are subject to coagulation and recovery, and the purpose of use of the slurry is not limited. In addition, slurries that have been subjected to some kind of treatment are also applicable, such as pulverized coal-water slurry in which coarse particles are removed from the coal-water slurry in advance, or coal-water slurry in which water is added or partially dehydrated.

The coal concentration in the coal-water slurry immediately before the aggregation operation may be anywhere from 1 to 65%, but preferably from 5 to 5%.
0%, more preferably 10-40%.

The oil added to the coal-water slurry is crude oil or various fractions obtained from crude oil, such as kerosene, light oil, A heavy oil, B heavy oil, C heavy oil, etc., tar or true rock oil, ethylene cracked residual oil, or various blends. Refers to oils commonly used as fuel, mineral oils such as lubricating oils and cleaning oils, and also includes mixtures thereof. It is also possible to use oils that are insoluble in water, such as benzene, toluene, dichloromethane, and animal and vegetable oils. Among them'
Heavy oils such as cC heavy oil tar and residual oil are particularly preferred because they are inexpensive. It is sufficient to use this oil in an amount of 20% or less of the coal in the coal-water slurry to be subjected to flocculation treatment, and since the effect of the additive of the present invention is very large, it is sufficient to use this oil in an amount of 10% or less, for example. 4. Coal can be completely agglomerated, so there is no need to add a large amount.

Next, the additive l)K according to the present invention has a molecular weight of 1.
It contains OOO to 600,000, preferably 3,000 to 300,000 polyether or polyether derivative as an essential component.

The polyether referred to here can be represented by the general formula 2 (%), where 2 is a starting material residue for the reaction having various functional groups, and various alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide, etc. Generally, an addition reaction may be carried out using a catalyst such as an alkali or an acid under pressure. Furthermore, ethylene chlorohydrin and ethylene carbonate can also be reacted. R is an alkylene oxide residue, such as ethylene, propylene, butylene group, etc., and is the number of moles of nFi alkylene oxide.

The ROFi may be used alone or in combination of two or more types, and the arrangement order thereof may remain the same and may be a block copolymerization type or a random copolymerization type.

Examples of the starting materials for Z include aliphatic alcohols, alicyclic alcohols, aromatic alcohols, aliphatic amines, alicyclic amines, aromatic amines, the above polyhydric alcohols, the above polyhydric amines, and phenol. Amides, aliphatic carboxylic acids, alicyclic carboxylic acids, aromatic carbon I
II! and derivatives of these containing one or more functional groups in the molecule, water, ammonia, urea, dicyandiamide, halogenated compounds, Vane F compounds, etc., which have a functional group that can react with alkylene oxide in the molecule. within 1
It is sufficient to have at least one.

In addition, m in the general formula is a number that is the same as or smaller than the functional number of the starting material, and it is possible to bond the alkylene oxide to all the functional numbers or only to a part of the functional numbers. means.

The above polyether has a molecular weight of 1,000 to 60
The amount of starting material and alkylene oxide to be charged may be adjusted so that the total amount is 1,000,000.

Further, the average molecular weight can be easily determined by measuring the OH value of the reaction product.

Also, polymers with a molecular weight of 3,000 to 300,000 are preferable for grass.

Further, derivatives of the above polyethers are also effective.

2) The additive K according to the present invention is a starting material containing at least one of alcohols, amines, carboxylic acids, and derivatives thereof having at least 3 or more active hydrogens, preferably 5 or more active hydrogens in the molecule. This is added with alkylene oxide to contain as an essential component polyester-chill having a molecular weight of 1,000 to 600,000, preferably 000 to 300,000.

The polyether mentioned here can be represented by the general formula 2 (%), where z is an alcohol having at least 311 or more active hydrogens, preferably 5 or more active hydrogens in the molecule;
Residues of amines, carboxylic acids and their derivatives. R
is an alkylene oxide residue, ethylene, propylene,
A butylene group, etc., and n is a value determined by the degree of polymerization of alkylene oxide. It is the number of active hydrogens that m fi Z has, and is at least 3 or more, preferably 5 or more.

RO may be used alone or in two or more types, and the arrangement order thereof may be a block copolymerization type or a random copolymerization type.

