CN105731870A - Grinding aid used for cement and preparation method thereof - Google Patents

Grinding aid used for cement and preparation method thereof Download PDF

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Publication number
CN105731870A
CN105731870A CN201610033550.2A CN201610033550A CN105731870A CN 105731870 A CN105731870 A CN 105731870A CN 201610033550 A CN201610033550 A CN 201610033550A CN 105731870 A CN105731870 A CN 105731870A
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sodium
cement
grinding aid
lubricant
parts
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不公告发明人
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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039Premixtures of ingredients
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/52Grinding aids; Additives added during grinding

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

The invention discloses a grinding aid used for cement. The grinding aid is prepared from the following raw materials in parts by weight: 0.1-0.15 part of ethylenediamine tetra(methylenephosphonic acid) sodium salt, 12-14 parts of molasses, 4.8-6.6 parts of sodium thiosulfate, 5.6-8.3 parts of sodium hexametaphosphate, 1.8-3.4 parts of aminotrimethylenephosphonic acid sodium salt, 7-13 parts of waste industrial lubricating oil, 15-19 parts of sodium dodecylbenzene sulfonate, 0.65-0.95 part of alpha-olefin sodium sulfonate, 4.6-6.5 parts of sorbitol, 17-20 parts of diethylene glycol, 0.06-0.42 part of dibutyl phthalate, 0.25-0.5 part of trioctyl trimellitate, 0.06-0.11 part of chlorinated paraffin, 0.16-0.32 part of dioctyl phthalate, 0.06-0.08 part of a silicone lubricant, 0.07-0.09 part of a fluorine-containing lubricant, and 0.08-0.18 part of Tween-80. The grinding aid used for cement further has the excellent effects that: the formula design is simple, and the production steps are simplified; and the produced grinding aid used for cement is good in grinding aid effect, is good in reinforcing effect, and can completely meet the market requirement.

Description

A kind of grinding aid for cement and preparation method
Technical field
The present invention relates to building material technical field, particularly relate to a kind of grinding aid for cement and preparation method.
Background technology
Cement grinding is one important procedure in manufacture of cement, and it is by clinker and retarder by mechanical means With the material grinding such as performance adjustment material to suitable granularity, to meet cement slurry and condense, hardening requirement.In powder-grinding process In, material particles is progressively refined by equipment fine grinding, and specific surface area increases, and its surface is charged because of chemical bond rupture, grain Son mutually absorption can form caking or sticky on abrasive body and liner plate, makes mill efficiency decline, adds the consumption of the energy. Research shows, adds chemical agent and can improve process of lapping, improve grinding efficiency or capacity usage ratio in process of lapping, this Class chemical agent is called grinding aid.
China was once utilizing spent pulping liquor, coal etc. to make grinding aid at the beginning of the 50's of 20th century, 20 century 70s, Bu Shaoqi Industry and R&D institution have extensively carried out the research work about grinding aid.20th century the mid-80, building materials institute and Tianjin of country First lightization be proposed N series and S series cement grinding aid.During material is by grinding, when grain diameter is reduced to After micron order, quality is in uniformly, defect reduces, intensity and hardness increase, and grindability deteriorates;Meanwhile, because of specific surface area and table Face can significantly increase, and subparticle mutual conglomeration aggregation tendency is remarkably reinforced.If not taking certain technological measure, Jiu Huiyin Play mill efficiency decline, per unit area yield power consumption by significantly raised.After especially China implements cement new-standard, intensity index and fineness are wanted Asking and all increase, this just makes grinding aid more cause the concern of vast cement production enterprise.
