JP2018057988A - Dispersant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel use of an acid-hydrolyzed liquid, which has been used only as fuel, wherein the acid-hydrolyzed liquid is obtained by acid-hydrolyzing a lignocellulose material: specifically, the acid-hydrolyzed liquid is obtained through a process for hydrolyzing a lignocellulose material before kraft digestion to obtain a dissolved pulp.SOLUTION: A dispersant contains an acid-hydrolyzed liquid obtained by treating a lignocellulose material in hot water at 130-190°C for 30-400 minutes.SELECTED DRAWING: None

Description

  The present invention relates to a dispersant containing an acid hydrolysis solution obtained by subjecting a lignocellulosic material to an acid hydrolysis treatment.

  In order to produce dissolving pulp from a lignocellulosic material, it is necessary to selectively remove hemicellulose and lignin in the lignocellulosic material to increase the purity of the cellulose. As an index representing cellulose purity, α-cellulose content is generally used, and the higher the value, the higher the quality of dissolved pulp.

  Two methods of dissolving pulp have been known for a long time: acidic sulfite cooking method and hydrolysis-kraft cooking method. In acidic sulfite cooking method, many hemicelluloses and lignin in lignocellulosic material are digested. In the hydrolysis-kraft cooking method, most of the hemicellulose is removed by acid hydrolysis in the hydrolysis step, and a small amount of hemicellulose and most of the lignin are removed by subsequent kraft cooking. In the hydrolysis process, simply adding water to the lignocellulosic material and heating, the acetyl group in hemicellulose is eliminated to produce acetic acid, which automatically becomes acidic and acid hydrolysis proceeds. It is carried out without adding from the outside (Patent Document 1, Patent Document 2).

JP 2012-219416 A Japanese Patent No. 2984798

  The techniques described in Patent Documents 1 and 2 are performed for the purpose of obtaining dissolved pulp, and the use of the acid hydrolysis treatment liquid obtained in the hydrolysis step is described as black produced in the cooking step. It was not used other than being used as energy in the pulp manufacturing process in the factory as a fuel together with the liquid.

  Therefore, the present invention provides a hydrolyzed liquid obtained by acid hydrolysis treatment of a lignocellulosic material, specifically, an acid hydrolysis obtained in a step of hydrolyzing the lignocellulosic material before kraft cooking to obtain a dissolved pulp. It aims at providing the utilization method of the decomposition processing liquid other than the fuel.

The present invention provides the following (1) to (6).
(1) In a dispersant composition containing an acid hydrolysis treatment liquid obtained by acid hydrolysis treatment of a lignocellulosic material, the acid hydrolysis treatment liquid converts the lignocellulosic material to heat at a temperature of 130 to 190 ° C. A dispersant composition obtained by acid hydrolysis treatment in water for 30 to 400 minutes.
(2) The dispersant according to (1), which contains at least one compound selected from the following (A) to (C).
(A) Carboxyl group and / or salt-containing compound (B) Compound having acid group and polyalkylene glycol chain (C) Sulfonic acid group and / or salt-containing polymer compound

(3) The dispersant according to any one of (1) to (2), which is a dispersant for inorganic substances.
(4) The dispersant according to any one of (1) to (2), which is a dispersant for organic substances.
(5) The dispersant according to any one of (1) to (2), which is a dispersant for cement.
(6) A dispersion composition containing the dispersant, the dispersant, and the dispersion medium according to any one of (1) to (5).

  According to the present invention, a hydrolyzed liquid obtained by acid hydrolysis treatment of a lignocellulosic material, specifically, acid hydrolysis obtained in a step of hydrolyzing the lignocellulosic material before kraft cooking to obtain dissolved pulp. Utilization methods other than the fuel of the decomposition treatment liquid can be provided.

Specifically, a dispersant having excellent dispersibility with respect to inorganic substances, organic substances, cements, and the like can be provided. In particular, when used as a dispersant for cement, it has excellent dispersibility and setting delay compared with conventional AE water reducing agents (lignin sulfonates, sodium gluconate).

  The present invention relates to a dispersant composition comprising an acid hydrolysis treatment liquid obtained by treating a lignocellulose material in hot water at a temperature of 130 to 190 ° C. for 30 to 400 minutes.