At least 3 or more active hydrogen atoms in the molecule represented by 2,
Preferably, alcohols, amines, carboxylic acids, and derivatives thereof having 5 or more alcohols, amines, carboxylic acids, and derivatives thereof. Alcohols with 3 hydrogens, alcohols with 4 active hydrogens such as diglylythin, pentaeryth Q)-ol, sorbitan, sorbitol, glue
Alcohols having 5 active hydrogen side plates/tops such as carbonaceous alcohol, Cylose, partially saponified polyvinyl acetate, partially saponified polyvinyl acetate copolymer, cellulose, and starch are useful; 3m even for various derivatives such as partially esterified alcohols containing active hydrogen.
If the above active hydrogen remains, it can be used.

In addition, amines and Mori, amines with three active hydrogens,
For example, amines having 4 active hydrogens such as ammonia, beef tallow propylene diamine, etc., such as ethylene diamine,
Amines having 5 or more active hydrogens, such as tetramethylenediamine, hexamethylenediamine, phenylenediamine, benzidine, and V-chlorohexyldiamine, such as diethylenetriamine, triethylenetetramine, and tetraethylenebentamine, are useful; Even various derivatives such as partial amides of amines having active hydrogens can be used as long as three or more active hydrogens remain.

Furthermore, carboxylic acids include carboxylic acids having three active hydrogen atoms, such as hemimelitic acid, trimellidic acid, and trimesic acid, and carboxylic acids having four active hydrogen atoms, such as butanetetracarboxylic acid, pyromellitic acid, ethylenediaminetetraacetic acid, etc. , carboxylic acid having active hydrogen 5II or more, such as acrylic #mounting body, acrylic acid copolymer, maleic anhydride polymer, maleic anhydride copolymer, methacrylic acid polymer, methacrylic acid copolymer, acrylic acid or methacrylic acid Partially saponified products of acid ester polymers and copolymers are useful, and various derivatives of these partially esterified products can also be used.

First, 2 does not matter even if the same molecule contains different functional groups. Examples include glitan, malic acid, monoethanolamine, yethanolamine, tartaric acid, aminoethylethanolamine, and the like.

The additive 3) K according to the present invention is an organic compound having one or more, preferably two or more, phenolic OH groups in the molecule and having two or more, preferably three or more, total active hydrogens. It contains as an essential component a polyether made by reacting a compound with an alkylene oxide to have a molecular weight of 1,000 to 600,000, preferably 7,000 to 300,000.

The polyether mentioned here has the general formula %formula%)) and zFi is the residue of the above starting material.

R1d is a residue of an alkylene oxide such as ethylene, propylene, or ethylene, ethylene chlorohydrin, or ethylene carbonate, and n is a number determined by the degree of polymerization of the alkylene oxide.

m is the number of active hydrogen atoms including the phenolic OH group of 2, and is at least 2 or more, preferably 3 or more. RO may be a single substance or two or more types, and the arrangement order thereof may be a single tt, a block copolymerization type, or a random copolymerization type.

Examples of zIK and corresponding starting materials include:

(1) Polyhydric phenols, such as catechol, resorcinol, hydroquinone, pyrogallol (2) Polyhydric naphthols, such as dioxynaphthalene and triochynaphthalene such as naphresorcin and α-naphthohydroquinone (33) One or more hydrogens,
Good 11. < is a substitution containing two or more) - No/&, such as aminophenol, ester-benzened gallic acid (41 phenol, resorcinol, naphthol or substituted phenol, such as metacresol, metacresol,
Condensation of aldehydes such as methane, thylphenol, orthocresol, valaclesol, 2.6-xylenol, etc. with aldehydes 1, such as fortaldehyde F, acetaldehyde, benzaldehyde, or ketones, such as acetone, under acidic or oxidative catalysis. Among condensates, condensates (5) having at least two or more phenolic OH groups Substituted phenols having one or more, preferably two or more active hydrogens in addition to phenolic OH, such as aminophenol, oxybenzoic acid, Condensates of gallic acid, etc., and aldehydes, such as formaldehyde, acetaldehyde, benzaldehyde, or ketones, such as acetone, under acidic or basic catalysts Condensates having at least two or more phenolic OH groups Here, the phenolic OH group means a 90H group directly bonded to the aromatic ring of phenol, naphthol, substituted phenol, substituted naphthol, polyhydric phenol, polyhydric naphthol, etc.