According to final form, grinding aid can be divided into;Solid, liquids and gases grinding aid.Solid grinding aid has: stearic acid Salt, silica sol, aquadag, white carbon black, flyash, Gypsum Fibrosum etc.;Liquid helps mushroom agent to have: organosilicon, triethanolamine, second Glycol, propylene glycol, polyacrylate, polycarboxylate etc.;Gas grinding aid has: the polar substances of vaporous and nonpolar property thing Matter etc..Can be divided three classes by chemical constitution grinding aid: polymer-inorganic salt, polymerization organic salt and complex chemical compound.Domestic mostly Using technical pure polymerization organic salt and inorganic salt is the main component of grinding aid, relatively costly, and technical-economic index is inadaptable real The border condition of production, product adaptation face is narrower.
Application publication number CN 102643043 A(application number 201210098400.1) Chinese invention patent document public Open a kind of cement grinding aid, including the component of following weight portion: water 55-65%;Sodium nitrite 10-12%;Nacl 8- 10%;Wood calcium 3-5%;Sodium acetate 3-5%;Triethanolamine 5-8%;Ethylene glycol 3-5%.Application publication number CN 103693880 A(application number 201310705192.1) Chinese invention patent document disclose a kind of cement grinding aid, including ethylene glycol, have Machine ammonium salt and water, be also added into diethylene glycol 5-10 part, soda 5-15 part, alkyl polyglycoside 5-10 part, cystine 10-15 part.Shen Please publication No. CN 104446114 A(application number 201410658029.9) Chinese invention patent document disclose a kind of cement Grinding aid, is made up of the component of following weight proportion: diethanol monoisopropanolamine 10-15 part, triethanolamine 3-5 part, sodium acetate 4-6 part, sodium thiosulfate 6-10 part, sodium chloride 10-12 part, hydroxyethyl cellulose 6-8 part, black liquid 15-18 part.
Existing grinding aid cost is high, volume is big, and mill efficiency is low, and cement performance improves undesirable, needs the most excellent Change.
Summary of the invention
For the deficiencies in the prior art, it is an object of the invention to provide a kind of one preparing simple, scientific formulation for The grinding aid of cement and preparation method, this grinding aid cost of manufacture is low, grinding aid function admirable.
The technical scheme is that
A kind of grinding aid for cement, is prepared from by following raw materials according, is weight portion: ethylene diamine tetra methylene phosphonic acid sodium 0.1- 0.15;Molasses 12-14;Sodium thiosulfate 4.8-6.6;Sodium hexameta phosphate 5.6-8.3;ATMP sodium 1.8-3.4;Useless Industrial lubricant 7-13;Dodecylbenzene sodium sulfonate 15-19;α-sodium olefin sulfonate 0.65-0.95;Sorbitol 4.6-6.5;Diethyl Glycol 17-20;Dibutyl phthalate 0.06-0.42;Trioctyl trimellitate (TOTM) 0.25-0.5;Chlorinated paraffin 0.06-0.11; Dioctyl phthalate 0.16-0.32;Silicone lubricant 0.06-0.08;Fluorinated lubricant 0.07-0.09;Live in surface Property agent tween 80 0.08-0.18.
Preferably in scheme, ethylene diamine tetra methylene phosphonic acid sodium 0.12-0.13;Molasses 12.5-13.5;Sodium thiosulfate 5.4- 6.0;Sodium hexameta phosphate 6.6-7.3;ATMP sodium 2.3-2.9;Useless industrial lubricant 9-11;DBSA Sodium 16-18;α-sodium olefin sulfonate 0.75-0.85;Sorbitol 5.2-5.9;Diethylene glycol 18-19;Dibutyl phthalate 0.16-0.32;Trioctyl trimellitate (TOTM) 0.35-0.4;Chlorinated paraffin 0.08-0.09;Dioctyl phthalate 0.2-0.28; Silicone lubricant 0.065-0.075;Fluorinated lubricant 0.075-0.085;Surface active agent tween-80 0.1-0.16.