  The dispersant composition containing an acid hydrolyzed product obtained by acid hydrolyzing a lignocellulosic material within the above temperature and time range is an excellent dispersion for various inorganic substances (especially cement) and various organic substances. Have sex. Examples of the acid hydrolysis treatment liquid include an acid hydrolysis treatment liquid obtained in a step of hydrolyzing a lignocellulosic material before kraft cooking to obtain a dissolved pulp.

(Lignocellulose material)
In the present invention, lignocellulosic material is not particularly limited, but non-wood represented by conifers, wood represented by hardwood, bamboo, sugar cane (bagasse), banana, kenaf, etc. can be used, These may be used alone or in combination of two or more.

  Examples of coniferous trees are spruce, todomatsu, red pine, black pine, larch, cedar, cypress, western larch, radiata pine, black spruce, white spruce, western hemlock, southern pine, balsam fur, larch, jack pine, douglas fir, etc. Can be mentioned. As an example of a broad-leaved tree, Eucalyptus wood can be mentioned as a suitable example.

  In the present invention, when using the above wood as the lignocellulosic material, it is preferable to use it in a certain size or less. That is, it is efficient to use wood in chips or powders. The specific size may be a size generally used for pulp or papermaking (for example, a length of 15 to 20 mm in the grain direction, a width of 12 to 25 mm, a thickness of about 10 mm or less), but penetrates hot water. In order to facilitate the extraction and increase the efficiency of extraction and hydrolysis, it is desirable that one side has a size of 3 to 6 mm.

(Acid hydrolysis treatment)
In the present invention, the acid hydrolysis treatment method of the lignocellulosic material is not particularly limited, but a method using an organic acid liberated from the lignocellulosic material by blowing high temperature steam into the lignocellulosic material, lignocellulose, Examples thereof include a method for treating a cellulose substance in an acid solution. The hydrolysis treatment liquid may contain the above organic acid and acid solution. Examples of the organic acid include acetic acid and oxycarboxylic acids, and examples of the acid solution include sulfuric acid and sulfurous acid.

  The conditions for the hydrolysis treatment are not particularly limited, but the liquid ratio of water or a liquid phase or vapor phase of mineral acid of 2% by mass or less to organic liquor and lignocellulosic material such as wood chips (of lignocellulosic material). The ratio of water, or a mineral acid or organic acid of 2% by mass or less to the absolute dry weight) is preferably in the range of 1 to 10, and the liquid ratio is more preferably 2 to 5, and more preferably 2.5 to 3.5. preferable. By adjusting the liquid ratio within this range, it is possible to efficiently extract substances having excellent dispersibility with respect to various dispersions from lignocellulosic substances.

  As treatment conditions for acid hydrolysis, it is important that the treatment temperature is 130 to 190 ° C., preferably 165 to 185 ° C., and the treatment time is 30 to 400 minutes, preferably 36 to 150 minutes.

  By subjecting to acid hydrolysis at a treatment temperature of 130 ° C. or higher, a substance having excellent dispersibility with respect to various dispersions can be extracted from the lignocellulosic substance in the resulting acid hydrolysis liquid treatment liquid, By performing an acid hydrolysis treatment at a treatment temperature of 190 ° C. or lower, it is possible to extract from a lignocellulosic material without decomposing a material having excellent dispersibility with respect to various dispersions.

  In addition, by setting the treatment time to 30 minutes or longer, it is possible to extract substances having excellent dispersibility for various dispersions from the lignocellulosic material, while the treatment time is set to 400 minutes or less. Thus, the lignocellulosic material can be extracted from the lignocellulosic material without decomposing the material having excellent dispersibility with respect to various dispersions.

  In the present invention, the acid hydrolysis treatment temperature and time are preferably adjusted so that the Pf value (P factor) represented by the following formula is 350 to 900, preferably 500 to 800. .

Pf = ∫ln-1 (40.48-15106 / T) dt (Formula 1)
[Wherein T represents the absolute temperature of the prehydrolysis waste liquid]

  The P factor is an index representing the total amount of heat given until the treatment of the lignocellulosic material with water or 2% by mass or less of mineral acid or organic acid is completed.

  When Pf is 350 or more, a substance having excellent dispersibility with respect to various dispersions can be extracted from the lignocellulose material. On the other hand, when Pf is 900 or less, from the lignocellulose material. It is possible to extract from a lignocellulosic material without decomposing a material having excellent dispersibility with respect to various dispersions.