The additive a) Ic according to the present invention has a molecular weight of 1.00.
A polyether compound having a weight of 0 to 600,000, preferably 20,000 to 20,000, crosslinked with at least one selected from polyvalent isocyanates, polyvalent epoxy V1 polyvalent aldehyde compounds, is used.

Here, the polyether compound refers to alkylene oxide QV
for example, a homopolymer or copolymer of at least one of ethylene oxide, propylene oxide, or butylene oxide, ethylene chlorohydrin, and ethylene carbonate, and one or more, preferably two or more, of various active hydrogen groups. For the starting materials having the above alkylene oxide and ethylene chlorohydrin,
It is arbitrarily selected from '4' in which at least one type of ethylene carbonate is polymerized to give a predetermined molecular weight. Here, when performing addition polymerization using two or more types of alkylene oxides, the addition mode may be random or block. It is effective to crosslink such polyether compounds either singly or as a mixture of two or more thereof.Of course, it is also possible to crosslink a single polyether compound and then blend two or more thereof.

Active hydrogen groups include alcoholic hydroxyl groups, -amino groups, carboxylic acid groups, phenolic OH groups, etc. Examples of starting materials containing one or more of these groups include the following.

Examples of alcohols include alcohols having one active hydrogen, such as ethyl alcohol, butyl alcohol, octyl alcohol &+! ", Alcohols with 2 active hydrogens, such as ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, gtylene gelylcol, polybutanediol, bentanediol, hecanediol, etc., 3 active hydrogens Alcohols having 4 active hydrogen groups, such as glycerin, butanetriol, hexanetriol, trimethylolpropane, triethanolamine, etc. Alcohols having 5 or more active hydrogen groups, such as diglycerin, pentaerythritol, etc. , such as sorbitan, sorbitol, glucose, Shakrose, partially saponified polyvinyl acetate,
Partially saponified polyvinyl acetate copolymers, cellulose, starch, etc. are useful, and even derivatives such as partially esterified alcohols having two or more active hydrogens have one or more active hydrogens. If there are any left, you can use them.

In addition, examples of amines include amines having one active hydrogen such as dimethylamine and N-methyllaurylamine, amines having two active hydrogens such as methylamine, nealamine, propylamine, butylamine, allylamine, amylamine, etc. octylamine, dodecylamine, laurylamine, tetradeylamine, bentadeylamine, octadeylamine, beef tallow alkylamine, di-alkylamine, aniline, p-)luidine, m
- Amines with 3 active hydrogens, such as toluidine, nitroaniline, benzylamine, chloraniline, P-dode V-rubenzylamine, V-chlorohexylamine; amines with 4 active hydrogens, such as ammonia, tallow propylene diamine, etc. , such as ethylenediamine, tetramethylenediamine, hexamethylenediamine, phenylenediamine, benzidine, cyclohexyldiamine! 1. Amines having 5 or more active hydrogens, such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, etc., are useful, and various derivatives such as partial amides of amines having 2 or more active hydrogens are also useful. , can be used if one or more active hydrogen remains.

Examples of carboxylic acids include carboxylic acids having one active hydrogen, such as acetic acid, lauric acid, oleic acid, stearic acid, etc., and carboxylic acids having two active hydrogens, such as Scheller's acid, malonic acid, phthalic acid, and fumaric acid. , maleic acid, gulguric acid, adipic acid, azelaic acid, heptabasic acid, dodecanedioic acid, dimer acid, phthalic acid, isophthalic acid, terephthalic acid, O-7 enylene nyripic acid, etc., carboxylic acids having three active hydrogen atoms, For example, carboxylic acids having 4 active hydrogens such as hemimellic acid, trimellidic acid, trimesic acid, etc., such as butanetetracarboxylic acid, pyromellitic acid, ethylenediaminetetraIIP#, carboxylic acids having 5 or more active hydrogens, such as acrylic acid polymers , acrylic acid co-electropolymer, maleic anhydride polymer, maleic anhydride copolymer, methacrylic acid polymer, methacrylic acid copolymer,
Partially saponified copolymers of acrylic acid and methacrylic acid esters are useful, and various derivatives such as partially esterified products thereof can also be used.