More preferably, ethylene diamine tetra methylene phosphonic acid sodium 0.125;Molasses 13;Sodium thiosulfate 5.7;Sodium hexameta phosphate 7; ATMP sodium 2.6;Useless industrial lubricant 10;Dodecylbenzene sodium sulfonate 17;α-sodium olefin sulfonate 0.8;Sorbitol 5.5;Diethylene glycol 18.5;Dibutyl phthalate 0.24;Trioctyl trimellitate (TOTM) 0.38;Chlorinated paraffin 0.085;Adjacent benzene two Formic acid dioctyl ester 0.24;Silicone lubricant 0.07;Fluorinated lubricant 0.08;Surface active agent tween-80 0.13.
A kind of preparation method of the grinding aid for cement, step is as follows:
(1) α-sodium olefin sulfonate, dodecylbenzene sodium sulfonate, ATMP sodium and diethylene glycol are together joined instead Answer in still, add the deionized water of 1.2-1.8 times of described material quantity, be heated to 60-78 DEG C (being preferably heated to 66-72 DEG C), stir Mixing 0.8-2 hour, then add sodium hexameta phosphate, sorbitol and sodium thiosulfate in reactor, 40-60min(is preferred in stirring Stirring 45-55min), it is cooled to 30-46 DEG C (being preferably cooled to 34-42 DEG C), is stirred for 35-65min(and is preferably stirred for 45- 55min), obtain mixed solution A, standby;
(2) pouring in reactor by ethylene diamine tetra methylene phosphonic acid sodium, the deionized water adding 1.3-1.5 times amount (is preferably added to The deionized water of 1.35-1.45 times amount), stirring and dissolving, it is to slowly warm up to 80-88 DEG C (being preferably to slowly warm up to 82-86 DEG C), adds Enter chlorinated paraffin, molasses and useless industrial lubricant, stir, constant temperature 0.5-0.8 hour (preferably constant temperature 0.6-0.7 hour), Then stand and be cooled to 60 DEG C-74 DEG C, be sequentially added into dibutyl phthalate, dioctyl phthalate, tri trimellitate Monooctyl ester and surface active agent tween-80, constant temperature is refined 3-5 hour (preferably constant temperature is refined 3.5-4.5 hour), is obtained emulsion;
(3) step (2) gained emulsion is cooled to 25-45 DEG C (being preferably cooled to 30-40 DEG C), add silicone lubricant and Fluorinated lubricant is combined 35-65min(and is preferably combined 45-55min), obtain mixed solution B, standby;
(4) step (1) gained mixed solution A is joined in step (3) gained mixed solution B, mix homogeneously, regulate pH value PH value is preferably regulated for 7.6-8.8 for 7.2-9.2(), to obtain final product.
The preparation method of above-mentioned a kind of grinding aid for cement, preferred scheme is, adds 1.3-1.7 in step (1) The deionized water (being preferably added to the deionized water of 1.5 times of described material quantities) of the most described material quantity.
The preparation method of above-mentioned a kind of grinding aid for cement, preferred scheme is, stirring 1.2-1.6 in step (1) Hour (preferably stirring 1.4 hours).
The preparation method of above-mentioned a kind of grinding aid for cement, preferred scheme is, step (2) is cooled to 64 DEG C- 70 DEG C (being preferably cooled to 67 DEG C).
The preparation method of above-mentioned a kind of grinding aid for cement, preferred scheme is, silicone described in step (3) moistens Lubrication prescription is silicone powder.
The preparation method of above-mentioned a kind of grinding aid for cement, preferred scheme is, fluorinated described in step (3) moistens Lubrication prescription is perfluoro polyether oil.
Above-mentioned a kind of grinding aid for cement, preferred scheme is that the consumption of grinding aid accounts for the 0.01%-of cement total amount The consumption of the preferred grinding aid of 0.03%(accounts for the 0.015%-0.025% of cement total amount, and the consumption of grinding aid more preferably accounts for water The 0.02% of mud total amount).