  In the present invention, any water may be used for extraction, but water with lower hardness can provide a better extraction / hydrolysis effect. The range of hardness is not particularly limited, but is preferably 100 or less, and more preferably 50 or less.

  Although the hydrolysis treatment liquid obtained by the hydrolysis treatment can be used as it is, it is preferable to concentrate to a solid content of 20 to 50% using an evaporator. By increasing the solid content by concentration, it is possible to prevent corruption, reduce logistics costs, and improve handling.

In order to suppress precipitation of suspended substances contained in the acid hydrolysis treatment liquid obtained by acid hydrolysis treatment of the lignocellulosic material of the present invention, the pH of the acid hydrolysis treatment liquid is raised to 8 or higher to suspend the suspension. The substance can be solubilized. In addition, since the cement composition is alkaline, the precipitate is dissolved in the cement composition even if the acid hydrolysis treatment liquid containing the precipitated suspended substance is used as it is. It is suitably used for cement.

  In the present invention, as long as the characteristics of the present invention are not impaired, neutralization can be performed by using an alkali and / or a mixture of alkali and sodium sulfide, a cooking white liquor, or the like as the prehydrolysis solution. It is. It is also possible to denature the reducing sugars in the acid hydrolysis solution under hot alkaline conditions. Furthermore, it is also possible to use an acid "hydrolysis treatment solution after extracting furans such as furfural.

(To be dispersed)
Although the to-be-dispersed material disperse | distributed using the dispersing agent containing the hydrolysis waste liquid of this invention is not specifically limited, A various inorganic substance and organic substance are mentioned. The shape of the dispersion target is not particularly limited, and examples thereof include powder, particles, granules, fibers, and flat plates.

  Specific examples of inorganic substances include silicates such as kaolin, aluminum silicate, clay, talc, mica, calcium silicate, sericite, bentonite; calcium carbonate, magnesium carbonate, barium carbonate, basic lead carbonate, etc. Carbonates such as calcium sulfate and barium sulfate; chromates such as strontium chromate and pigment yellow; molybdates such as zinc molybdate, calcium molybdate and magnesium molybdate; alumina, antimony oxide, titanium oxide, Metal oxides such as cobalt oxide, triiron tetraoxide, ferric trioxide, trilead tetraoxide, lead monoxide, chromium oxide green, tungsten trioxide, yttrium oxide; aluminum hydroxide, magnesium hydroxide, calcium hydroxide, Iron hydroxide, Metachi Metal hydroxides such as acids; Metal carbides such as silicon carbide, tungsten carbide, boron carbide, titanium carbide; Aluminum nitride, silicon nitride, boron nitride, zirconia, barium titanate, satin white, carbon black, graphite, chrome yellow , Mercury sulfide, ultramarine, Paris blue, titanium yellow, chrome vermillion, lithopone, copper acetoarsenite, nickel, silver, palladium, lead zirconate titanate, etc., but are not limited thereto. . These inorganic substances generally have an average particle size of 100 μm or less, preferably 0.1 μm or more and 50 μm or less. These inorganic substances may be used alone or in combination of two or more.

  Specific examples of the organic substance include, for example, phospho yellow, disazo yellow, disazo orange, naphthol red, copper phthalocyanine pigment, phosphomolybdenum tungstate, tannate, katanol, tamol lake, isoindolinone ero greenish, iso Organic pigments such as indolineine ethoredish, quinacridone, dioxazine violet, perinone orange, perylene vermilion, perylene cullet, perylene red, perylene maroon; synthesis of polycarbonate, polyvinyl chloride, polymethyl methacrylate, fluorine resin, etc. Resin; Aluminum stearate, zinc stearate, calcium stearate, magnesium stearate, zinc stearate / calcium stearate composite, stearin Lead, cadmium stearate, barium stearate, calcium laurate, although such metal soaps such as zinc laurate and the like, but is not limited thereto. These organic substances generally have an average particle size of 100 μm or less, preferably 0.1 μm or more and 50 μm or less. These organic substances may be used alone or in combination of two or more.