Further, examples of phenols include phenol, cresol, alkylphenol, resordin, catechol, and hydroquinone, and examples of compounds having a 4-other aromatic group include naph)-ols. Compounds having these aromatic OH groups or formalin condensates thereof having at least one phenolic OR group are also useful.

Furthermore, substances containing different types of active hydrogen in the same molecule, such as lactic acid, glycols, N-substituted alkylglycine, glycine, malic acid, monoethanolamine, jetanolamine, tartaric acid, and aminoethylethanolamine, etc. I don't mind.

In addition, examples of polyvalent isocyanate compounds include hexamethylene diisocyanate, silylene diisocyanate, metaxylene diisocyanate, 1.5 naphthylene diiso V ane), 4.4' diphetylmethane diisonanate, etc.), and polyvalent epoxy compounds. Examples include diglycidyl bisphenol A, diglycidyl ethylene glycol, and diglycidyl tetraoxyethylene glycol.

When a crosslinking agent is applied to these polyether compounds, the proportion of the crosslinking agent used is arbitrary, but generally it is 0.05 to 5 equivalents, preferably 0.05 to 5 equivalents, based on the terminal hydroxyl group equivalent of the polyether. 1 to 3 equivalents are used.

The crosslinking conditions include mixing a polyether compound and a crosslinking agent, and heating the mixture at 40 to 150°C, preferably at 50 to 120°C, while stirring.
Heating is carried out in the range of 0.degree. C., and if necessary, an acid or base catalyst commonly used for crosslinking can be used.

The additive mentioned in 5) according to the present invention has a molecular weight of 1.000.
~600,000, preferably d2. ooo~20,000 polyether compound is reacted with monopolycarboxylic acid or phytopolycarboxylic acid to effect intramolecular or intermolecular crosslinking.

This polyether compound referred to in ζ is as described in Section 4 above.

In addition, the polyvalent carboxylic acids and polyvalent carboxylic acid halides used for crosslinking here include the polyvalent carboxylic acids in the above classification, which can be used in their tt, adipine monochlorophyte, azefin acid dichloride, Vella acid dichloride, and phthalate. Halides such as acid dichlorides are also useful.

Polyvalent carboxylic acid or polyvalent carboxylic acid hafide is OH
It is well known that groups can be crosslinked, and crosslinking can be easily carried out under normal esterification reaction conditions.

The proportion of the crosslinking agent to be used is arbitrary, but it is generally used in an amount of 0.05 to 5 equivalents, preferably 0.1 to 3 equivalents, based on the terminal hydroxyl group equivalent of the polyether.

As for the crosslinking conditions, when using a polyhydric carboxylic acid, the polyether compound and the crosslinking agent are heated at 60''C to 250℃ under reduced pressure as necessary in the presence or absence of an inert solvent.
C., preferably in the range of 80.degree. C. to 220.degree. C., to achieve the desired purpose. In this case, one conventional esterification strategy can be used to facilitate the reaction.

In addition, when using polyhydric carboxylic acid parite, the polyether compound and the crosslinking agent are mixed together in the presence of an inert solvent, and then an inert gas is passed through in order to facilitate dehydrogenation in the absence of an inert solvent. Alternatively, using a known agent that can easily capture the generated hydrogen halide,
By carrying out the reaction at 0"Q, preferably in the range of 0°C to 120°C, the objective can be easily achieved.

The additive 6) K according to the present invention is a compound obtained by condensing a polyether compound with an aromatic compound as a starting material and a molecular weight of 1,000 to 60,000, preferably 2,000 to 20,000 using formalin. Use.