A kind of grinding aid compatibility science for cement of gained of the present invention, preparation technology is the most efficient.In addition, this Bright excellent results is also manifested by:
1, gained grinding aid of the present invention is by non-useless industrial lubricant recycling, greatly reduces the production cost of product, carries The high utilization rate of resource;
2, gained grinding aid of the present invention is remarkably improved cement quality and performance, and its addition content is only the 0.01%-of cement consumption 0.03%, it is remarkably improved the anti-folding of cement early anaphase, comprcssive strength;
3, gained grinding aid of the present invention, it is possible to increase the grinding fineness of cement, especially adds and intensity plays enhancement effect Granule content in the range of 3-30 μm;
4, inventive formulation designs simple, production stage simplification, and the cement grinding aid grinding-aid effect of production is good, reinforced effects is good, It is entirely capable of meeting the market demand.
Detailed description of the invention
Describe technical scheme in detail below in conjunction with embodiment and test example, but protection domain is not limited to this.
Embodiment 1 one kinds, for the grinding aid of cement, is prepared from by following raw materials according, is weight portion (3.5kg/ part): 0.15 part of ethylene diamine tetra methylene phosphonic acid sodium;14 parts of molasses;6.6 parts of sodium thiosulfate;Sodium hexameta phosphate 8.3 parts;Amino three methene Alendronate 3.4 parts;Useless industrial lubricant 13 parts;Dodecylbenzene sodium sulfonate 19 parts;α-sodium olefin sulfonate 0.95 part;Sorbitol 6.5 part;Diethylene glycol 20 parts;Dibutyl phthalate 0.42 part;Trioctyl trimellitate (TOTM) 0.5 part;Chlorinated paraffin 0.11 part; Dioctyl phthalate 0.32 part;Silicone lubricant 0.08 part;Fluorinated lubricant 0.09 part;Surface active agent tween- 80 0.18 parts.
A kind of preparation method for the grinding aid of cement is:
(1) α-sodium olefin sulfonate, dodecylbenzene sodium sulfonate, ATMP sodium and diethylene glycol are together joined instead Answer in still, add the deionized water of 1.2 times of described material quantities, be heated to 60 DEG C, stir 0.8 hour, then add in reactor Enter sodium hexameta phosphate, sorbitol and sodium thiosulfate, stir 40min, be cooled to 30 DEG C, be stirred for 35min, obtain mixed solution A, Standby;
(2) ethylene diamine tetra methylene phosphonic acid sodium is poured in reactor, add the deionized water of 1.3 times amount, stirring and dissolving, slowly rise Temperature, to 80 DEG C, adds chlorinated paraffin, molasses and useless industrial lubricant, stirs, constant temperature 0.5 hour, then stands and is cooled to 60 DEG C, it is sequentially added into dibutyl phthalate, dioctyl phthalate, trioctyl trimellitate (TOTM) and surfactant and tells Temperature-80, constant temperature is refined 3 hours, is obtained emulsion;
(3) step (2) gained emulsion is cooled to 25 DEG C, adds silicone lubricant (silicone powder) and fluorinated lubricant (perfluoro polyether oil) is combined 35min, obtains mixed solution B, standby;
(4) step (1) gained mixed solution A is joined in step (3) gained mixed solution B, mix homogeneously, regulate pH value It is 7.2, to obtain final product.
Embodiment 2 one kinds, for the grinding aid of cement, is prepared from by following raw materials according, is weight portion (1.5kg/ part): 0.15 part of ethylene diamine tetra methylene phosphonic acid sodium;14 parts of molasses;6.6 parts of sodium thiosulfate;Sodium hexameta phosphate 8.3 parts;Amino three methene Alendronate 3.4 parts;Useless industrial lubricant 13 parts;Dodecylbenzene sodium sulfonate 19 parts;α-sodium olefin sulfonate 0.95 part;Sorbitol 6.5 part;Diethylene glycol 20 parts;Dibutyl phthalate 0.42 part;Trioctyl trimellitate (TOTM) 0.5 part;Chlorinated paraffin 0.11 part; Dioctyl phthalate 0.32 part;Silicone lubricant 0.08 part;Fluorinated lubricant 0.09 part;Surface active agent tween- 80 0.18 parts.