  The dispersion medium for dispersing the above inorganic substance and / or organic substance using the dispersant containing the hydrolysis waste liquid of the present invention is not particularly limited, but includes, for example, water; kerosene, light oil, kerosene, etc. Fuel oils; aliphatic hydrocarbons such as hexane, isohexane, cyclohexane, methylcyclohexane, isooctane; aromatic hydrocarbons such as benzene, toluene, xylene, cresol; ethanol, methanol, isopropyl alcohol, butyl alcohol, pentyl alcohol Alcohols such as ethyl acetate, dioctyl phthalate, etc .; ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol , Ethylene glycol monobutyl ether, carbitol, monoglyme, diglyme, tetraglyme, methyl cellosolve, butyl cellosolve and other ethers; butanediol, pentanediol, hexanediol and other diols; 1,1,1-trichloroethane, trichloroethylene , Halogenated hydrocarbons such as dichloroethylene and chlorodifluoromethane; ketones such as methyl isoamyl ketone, methyl isobutyl ketone, acetone and methyl ethyl ketone; terpineol, liquid paraffin, mineral spirit, N- (2-hydroxyethyl) pyrrolidone, glycerin, etc. Is mentioned. Of these dispersion media, water is particularly preferred. These dispersion media may be used alone or in combination of two or more.

(Addition of dispersion medium and dispersant)
When using the acid hydrolysis treatment of the present invention, the method of mixing with the dispersion medium is not particularly limited. For example, the acid hydrolysis treatment liquid of the present invention may be mixed with the dispersion medium before adding the dispersion, or the acid hydrolysis treatment liquid of the present invention may be added to the dispersion medium simultaneously or sequentially. Also good. Or after mixing a to-be-dispersed material with a dispersion medium previously, you may add the acid hydrolysis process liquid of this invention later.

(Amount of dispersant used, combined use with other dispersants)
The amount used of the acid hydrolysis treatment liquid of the present invention may be appropriately adjusted according to the type and amount of the dispersion, and is not particularly limited. For example, for 100 parts by mass of the dispersion The amount is preferably 0.001 part by mass or more and 10 parts by mass or less. The dispersion medium is usually used in an amount of 20 to 1,000 parts by mass with respect to 100 parts by mass of the dispersion.

  The dispersant of the present invention can be used in combination with a hydrolysis waste liquid and at least one compound selected from the following (A) to (C). (A) A carboxyl group and / or a salt-containing compound thereof, (B) a compound having an acid group and a polyalkylene glycol chain, (C) a sulfonic acid group and / or a salt-containing compound thereof.

  Examples of the (A) carboxyl group and / or salt-containing compound thereof include, but are not limited to, sodium polyacrylate and sodium gluconate.

  (B) As a compound having an acid group and a polyalkylene glycol chain, a copolymer of (poly) oxyethylene methacrylate and (meth) acrylic acid and / or a salt thereof, (poly) oxyethylene allyl ether and (meth) acrylic Copolymer with acid and / or salt thereof, (poly) oxyethylene allyl ether and maleic anhydride copolymer and / or salt thereof, (poly) oxy of 3-methyl-3-buten-1-ol Copolymer of ethylene adduct and (meth) acrylic acid and / or salt thereof, (poly) oxyethylene adduct of 3-methyl-3-buten-1-ol and maleic anhydride and / or its Examples include, but are not limited to, salts.

  Examples of the (C) sulfonic acid group and / or a salt-containing compound thereof include sodium lignin sulfonate and naphthalene sulfonic acid, but are not limited thereto.

  When the acid hydrolysis treatment liquid of the present invention and the compounds (A) to (C) are used in combination, the weight ratio when the two components are used in combination is the acid hydrolysis treatment liquid / (A) to (C ) = 1 to 99/1 to 99, and the weight ratio when the three components are used in combination is different from the acid hydrolysis solution / (A) to (C) compound 1 type (1) / (1). (A)-(C) 1 type compound (2) = 1-99 / 1-99 / 1-99 The weight ratio in the case of using 4 components together is an acid hydrolysis process liquid / (A)-(C 1 type of compound (2) / (1) different from 1 type of compound (1) / (1) (1) / (1), 1 type of (A) to (C) different from (2) Compound (3) = 1 to 99/1 to 99/1 to 99/1 to 99.