Molecular weight 1,0 using the aromatic compound mentioned here as a starting material
000,000-600,000, preferably Ifi2. Ooo ~ 20,000 polyether compounds (hereinafter referred to as polyethers) are compounds containing aromatic groups and one or more active hydrogen groups as starting materials, and alkylene oxides such as ethylene oxide, propylene oxide, or ethylene oxide; At least one of ethylene chlorohydrin and ethylene carbonate is added and twisted to give a predetermined molecular weight. In this case, when there are two or more types of alkylene oxides, the copolymerization type may be random copolymerization or block copolymerization.

As the compound having an aromatic group and an active hydrogen, the following compounds can be arbitrarily used.

・Alkylene oxide adducts of alkyl-substituted phenols such as cate, kohl, resorcinol, hydroquinone, pyrogallol, nonylphenol, octylphenol, and dodecylphenols ・Alkylene oxide adducts of condensed phenols such as bisphenol A1 and bisphenol 8 ・Naftresorcin, α - Alkylene oxide adducts of naphthols such as dioxynaphthalene such as naphthovitroquinone Generally, phenolic resins, xylene m fat K As represented by, when formalin is reacted under acidic conditions, between aromatic rings, It is known to have methylene bridges.

Therefore, as in the present invention, the above-mentioned known techniques for IL condensation of polyether compounds using formalin can be used, but generally it is carried out as follows.

That is, 0j-10 equivalents of formalin, preferably 0.5 to 5 equivalents, and 0.05 to 0.005 equivalents of acidic catalyst are added to 60 to 100 equivalents of polyether compound.
℃, stirred for 1 to 3 hours, and then heated to 100℃.
The reaction is completed by raising the temperature to 180°C.

Next, the additive referred to in 7) according to the present invention has a molecular weight of 1.
It is characterized by using a compound in which a polyether compound having a molecular weight of 0.000 to 600,000, preferably 2,000 to 20,000, is crosslinked in the presence of a peroxide (fusical generating catalyst).

The polyether compound referred to here is the one described in 4 above.

In addition, examples of the peroxide (radical generating catalyst) mentioned here include hydrogen peroxide, benzoyl peroxide, Zita-Vyary-butyl peroxide, Kiemene oxide V-do, dicumyl peroxide, etc. Used arbitrarily.

The peroxide (fusical generating catalyst) can be used in any proportion in the range of 0.05% to 10% by weight, preferably 0.1% to 5% by weight, based on the polyether.

For example, Journal
oj Applied Polymer 5cien
These known techniques can be applied directly to the crosslinking of the present invention. A predetermined amount of peroxide is mixed with general Kit polyethers in the presence or absence of a solvent, and the temperature is 50 to 250"Q, preferably 70°C.
The target substance can be obtained by reacting at a temperature of ~180°C and distilling off the solvent if necessary.

The additive according to 8) of the present invention contains at least 4 ethylene oxides and propylene oxides in the molecule,
The content of ethylene oxide is 3 to 80%, preferably 1
0 to 50%, and its molecular weight is 1.000 to 6
00,000, preferably 70,000 to 300,000 as an essential component.

The polyether compound referred to herein can be represented by the general formula 2, where 2 is a residue of a reaction starting material having various functional groups. In general, an addition reaction between ethylene oxide (ethylene chlorohydrin or ethylene carbonate may also be used) and propylene oxide using such starting materials is carried out under pressure using a catalyst such as an alkali or an acid. In addition, other alkylene oxides such as butylene oxide (including tetofhydro-7) may be used in combination, if necessary. R is an alkylene oxide residue, and n is the number of moles of alkylene oxide added. On the other hand, mq is a number corresponding to the number of active hydrogens of the starting material, and is the number of alkylene oxide bonds to the active hydrogens. The alkylene oxide addition solubility is determined when the molecular weight of the polyether compound is from 1.000 to
600,000, preferably 7,000 to 30,000, and the content of ethylene oxide groups is 93 to 80% based on the molecular weight of the final polyether compound, preferably 1
The additive of the present invention can be easily obtained by reacting ethylene oxide, ethylene chlorohydrin, ethylene carbonate, etc. to a concentration of 0 to 50%. In addition, the arrangement order of the ethylene oxide group and the propylene oxide group, and if necessary, other alkylene oxide groups, may be either a block copolymerization type or a random copolymerization type, but it is preferably a block copolymerization type. It is preferable that part or all of the group be bonded to the terminal.