A kind of preparation method for the grinding aid of cement is:
(1) α-sodium olefin sulfonate, dodecylbenzene sodium sulfonate, ATMP sodium and diethylene glycol are together joined instead Answer in still, add the deionized water of 1.8 times of described material quantities, be heated to 78 DEG C, stir 2 hours, then add in reactor Sodium hexameta phosphate, sorbitol and sodium thiosulfate, stir 60min, be cooled to 46 DEG C, be stirred for 65min, obtain mixed solution A, standby With;
(2) ethylene diamine tetra methylene phosphonic acid sodium is poured in reactor, add the deionized water of 1.5 times amount, stirring and dissolving, slowly rise Temperature, to 88 DEG C, adds chlorinated paraffin, molasses and useless industrial lubricant, stirs, constant temperature 0.8 hour, then stands and is cooled to 74 DEG C, it is sequentially added into dibutyl phthalate, dioctyl phthalate, trioctyl trimellitate (TOTM) and surfactant and tells Temperature-80, constant temperature is refined 5 hours, is obtained emulsion;
(3) step (2) gained emulsion is cooled to 45 DEG C, adds silicone lubricant (silicone powder) and fluorinated lubricant (perfluoro polyether oil) is combined 65min, obtains mixed solution B, standby;
(4) step (1) gained mixed solution A is joined in step (3) gained mixed solution B, mix homogeneously, regulate pH value It is 9.2, to obtain final product.
Embodiment 3 one kinds, for the grinding aid of cement, is prepared from by following raw materials according, is weight portion (3kg/ part): second Diamidogen four methene Alendronate 0.12 part;12.5 parts of molasses;5.4 parts of sodium thiosulfate;Sodium hexameta phosphate 6.6 parts;Amino three methene Alendronate 2.3 parts;Useless industrial lubricant 9 parts;Dodecylbenzene sodium sulfonate 16 parts;α-sodium olefin sulfonate 0.75 part;Sorbitol 5.2 Part;Diethylene glycol 18 parts;Dibutyl phthalate 0.16 part;Trioctyl trimellitate (TOTM) 0.35 part;Chlorinated paraffin 0.08 part;Adjacent Dioctyl phthalate 0.2 part;Silicone lubricant 0.065 part;Fluorinated lubricant 0.075 part;Surface active agent tween-80 0.1 part.
A kind of preparation method for the grinding aid of cement is:
(1) α-sodium olefin sulfonate, dodecylbenzene sodium sulfonate, ATMP sodium and diethylene glycol are together joined instead Answer in still, add the deionized water of 1.3 times of described material quantities, be heated to 66 DEG C, stir 1.2 hours, then add in reactor Enter sodium hexameta phosphate, sorbitol and sodium thiosulfate, stir 45min, be cooled to 34 DEG C, be stirred for 45min, obtain mixed solution A, Standby;
(2) ethylene diamine tetra methylene phosphonic acid sodium is poured in reactor, add the deionized water of 1.35 times amount, stirring and dissolving, slowly It is warming up to 82 DEG C, adds chlorinated paraffin, molasses and useless industrial lubricant, stir, constant temperature 0.6 hour, then stand cooling To 64 DEG C, it is sequentially added into dibutyl phthalate, dioctyl phthalate, trioctyl trimellitate (TOTM) and surfactant and tells Temperature-80, constant temperature is refined 3.5 hours, is obtained emulsion;
(3) step (2) gained emulsion is cooled to 30 DEG C, adds silicone lubricant (silicone powder) and fluorinated lubricant (perfluoro polyether oil) is combined 45min, obtains mixed solution B, standby;
(4) step (1) gained mixed solution A is joined in step (3) gained mixed solution B, mix homogeneously, regulate pH value It is 7.6, to obtain final product.