(Cement dispersant)
The dispersant containing the acid hydrolysis treatment liquid of the present invention can be used for various applications, but is particularly suitable as a cement dispersant. Therefore, the case where the hydrolysis waste liquid of the present invention is used as a cement dispersant will be described in detail below.

  When the dispersant containing the acid hydrolysis treatment liquid of the present invention is used as a cement dispersant, it may be used in the form of an aqueous solution, or a hydroxide of a divalent metal such as calcium or magnesium after the reaction. Neutralized with a polyvalent metal salt and then dried, supported on inorganic powder such as silica fine powder and dried, using a drum-type drying device, a disk-type drying device or a belt-type drying device After drying and solidifying into a thin film on a support, it may be pulverized or dried and solidified by a spray dryer to be used as a powder. Also, the hydrolyzed waste liquid of the present invention is blended in advance with a water-free cement composition such as cement powder or dry mortar, and used as a premix product for plastering, floor finishing, grout, etc. Alternatively, it may be blended when the cement composition is kneaded.

  The dispersant containing the acid hydrolysis treatment liquid of the present invention is useful as a cement dispersant, and can be used for various hydraulic materials, that is, cement compositions such as cement and gypsum and other hydraulic materials. . Specific examples of a hydraulic composition containing such a hydraulic material, water, and the cement dispersant of the present invention, and further containing fine aggregate (such as sand) and coarse aggregate (such as crushed stone) as necessary. Examples thereof include cement paste, mortar, concrete, and plaster.

  Among the hydraulic compositions, a cement composition that uses cement as a hydraulic material is the most common, and the cement composition contains the hydrolysis waste liquid of the present invention, cement, and water as essential components. Such a cement composition is one of the preferred embodiments of the present invention.

  The cement used in the cement composition is not particularly limited, and specific examples include, for example, Portland cement (ordinary, early strength, very early strength, moderate heat, sulfate resistance, and respective low alkalis). Shape), various mixed cements (blast furnace cement, silica cement, fly ash cement), white Portland cement, alumina cement, super fast cement (1 clinker fast cement, 2 clinker fast cement, magnesium phosphate cement), grout cement , Oil well cement, low exothermic cement (low exothermic blast furnace cement, fly ash mixed low exothermic blast furnace cement, high content belite cement), ultra high strength cement, cement-based solidified material, eco-cement (city waste incineration ash, sewage sludge) Cement made from one or more types of incinerated ash) And so on. Furthermore, fine powder such as blast furnace slag, fly ash, cinder ash, clinker ash, husk ash, silica fume, silica powder, limestone powder, or gypsum may be added to the cement composition. Aggregates include gravel, crushed stone, granulated slag, recycled aggregate, etc., as well as silica, clay, zircon, high alumina, silicon carbide, graphite, chrome, chromia, magnesia Refractory aggregates such as can be used.

  In the above cement composition, the unit water amount per 1 m 3, the amount of cement used, and the water / cement ratio (mass ratio) are preferably 100 kg / m 3 or more and 185 kg / m 3 or less, more preferably 120 kg / m 3. The amount of cement used is preferably 200 kg / m3 or more and 800 kg / m3 or less, more preferably 250 kg / m3 or more and 800 kg / m3 or less, and the water / cement ratio (mass ratio) is 175 kg / m3 or less. Preferably it is 0.1 or more and 0.7 or less, More preferably, it is 0.2 or more and 0.65 or less, and it can be used widely from poor blending to rich blending. The dispersant containing the hydrolysis waste liquid of the present invention has a high water reduction rate region, that is, a water / cement ratio (mass ratio) of 0.15 or more and 0.5 or less (preferably 0.15 or more and 0.4 or less. ) Can also be used in areas where the water / cement ratio is low, and it can be used for both high-strength concrete with a large amount of unit cement and a small water / cement ratio, and poor-mixed concrete with a unit cement amount of 300 kg / m3 or less. It is valid.

  In the above cement composition, the amount of the dispersant containing the hydrolysis waste liquid of the present invention is, for example, when used for mortar or concrete using hydraulic cement, in terms of solid content, with respect to the mass of cement. Preferably, it is 0.001 mass% or more and 10.0 mass% or less. Such a blending amount brings various preferable effects such as a reduction in unit water amount, an increase in strength, and an improvement in durability. When the blending amount of the dispersant containing the hydrolysis waste liquid of the present invention is less than 0.001% by mass, the dispersion performance may not be sufficiently exhibited. On the contrary, if the blending amount of the dispersant containing the hydrolysis waste liquid of the present invention exceeds 10.0% by mass, the effect of improving the dispersibility is substantially saturated, and the hydrolysis of the present invention is more than necessary. A dispersing agent containing the decomposition waste liquid is used, which may increase the manufacturing cost.

  The cement composition has high dispersibility and dispersion retention performance even in a high water reduction rate region, and exhibits sufficient initial dispersibility and viscosity reduction even at low temperatures, and has excellent workability. To ready mixed concrete, concrete for concrete secondary products (precast concrete), concrete for centrifugal molding, concrete for vibration compaction, steam-cured concrete, shotcrete, etc. Is required to have high fluidity such as concrete with a thickness of 22 cm or more and 25 cm or less, high fluidity concrete (concrete with a slump value of 25 cm or more, slump flow value of 50 cm or more and 70 cm or less), self-filling concrete, self-leveling material, etc. Mortar or concrete Also effective.

  Moreover, the said cement composition can contain the other conventionally well-known cement additive (material) which is illustrated to following (1)-(11).

  (1) Water-soluble polymer material: unsaturated carboxylic acid polymer such as polyacrylic acid (sodium), polymethacrylic acid (sodium), polymaleic acid (sodium), sodium salt of acrylic acid / maleic acid copolymer; methylcellulose Nonionic cellulose ethers such as ethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, carboxyethyl cellulose, hydroxypropyl cellulose; alkylated or hydroxyalkylated derivatives of polysaccharides such as methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose A hydrophobic substituent in which some or all of the hydrogen atoms of the hydroxy group have a hydrocarbon chain having 8 to 40 carbon atoms as a partial structure; A polysaccharide derivative substituted with an ionic hydrophilic substituent having a sulfonic acid group or a salt thereof as a partial structure; yeast glucan, xanthan gum, 6-1.3 glucan (which may be linear or branched) , For example, polysaccharides produced by microbial fermentation such as curdlan, paramylon, pachyman, scleroglucan, laminaran); polyacrylamide; polyvinyl alcohol; starch; starch phosphate; sodium alginate; gelatin; A copolymer of acrylic acid having an amino group therein and its quaternary compound.

  (2) Polymer emulsion: Copolymers of various vinyl monomers such as alkyl (meth) acrylate.

  (3) Curing retarders other than oxycarboxylic acid compounds: monosaccharides such as glucose, fructose, galactose, saccharose, xylose, apiose, ribose, isomerized sugar, oligosaccharides such as disaccharide and trisaccharide, or dextrin Oligosaccharides or polysaccharides such as dextran, sugars such as molasses containing them; sugar alcohols such as sorbitol; magnesium fluorosilicate; phosphoric acid and its salts or boric acid esters; aminocarboxylic acid and its salts; Protein; Humic acid; Tannic acid; Phenol; Polyhydric alcohol such as glycerol; Aminotri (methylenephosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephos Phosphate) and alkali metal salts thereof, such as phosphonic acid and derivatives thereof such as alkaline earth metal salts.

  (4) Early strengthening agents / accelerators: soluble calcium salts such as calcium chloride, calcium nitrite, calcium nitrate, calcium bromide and calcium iodide; chlorides such as iron chloride and magnesium chloride; sulfates; potassium hydroxide; Sodium hydroxide; carbonate; thiosulfate; formate such as formic acid and calcium formate; alkanolamine; alumina cement; calcium aluminate silicate.

  (5) Antifoaming agents other than oxyalkylene-based: mineral oil-based antifoaming agents such as coconut oil and liquid paraffin; fat and oil-based antifoaming agents such as animal and vegetable oils, sesame oil, castor oil, and these alkylene oxide adducts; oleic acid and stearic acid Fatty acid-based antifoaming agents such as these alkylene oxide adducts; Fatty acid ester-based antifoaming agents such as glycerin monoricinoleate, alkenyl succinic acid derivatives, sorbitol monolaurate, sorbitol trioleate, natural wax; octyl alcohol, hexadecyl Alcohol-based antifoaming agents such as alcohol, acetylene alcohol and glycols; Amide-based antifoaming agents such as acrylate polyamines; Phosphate-based antifoaming agents such as tributyl phosphate and sodium octyl phosphate; Aluminum stearate, calcium oleate, etc. Metal soap-based antifoaming agent; dimethyl silicone oil, silicone paste, silicone emulsion, organically modified polysiloxane (polyorganosiloxane such as dimethylpolysiloxane), silicone-based antifoaming agent such as fluorosilicone oil, and the like.