The additive referred to in 9) according to the present invention has a molecular weight of 1.000.
~600,000, preferably 2,000 to 300,000, containing as an essential component at least one or more of the acids of sulfonated, sulfuric acid esters, or phosphoric acid esters of polyether compounds, or their counter ions. It is characterized by

The polyether compound referred to here is the same as that described in 4)K.

In addition, OH groups other than polyether compounds such as those mentioned above 1
These polyether compounds also include crosslinked polyethers in which one or more polyethers remain in the molecule.

That is, a polyether compound having two or more OH groups, the polyhydric (two or more active hydrogen) carboxylic acids explained above, dicrophyte adipic acid, dicrophyte azelaic acid, s/= dicrophyte oxalate, dicrophyte phthalate, etc. Polycarboxylic acid halides are reacted to form intramolecular or intermolecular crosslinks, and polyethers having two or more OH groups are combined with tolylene diisocyanate, metaxylene diisocyanate, and hexamethylene diisocyanate. Polyvalent isoneanate such as tholianate, Gigli V
Intra-molecular or Various crosslinked products, such as those with intermolecular crosslinking, may also be used.

The above-mentioned polyether compounds in which at least one OH group remains in the molecule and have a molecular weight of 1,000 to 600,000, preferably 1,000,000 to 2,000 to 300,000 are, for example, sulfuric acid, fuming sulfuric acid, It easily reacts with chlorosulfonic acid, acidic sodium sulfate, sulfamic acid, etc., and can introduce a sulfonic acid group or a sulfuric acid ester group into the molecule. If a sulfonic acid group is introduced into the aromatic ring or aliphatic double bond,
It is possible to obtain the additive according to the present invention.

Also. Naturally, compounds having both a sulfonic acid group and a sulfuric acid ester group in one molecule are also effective.

In addition, if the OH groups of the polyethers are reacted with, for example, phosphorus pentoxide, metaphosphoric acid, thiophosphine, etc. in any ratio, monoesters, V-esters, and polyesters can be produced to obtain the additive of the present invention. can.

Such additives of the invention are used either in their acid form or preferably as counterion bottles. For example, metal cylinders and ammonium salts such as thorium, potassium, calcium, magnesium, aluminum, iron, lead, and nickel, as well as amine salts of the above-mentioned amine bottles and compounds containing quaternized N, are useful; Either the acid or the base may be in excess.

It is of course possible to use the additive of the present invention alone or as a mixture of the additives of the present invention, but it may also be used in combination with one type or multiple types of other surfactants.

Since the additive of the present invention exhibits a very excellent flocculating effect, the amount added is preferably 0.005 to 1% by weight, based on the coal in the coal-water slurry to be flocculated.
．． An amount of 0.01 to 0.5 weight layer is sufficient. The additive of the present invention may be added directly to the slurry, dissolved in a solvent such as isopropyl alcohol, ethylcellosolve, butylcellosorg, etc. and then added to the slurry, or dissolved in the oil used in advance and then added to the slurry.

Further, the present bulking agent may be added together with oil in the form of lIC07W type emulsified thread. That is, since the effect of the additive of the present invention is excellent, there is no need to particularly limit the method of addition.

The effect of the additive of the present invention does not change even if the coal-water slurry is heated up to that point, and even if an alkali or the like is added to adjust the pH of the slurry.

The basic method of flocculation treatment is to simply add oil and additives to a coal-selected water souffle, or to treat coal with oil and additives to create a water slurry, followed by stirring. All you need to do is perform the following operations, and either the patch type or continuous type may be used. In addition, since this additive exhibits an extremely excellent flocculating effect, there is no need to use a special stirrer; just use an ordinary stirrer and low-shear stirring.
Promptly causes agglomeration.

Since the aggregate is granulated into large particles, it is dehydrated to #slb by a filtration method, a centrifugation method, or the like. Note that due to the ash separation present in the coal and the unique effect of this additive, it is not aggregated and floats in the water, so it is separated from the coal in this process.