Embodiment 4 one kinds, for the grinding aid of cement, is prepared from by following raw materials according, is weight portion (2kg/ part): second Diamidogen four methene Alendronate 0.13 part;13.5 parts of molasses;6.0 parts of sodium thiosulfate;Sodium hexameta phosphate 7.3 parts;Amino three methene Alendronate 2.9 parts;Useless industrial lubricant 11 parts;Dodecylbenzene sodium sulfonate 18 parts;α-sodium olefin sulfonate 0.85 part;Sorbitol 5.9 part;Diethylene glycol 19 parts;Dibutyl phthalate 0.32 part;Trioctyl trimellitate (TOTM) 0.4 part;Chlorinated paraffin 0.09 part; Dioctyl phthalate 0.28 part;Silicone lubricant 0.075 part;Fluorinated lubricant 0.085 part;Surfactant is told Temperature-80 0.16 parts.
A kind of preparation method for the grinding aid of cement is:
(1) α-sodium olefin sulfonate, dodecylbenzene sodium sulfonate, ATMP sodium and diethylene glycol are together joined instead Answer in still, add the deionized water of 1.7 times of described material quantities, be heated to 72 DEG C, stir 1.6 hours, then add in reactor Enter sodium hexameta phosphate, sorbitol and sodium thiosulfate, stir 55min, be cooled to 42 DEG C, be stirred for 55min, obtain mixed solution A, Standby;
(2) ethylene diamine tetra methylene phosphonic acid sodium is poured in reactor, add the deionized water of 1.45 times amount, stirring and dissolving, slowly It is warming up to 86 DEG C, adds chlorinated paraffin, molasses and useless industrial lubricant, stir, constant temperature 0.7 hour, then stand cooling To 70 DEG C, it is sequentially added into dibutyl phthalate, dioctyl phthalate, trioctyl trimellitate (TOTM) and surfactant and tells Temperature-80, constant temperature is refined 4.5 hours, is obtained emulsion;
(3) step (2) gained emulsion is cooled to 40 DEG C, adds silicone lubricant (silicone powder) and fluorinated lubricant (perfluoro polyether oil) is combined 55min, obtains mixed solution B, standby;
(4) step (1) gained mixed solution A is joined in step (3) gained mixed solution B, mix homogeneously, regulate pH value It is 8.8, to obtain final product.
Embodiment 5 one kinds, for the grinding aid of cement, is prepared from by following raw materials according, is weight portion (2.5kg/ part): 0.125 part of ethylene diamine tetra methylene phosphonic acid sodium;13 parts of molasses;5.7 parts of sodium thiosulfate;Sodium hexameta phosphate 7 parts;Amino three methene phosphine 2.6 parts of sodium of acid;Useless industrial lubricant 10 parts;Dodecylbenzene sodium sulfonate 17 parts;α-sodium olefin sulfonate 0.8 part;Sorbitol 5.5 Part;Diethylene glycol 18.5 parts;Dibutyl phthalate 0.24 part;Trioctyl trimellitate (TOTM) 0.38 part;Chlorinated paraffin 0.085 Part;Dioctyl phthalate 0.24 part;Silicone lubricant 0.07 part;Fluorinated lubricant 0.08 part;Surfactant is told Temperature-80 0.13 parts.
A kind of preparation method for the grinding aid of cement is:
(1) α-sodium olefin sulfonate, dodecylbenzene sodium sulfonate, ATMP sodium and diethylene glycol are together joined instead Answer in still, add the deionized water of 1.5 times of described material quantities, be heated to 69 DEG C, stir 1.4 hours, then add in reactor Enter sodium hexameta phosphate, sorbitol and sodium thiosulfate, stir 50min, be cooled to 38 DEG C, be stirred for 50min, obtain mixed solution A, Standby;
(2) ethylene diamine tetra methylene phosphonic acid sodium is poured in reactor, add the deionized water of 1.4 times amount, stirring and dissolving, slowly rise Temperature, to 84 DEG C, adds chlorinated paraffin, molasses and useless industrial lubricant, stirs, constant temperature 0.65 hour, then stands and is cooled to 67 DEG C, it is sequentially added into dibutyl phthalate, dioctyl phthalate, trioctyl trimellitate (TOTM) and surfactant and tells Temperature-80, constant temperature is refined 4 hours, is obtained emulsion;
(3) step (2) gained emulsion is cooled to 35 DEG C, adds silicone lubricant (silicone powder) and fluorinated lubricant (perfluoro polyether oil) is combined 50min, obtains mixed solution B, standby;
(4) step (1) gained mixed solution A is joined in step (3) gained mixed solution B, mix homogeneously, regulate pH value It is 8.2, to obtain final product.
Ethylene diamine tetra methylene phosphonic acid sodium: character: yellowish-brown transparency liquid.Ethylene diamine tetra methylene phosphonic acid sodium is nitrogenous organic many Unit's phosphonic acids, belongs to cathode type corrosion inhibiter, compared with inorganic polyphosphate, corrosion inhibition rate height 3-5 times.Water-miscible, nontoxic pollution-free, Chemical stability and temperature tolerance are good, still have good scale inhibition effect at 200 DEG C.EDTMPS can be dissociated into 8 in aqueous Negative ions, thus multiple netted complex of monomer structure macromole can be formed with multiple metal ion-chelants, loosely divide Dissipate in water, make calcium dirt normal crystallization be destroyed.EDTMPS is good to the scale inhibition effect of calcium sulfate, barium sulfate scale.
ATMP sodium: ATMP sodium is synthesized by two steps: the first step: ammonium chloride and water are mixed, Stirring, to dissolving, then adds formalin, is warming up to 55 DEG C, is slowly added dropwise tri-chlorination with constant pressure funnel under room temperature Phosphorus, time for adding is 40-60min, stablizes 10min after dropping, is then to slowly warm up to reflux state, and 1-1.5 is little in backflow Time, separated, purify after, prepare ATMP;Second step: the ATMP that the first step is prepared and hydrogen-oxygen Change sodium to occur to neutralize reaction, prepare ATMP sodium (ATMP five sodium-salt).Property use: be mainly used in Boiler water process, oil field reinjection water system, industry and municipal cleansing water process and the corrosion inhibition for metal of cold water process.Can be as logical With type low cost antisludging agent, zinc salt and phosphate being had preferable corrosion inhibition, chelating ability is preferable.
Dodecylbenzene sodium sulfonate: be called for short SDBS, white or faint yellow powdery or chip solid.Difficult volatilization, soluble in water, It is dissolved in water and forms translucent solution.To alkali, diluted acid, hard water stable chemical nature.Application: dodecylbenzene sodium sulfonate is that one changes In kind emulsion, the various surface tension constituted between phase, are allowed to be formed the material of uniform and stable dispersion or emulsion. Being conventional anionic surfactant, have good surface activity, hydrophilic is relatively strong, effectively reduces oil-water interface Tension force, reaches emulsification.Therefore dodecylbenzene sodium sulfonate is in emulsion preparations such as cosmetics, food, printing and dyeing assistant, pesticide In obtain wide application.
α-sodium olefin sulfonate: α-sodium olefin sulfonate (AOS) is a kind of anion surfactant, in finite concentration scope In, the surface tension of water can be down to about 30-40mN.m-1 from 72mN.m-1 by AOS.It has excellent foam performance, anti-hard Outlet capacity and biodegradability.Have extensively at textile and dyeing industry, petrochemical and the aspect such as tertiary oil recovery, industry cleaning link General application.AOS can be as concrete density modifier, foamed wallboard, fire-fighting foam.Be alternatively arranged as farm chemical emulgent, Wetting agent etc..
Diethylene glycol: for colourless or pale yellow oily liquid body.Freezing point-6.5 DEG C, relative density 1.1164(20/4 DEG C), Index of refraction 1.4475.Can be miscible with ethanol, ether, acetone and ethylene glycol, insoluble in benzene and carbon tetrachloride, it is dissolved in water.Acrid in the mouth is peppery And micro-sweet, there is hygroscopicity.It is mainly used as solvent, such as the solvent of cellulose nitrate, rubber, resin, oils and fats, paint, family's medicine etc., also may be used Make the plasticizer of resin, Nicotiana tabacum L. antidesiccant, fiber lubricant and the desiccant etc. of natural gas.