  (6) AE agent: resin soap, saturated or unsaturated fatty acid, sodium hydroxystearate, lauryl sulfate, ABS (alkyl benzene sulfonic acid), LAS (linear alkyl benzene sulfonic acid), alkane sulfonate, polyoxyethylene alkyl (phenyl) ether , Polyoxyethylene alkyl (phenyl) ether sulfate or a salt thereof, polyoxyethylene alkyl (phenyl) ether phosphate or a salt thereof, protein material, alkenyl sulfosuccinic acid, α-olefin sulfonate, and the like.

  (7) Other surfactants: aliphatic monohydric alcohols having 6 to 30 carbon atoms in the molecule such as octadecyl alcohol and stearyl alcohol, and 6 to 30 carbon atoms in the molecule such as abiethyl alcohol Molecule such as monocyclic mercaptan having 6 to 30 carbon atoms in the molecule such as alicyclic monohydric alcohol, dodecyl mercaptan, alkylphenol having 6 to 30 carbon atoms in the molecule such as nonylphenol, dodecylamine, etc. 10 moles or more of an alkylene oxide such as ethylene oxide or propylene oxide is added to an amine having 6 to 30 carbon atoms in the molecule, or a carboxylic acid having 6 to 30 carbon atoms in the molecule such as lauric acid or stearic acid. Polyalkylene oxide derivatives having alkyl or alkoxy groups Alkyl diphenyl ether sulfonates having two sulfone-containing phenyl groups that may be substituted as ether bonds; various anionic surfactants; various cationic interfaces such as alkylamine acetate and alkyltrimethylammonium chloride Activators; various nonionic surfactants; various amphoteric surfactants;

  (8) Waterproofing agent: fatty acid (salt), fatty acid ester, fats and oils, silicone, paraffin, asphalt, wax and the like.

  (9) Rust preventive: nitrite, phosphate, zinc oxide and the like.

  (10) Crack reducing agent: polyoxyalkyl ether and the like.

  (11) Expansion material: Ettlingite, coal, etc.

  Other conventionally known cement additives (materials) include cement wetting agents, thickeners, separation reducing agents, flocculants, drying shrinkage reducing agents, strength enhancers, self-leveling agents, rust preventives, colorants, anti-corrosion agents. Examples include mold agents. These conventionally known cement additives (materials) may be used alone or in combination of two or more.

  The present invention will be described more specifically with reference to the following examples, but the present invention is not limited thereto. In the examples, unless otherwise indicated, “%” means “% by weight” and “parts” means “parts by weight”. The numerical range shall include its end points.

  The lignocellulose hydrolysis waste liquid contains sugar, lignin, organic acid, oil, furan, ash and the like. Each component was measured under the measurement conditions shown below.

<Acid hydrolysis treatment liquid 1>
An absolute dry amount of 300 g of hardwood chips was placed in a 2.4 L volume autoclave, and water was added to adjust the liquid ratio to 3.2 L / kg. After hydrolysis at 170 ° C. for 30 minutes, the chip and the acid hydrolysis solution were separated with a 300 mesh filter cloth. Then, it concentrated so that it might become 20 weight% using a rotary evaporator, and the hydrolysis process liquid 1 was obtained.

<Acid hydrolysis treatment liquid 2>
300 g of softwood chips were put in a 2.4 L rotary autoclave and water was added to adjust the liquid ratio to 3.2 L / kg. After hydrolysis at 170 ° C. for 30 minutes, the chip and the acid hydrolysis solution were separated with a 300 mesh filter cloth. Then, it concentrated so that it might become 20 weight% using a rotary evaporator, and the hydrolysis process liquid 2 was obtained.