Although the theoretical basis for the excellent effects of the additives of the present invention is not based on Sada, it is probably because all of these additives have a special molecular structure and have a hydrophilic group. By adding it to the coal-water slurry together with oil, the oil can be added to the coal-water slurry to push the oil to the surface of the coal evenly, allowing the oil to adhere uniformly to the surface of the coal particles and coagulating the coal particles. This is thought to be because it is possible.

According to the present invention, it is possible to significantly increase the flocculation of pulverized coal and completely recover coal by simply adding the additive of the present invention to a water slurry together with oil and mixing without any complicated operations. .

Next, typical examples of the present invention will be shown.

Example: 1. Coal-water slurry with a predetermined coal concentration. Take an ooom glass beaker K 500F and mix using a stirrer with 3 blades. The additive of the present invention and the oil are each individually added thereto in sequence. Alternatively, oil in which a predetermined amount of the additive of the present invention is dissolved is added and mixed. Alternatively, the additive of the present invention is added and mixed with oil in an O/W type emulsification system.The agglomeration rate is determined by filtering the coal-water slurry that has undergone aggregation treatment through a 48-mesh IiK filter, and then calculating the agglomeration rate by filtering the coal-water slurry that has undergone aggregation treatment and remaining on the sieve. After drying, the coal was quantified and calculated using the following formula.

In addition, the right leg particle size in the water sfuji before being subjected to the test was 20
As with No. 0 bus 60% and 481 on 0.0%, if only 0 heavy oil was used at 20% of the stone foot, the agglomeration rate was as low as 34%, and the aggregation was insufficient. Even when other surfactants were used, the aggregation rate was as low as 39-56%, and the effect was weak.

On the other hand, if the additive of the present invention is used together with oil, the agglomeration rate will be 80%.
% or more, and the amount of oil used can be significantly reduced, demonstrating that the additive of the present invention has an extremely excellent flocculating effect.

Furthermore, the effect is almost the same whether this additive is added in an I/Co/W type emulsified system with oil or added without emulsifying oil, regardless of the method of addition. It was also demonstrated that the effect of the additive of the present invention was extremely excellent.

Claims (1)

[Scope of Claims] In recovering powdered coal from stone leg-water souffle using oil: 1) Molecular weight 1. OOo ~ 600,000, preferably ij 3
．． 000-300,000 polyether or polyether derivative. 2) Alcohols, amines, carboxylic acids, and derivatives thereof having at least 3 or more active hydrogens in the molecule, preferably 5 or more. 1
．． 000 to 600,000, preferably 0.000 to 300,000. 3) Adding an alkylene oxide to an organic compound having one or more, preferably two or more, -E phenolic OH groups and having two or more, preferably three or more total active hydrogens as a starting material, A polyether having a molecular weight of 1,000 to 600,000, preferably 7,000 to 300,000. 4) Molecular weight 1,000 to 600,000, preferably 2,000
A compound in which a polyether compound of ~20,000 is constructed using at least one selected from polyvalent isocyanate, polyvalent epoxy V, and polyvalent aldehyde compound. 5) Molecular weight 1,000 to 600,000, preferably 2. 'OO
A compound obtained by reacting a polyhydric carboxylic acid or a dihydric polycarboxylic acid compound with a polyether compound of 0 to 20,000 to cause intramolecular or intermolecular crosslinking. 6) Molecular weight from 1,000 using an aromatic compound as a starting material
A compound obtained by condensing 600,000, preferably 2,000 to 20,000 polyether compounds using formalin. 7) Molecular weight 1,000 to 600,000, preferably 2,000
A compound obtained by crosslinking ~20,000 polyether compounds in the presence of a peroxide (radical generating agent). 8) Contains at least an ethylene oxide group and a propylene oxide group in the molecule, and the content of ethylene oxide is 3 to 80% by weight, or 10 to 50% by weight, and the molecular weight is 1.000 to 1.000 600,000, preferably 70,000 to 300,000. 9) Molecular weight 1,000 to 600,000, preferably 2,000
Addition of at least one compound as an essential component from among the acids of 0 to 300,000 sulfonated polyether compounds, sulfuric acid esters, or phosphoric acid esters, or their counter ions. An additive for powdered coal flocculation that is characterized by: