JPS58215491A - Dispersant for coal/water slurry - Google Patents

Abstract

PURPOSE:To provide the titled dispersant containing specified polyether derivative and polyalkyleneimine (derivative) as effective ingredients and producing an aqueous slurry of coal which has good fluidity even at a high coal concentration. CONSTITUTION:The dispersant for coal/water slurry is prepared by mixing (A) 90-20pts.wt. polyether derivative with a molecular weight of 5,000-100,000 shown by the formula (where A is a residue of alcohol, phenol, amine, carboxylic acid or derivative thereof; R1 is a residue of 3-4C alkylene oxide; l is average mol no. of R1 added and is 0-100; m is average mol no. of ethylene oxide added and is 50-1,000; n is the number of functional groups) with (B) about 10- 80pts.wt. polyalkyleneimine (derivative) with an average molecular weight of 5,000-200,000 (e.g. polyethyleneimine or polypropyleneimine).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a dispersant for coal-water slurries. More particularly, the present invention relates to a dispersant that disperses 6-silicon powder in water and provides a fluidized coal-water slurry even with a high concentration of coal.

Petroleum, which has traditionally been widely used as an energy source,
Its price has increased significantly and there are concerns that it will run out.

Therefore, the challenge is to develop other energy sources that can provide a stable supply, and coal is about to become widely available again.
2- There is. However, the biggest problem in using coal is transportation problems due to the fact that coal is solid.

Conventionally, mined coal is pulverized into powder, which is made into a coal-water slurry, fluidized, and transported by pipeline.

On the other hand, COM (Coal-
Although oil (Oi l-M 1xture) is being tested, there are problems with stable supply and price since it uses oil, and high-concentration coal-water slurry will be considered as one of the coal utilization technologies in the future. is seen as promising.

This technology for slurrying coal into water is about to be used in an extremely wide range of coal uses, including direct coal combustion and gasification, in addition to the aforementioned coal pipeline transportation.
This has become an important issue in the use of coal. This coal-
It is preferable for the water slurry to be a highly concentrated slurry with a small water content from the economic and pollution prevention viewpoints. Especially in the case of direct combustion of coal water slurry, which can eliminate wastewater treatment and pollution problems, dehydration of coal water slurry, -3
- It is necessary to reduce the moisture content as much as possible in order to charge the water slurry of coal into a cyclone or turbulent burner and burn it directly in the furnace without performing any treatment such as drying. There is no need to mention the reason here, but
488 specification in detail.

However, when attempting to increase the concentration of Ishikawa powder in water using known techniques, the slurry becomes significantly thickened and loses fluidity.

Conversely, if the concentration of coal powder in water is reduced, transportation efficiency, combustion efficiency, etc. will be reduced, and if water slurry of coal is dehydrated and used, the dehydration and drying processes will also increase costs and cause pollution. There are problems such as causing problems.

Conventionally, various dispersants for coal-water slurries have been proposed to solve such problems. For example, surfactants such as sodium oleate, sodium dodecyl benzene sulfonate, alkyl allyl sulfonate, polyoxyethylene alkyl phenyl ether, and stearylamine hydrochloride, polyethylene glycol, poly=4 to acrylamide, and cellulose. , water-soluble polymers such as sodium polyacrylate, etc. However, both have insufficient fluidity and lack practicality.

As a result of intensive research to solve the above-mentioned problems with dispersants for coal-water slurries, the present inventors have discovered that certain polyether derivatives (I), polyalkylene imines, and polyalkylene imine derivatives The present inventors have completed the present invention by discovering that a composition containing one or more compounds (Ir) selected from the group consisting of: has an excellent effect as a dispersant for coal-water slurry.

That is, the present invention provides a dispersant for easily producing a coal-water slurry that has fluidity even at high concentrations.

That is, the dispersant for coal-water slurry of the present invention has the following formula: Residues of acids and their derivatives, R
+ is an alkylene oxide residue having 3 to 4 carbon atoms, t is the average number of added moles thereof, and m is the average number of added moles of ethylene oxide, and 50 to 10001n is the number of functional groups, and the molecular weight is 5000 to 10. 1,000 polyether derivatives (I); and (B) one or more compounds (II) selected from the group consisting of polyalkylene imines and polyalkylene imine derivatives. This invention relates to a dispersant for water slurry.

The coal used for the coal-water slurry is, for example, anthracite,
Any type of coal, such as bituminous coal, sub-bituminous coal, lignite, etc., can be used regardless of its type and origin, as well as its moisture content and chemical composition. Such coal can be milled by wet or dry grinding in a conventional manner to produce 200%
The standard for use is a mesh pass of 50% by weight or more, preferably 70 to 80% by weight. Further, the slurry concentration is 60 to 90% by weight based on pulverized coal, and if it is less than 60% by weight, it has no practical meaning in terms of economy, transportation efficiency, combustion efficiency, etc.

Polyether derivative (I) and compound (If) constituting the dispersant for coal-water slurry of the present invention can be produced by the following method.

The polyether derivative (I) having a molecular weight of 5,000 to 100,000 according to the present invention has the general formula A [(RlO)L(CH2CH20
)mH,l]n, where A is a residue of a reaction starting material having various functional groups having one or more active hydrogens in the molecule, and various alkylenes having 3 to 4 carbon atoms. An oxide such as propylene oxide or butylene oxide is generally subjected to an addition reaction under pressure using a catalyst such as an alkali or an acid, and then ethylene oxide is added in a similar manner.

R is an alkylene oxide residue having 3 to 4 carbon atoms.

E represents the average number of moles of alkylene oxide added from 0 to 100, and symbol (2) represents the average number of moles of ethylene oxide added from 50 to 1000. n is a number that is the same as or smaller than the functional number of the reaction starting material, and the alkylene oxide may be bonded to all of the functional number or only to a part of the functional number.

One type or two or more types of R10 may be used, and the arrangement thereof may be either a block type and/or a random type.

The active hydrogen groups mentioned here include alcoholic hydroxyl groups, phenolic hydroxyl groups, amino groups, carboxylic acid groups, etc.
A starting material containing one or more of these. Specific examples of these are as follows.

Alcohols containing one or more active hydrogen groups include ethyl alcohol, butyl alcohol, octyl alcohol, stearyl alcohol, ceryl alcohol, C12-
14 Secondary alcohol, (trade name Softanol@ manufactured by Nippon Shokubai Chemical), ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, butylene glycol, polybutylene glycol, butanediol, bentanediol, glycerin, butanetriol, hexanetriol, trimethylolpropane, triethanolamine, diglycer-8-phosphorus, pentaerythritol, sorbitan, sorbitol]-
-ol, glucose, sucrose, partially saponified polyvinyl acetate, cellulose, starch, etc. are useful.

In addition, examples of amines containing one or more active hydrogen groups include dimethylamine, methylamine, ethylamine, propylamine, butylamine, allylamine, amylamine,
Octylamine, dodecylamine, laurylamine, tetradecylamine, octadecylamine, tallow alkylamine, coconut alkylamine, aniline, toluidine, nitroamine, benzylamine, chloraniline, cyclohexylamine, ammonia, tallow propylene diamine, ethylenediamine, tetramethylene Diamines, phenylenediamine, benzidine, cyclohexyldiamine, diethylenetriamine, 1-lyethylenetetramine, tetraethylenepentamine, and the like are useful.

Examples of carboxylic acids containing one or more active hydrogen groups include acetic acid, lauric acid, oleic acid, stearic-9-acid, oxalic acid, malonic acid, phthalic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, and azelaic acid. , sebacic acid, dimer acid, phenylene diacetic acid, hemimelitic acid,
Various derivatives such as trimellidic acid, trimesic acid, pyromellitic acid, and ethylenediaminetetraacetic acid can also be used.

Phenols containing one or more active hydrogen groups include phenol, bisphenol, cresol, alkylphenol, resorcinol, catechol, hydroquinone, and other compounds with aromatic hydroxyl groups.
Useful.

Furthermore, compounds containing different types of active hydrogen groups in the same molecule, such as lactic acid, malic acid, glycolic acid, monoethanolamine, jetanolamine, and amino acids, can also be used.

Compounds constituting the dispersant for coal-water slurry of the present invention (
IF) can be produced by the method shown below.

The polyalkyleneimine of the present invention is a homopolymer-10- or copolymer consisting of at least one alkyleneimine monomer. The alkyleneimine monomer is 1
, 2-alkyleneimine (aziridine) and 1.3-
It is an alkyleneimine (azetidine), and its specific examples include ■tyrenimine, 1゜2-propyleneimine,
1.3-propyleneimine, 1-methylaziridine, 2
．． 2-dimethylaziridine, 1-ethylaziridine, 2
-ethylaziridine, 2-n-propylaziridine, 2
-isopropylaziridine, 2-n-butylaziridine, 2-isobutylaziridine, 1-<2-aminoethyl)aziridine, 1-(2-cyanoethyl)aziridine,
Examples include 1-(2-hydroxyethyl)aziridine.

Homopolymerization and copolymerization of alkyleneimine monomers into polyalkyleneimines are promoted with acid catalysts and are easily carried out by methods known per se. The types of copolymerization of alkyleneimine monomers are random copolymerization, block copolymerization,
Any one from Graph 1 to a common vehicle platform etc. may be used.

Typical polyalkylene E used in the present invention 1
1-mines are polyalkyleneimines and polypropyleneimines, which are produced on an industrial scale and are commercially available and ready for use.

Another preferred polyalkyleneimine is a poly(ethyleneimine-brobyleneimine) copolymer. The molecular weight of the polyalkyleneimine is not particularly limited, and a wide range of 600 to 1,000,000 is usually used, but a range of 5,000 to 200,000 is particularly preferred.

Polyalkylene imine derivatives are so-called modified polyalkylene derivatives made by reacting some of the amino groups of polyalkylene imine with a compound having a functional group that is reactive with amine groups, and making them soluble in water or a solvent mainly composed of water. It means Imin.

Specific examples of such polyalkylene imine derivatives include polyalkylene imine derivatives obtained by reacting a compound having an active double bond such as acrylamide or acrylonitrile; and polyalkylene imine derivatives obtained by reacting an aldehyde such as formaldehyde or acetaldehyde. Polyalkyleneimine-12- derivatives; examples include polyalkyleneimine derivatives obtained by reacting acid anhydrides such as succinic anhydride, but are not limited thereto. One type of polyalkyleneimine derivative may be used alone, or two or more types may be used in combination. Also polyalky 1
It can also be used in combination with nonimine.

The dispersant for coal-water slurry of the present invention contains a polyether derivative (I) and a compound (II) as active ingredients, and the ratio of these two to be used is not particularly limited. 10 to 80 parts by weight of the compound (Ir) to 90 to 20 parts by weight (however, the total of both is 100 parts by weight).

) ratio exhibits particularly excellent performance.

The dispersant for coal-water slurries of the present invention is used in pulverized coal-water slurries, but the amount added is not particularly limited and is effective over a wide range of amounts. It is used in a proportion of 0.05 to 3% by weight (dry basis), preferably 0.1 to 2% by weight.

= 13 To use the dispersant for coal-water slurry of the present invention, the polyether derivative (I) and the compound (IT) may be mixed in advance and then added at the time of slurry preparation, or The ether derivative (I) and the compound (I) may be added separately when preparing the slurry.

Alternatively, it may be mixed with coal in advance to form a slurry, or it may be dissolved in water in advance. Further, due to the nature of the dispersant, any device for slurrying coal in water may be used as the slurry device.

The scope of the present invention is not limited by these addition methods and slurry-forming methods.

Next, the dispersant for coal-water slurry of the present invention will be explained in more detail by giving comparative examples and examples, but of course the present invention is not limited thereto.

In the examples, unless otherwise specified, % means % by weight, and parts represent parts by weight.

Example-14- Aqueous solution containing predetermined amounts of various dispersants shown in Table-1 30.7
9.3 g of pulverized Blair\Nor charcoal e <moisture content 6.2%) such that a 200-mesh sieve is 75% bathed in g is stirred little by little at room temperature. After adding the entire amount, add 10.0OOR using Bomomiki No. (manufactured by Tokushuki Kako).
PM, prepare the coal-water slurry by stirring for 2 minutes.
The viscosity was measured at ℃ and the fluidity was evaluated.

The results are shown in Table-1. This indicates that the lower the viscosity, the better the fluidity.

The substances of the compound (■) shown in Table 1 are as follows.

11-1: Polyethyleneimine (molecular weight approximately 90,000) ■-
2: Polybrobyleneimine (molecular weight approximately 50,000) ■-3: Ethyleneimine (2.5 mol)/1.2 propylene imine (10 mol) copolymer (molecular weight approximately 120,000) TI-4: Acrylonitrile addition ( 0.1 mole) polyethyleneimine (molecular weight approximately 50,000) -15- 605-

Claims (1)

[Claims] (1) (△) General formula % Formula %] (wherein A represents alcohols, phenols, amines, carboxylic acids and derivatives thereof having one or more active hydrogens in the molecule) residue, R□ is a fullylene oxide residue having 3 to 4 carbon atoms, and t is the average number of added moles of O to 100.
, m is the average number of added moles of ethylene oxide, 50 to 10
00. (n is the number of functional groups) molecule m 5,000 to 100,000 polyether derivatives (1); (B) one or more selected from the group consisting of polyalkylene imines and polyalkylene imine derivatives; A dispersant for coal-water slurry, characterized by containing compound (IT)-1-. <2) Claim 1 in which the polyalkylene imine is polyethylene imine or polypropylene imine
Dispersant as described in section. (3) The dispersant according to any one of claims 1 to 2, wherein the polyalkylene imine or polyalkylene imine derivative has an average molecular weight of 5,000 to 200,000.