Examples 1-3, Comparative Examples 1-2
The fine aggregate, cement, water blended as shown in Table 1 and the acid hydrolysis treatment liquid (dispersing agent) shown in Table 2 were added, and the mortar flow and setting time in which the mortar was prepared by mechanical kneading with a mortar mixer were evaluated. . The above-mentioned mortar is filled in a hollow cylindrical mini slump cone with a bottom diameter of 20 cm, a top diameter of 10 cm and a height of 30 cm, and the average value of the two directions of the mortar diameter spread on the table when the mini slump cone is lifted vertically Was the mortar flow value. The smaller the amount added and the larger the mortar flow value, the better the performance of the dispersant. The mortar using each dispersing agent was tested by using an AE agent and an antifoaming agent and adjusting the air amount. The results are shown in Table 2.

  As for the setting time, mortar was poured into a container covered with a heat insulating material, and the change with time of the mortar temperature was examined using a time-dependent temperature measuring device, and the maximum temperature arrival time was defined as the setting time of the mortar. In general, the faster the setting time, the better.

普通ポルトランドセメント（宇部三菱セメント株式会社製、比重３．１６）
普通ポルトランドセメント（太平洋セメント株式会社製、比重３．１６）
普通ポルトランドセメント（株式会社トクヤマ製、比重３．１６）
水道水
陸砂：静岡県掛川産陸砂（細骨材、比重２．５９）
分散剤（固形分換算） 表２参照

Normal Portland cement (Mitsubishi Ube, Ltd., specific gravity 3.16)
Ordinary Portland cement (manufactured by Taiheiyo Cement Co., Ltd., specific gravity 3.16)
Normal Portland cement (Made by Tokuyama Co., Ltd., specific gravity 3.16)
Tap water Land sand: Land sand from Kakegawa, Shizuoka Prefecture (fine aggregate, specific gravity 2.59)
Dispersant (solid content conversion) See Table 2

※リグニンスルホン酸系セメント分散剤：日本製紙株式会社製、商品名：サンフローＲＨ
※※グルコン酸ナトリウム系セメント分散剤： 扶桑化学工業株式会社製、商品名：Ｃ−ＰＡＲＮ

* Lignin sulfonic acid cement dispersant: Nippon Paper Industries Co., Ltd., trade name: Sunflow RH
** Sodium gluconate cement dispersant: Fuso Chemical Industry Co., Ltd., trade name: C-PARN

<Examples 4 to 6, Comparative Example 3>
The fine aggregate, cement, water blended as shown in Table 3 and the dispersing agent shown in Table 4 were added, and the mortar flow and setting time in which the mortar was prepared by mechanical kneading with a mortar mixer were evaluated. The results are shown in Table 4.

セメント、陸砂は上記の物を使用。分散剤は表４を参照。

Use the above cement and land sand. See Table 4 for dispersants.

※重合体Ａは特開２０００−２３９５９５にて実施例１記載の重合体使用
※※重合体Ｂは特開２０１１−０５７４５９にて記載のＡ−１使用
※※※ナフタレンスルホン酸はナフタレンスルホン酸ホルムアルデヒド縮合物系分散剤（ （株）フローリック（製商品名フローリックＰＳ ））

* Polymer A uses the polymer described in Example 1 in JP2000-239595. * Polymer B uses A-1 described in JP2011-057459. ** Naphthalenesulfonic acid is formaldehyde naphthalenesulfonic acid. Condensate-based dispersant (Floric Co., Ltd. (trade name Floric PS))

Claims (6)

  In a dispersant composition containing an acid hydrolysis treatment liquid of lignocellulose material, the acid hydrolysis treatment liquid acid-treats lignocellulose material in hot water at a temperature of 130 to 190 ° C. for 30 to 400 minutes. Dispersant characterized by being obtained. The dispersant according to claim 1, comprising at least one compound selected from the following (A) to (C).
(A) Carboxyl group and / or salt-containing compound (B) Compound having acid group and polyalkylene glycol chain (C) Sulfonic acid group and / or salt-containing polymer compound   It is a dispersing agent for inorganic substances, The dispersing agent in any one of Claims 1-2 characterized by the above-mentioned.   It is a dispersing agent for organic substances, The dispersing agent in any one of Claims 1-2 characterized by the above-mentioned.   It is a dispersing agent for cement, The dispersing agent in any one of Claims 1-2 characterized by the above-mentioned.   A dispersion composition comprising the dispersant according to any one of claims 1 to 5, a dispersant, and a dispersion medium.