Dibutyl phthalate: character: for colourless oil liquid, flammable, there is aromatic odor.Vapour pressure 1.58kPa/ 200℃;Flash-point 172 DEG C;Fusing point-35 DEG C;Boiling point 340 DEG C;Dissolubility: dissolubility 0.04%(25 DEG C in water).Be soluble in ethanol, Ether, acetone and benzene.Dibutyl phthalate is the plasticizer that polrvinyl chloride is the most frequently used, and goods can be made to have good softness Property.Dibutyl phthalate is the fine plasticizer of NC Nitroncellulose, and gelatinisation ability is strong, for NC Nitroncellulose coating, There is good emollescence.Stability, resistance to deflection, cohesiveness and water proofing property are superior to other plasticizers;Additionally, also be used as Polyvinyl acetate, alkyd resin, NC Nitroncellulose, ethyl cellulose and neoprene, the plasticizer of nitrile rubber.
Trioctyl trimellitate (TOTM): character: transparent oily liquid, density (20 DEG C) 0.988, refractive power (n20D) 1.485, boiling Point (1 mmHg) 258 DEG C, fusing point: 46 DEG C.This product is a kind of heat-resisting and durable primary plasticizer, has polyester plasticizer concurrently and monomer increases The advantage moulding agent, intermiscibility, processability, low temperature properties are also excellent compared with polyester plasticizer.Electrical property is excellent.It is mainly used in 105 DEG C of levels Heatproof wire CABLE MATERIALS and other require the goods such as heat-resisting and the sheet material of durability, sheet material, sealing gasket.This product is also applicable to chlorine Ethylene copolymer, celluloid, ethyl cellulose, the multiple plastics such as polymethyl methacrylate.
Chlorinated paraffin: chlorinated paraffin (selecting chlorinated paraffin 42) is light yellow viscous liquid.Freezing point-30 DEG C, the closeest Spend 1.16(25/25 DEG C), water insoluble, it is dissolved in organic solvent and various mineral oil.Purposes: be applicable to various product fire-retardant it With.It is widely used in the industrial circles such as plastics, rubber, fiber and makees the surface conditioning agent of plasticizer, fabric and packaging material, bonding Material and the antiwear additive of the modifying agent of coating, high-tension lubrication and metal cutting process, antifungus agent, waterproofing agent, easer etc..
Dioctyl phthalate: character: colourless transparent liquid, proportion 0.9861(20/20), fusing point-50 DEG C, boiling point 386 DEG C (normal pressure), water insoluble, it is dissolved in most of organic solvents such as ethanol, ether, mineral oil.DOP is universal plasticizer, It is mainly used in adding of the high polymers such as the processing of polrvinyl chloride fat, can be additionally used in ground resin, acetate resin, ABS resin and rubber Work it can also be used to make paint, dyestuff, dispersant etc., the PVC of DOP plasticising can be used for manufacturer's fabricate-leather, agricultural film, packaging material, Cable etc..
Fluorinated lubricant: containing the syntholube of fluorine element.Most important have: perfluorocarbon, chloro-fluorocarbon and perfluor are poly- Ether oil.Also have fluorosilicon oil, fluorine-containing three, fluorine-containing nitrile, fluorinated ester and fluorine bromine oil etc..Feature: in perfluorocarbon and fluorochlorocarbon oil, due to The elecrtonegativity that fluorine (chlorine) atom in molecule is strong, C-F bond energy is higher than c h bond energy, and C-F, C-CL key is in the state of oxidation and C-H Key is in reducing condition, thus they there is prominent stability, anti-deep-etching, anti-Strong oxdiative, greasy property are good and decompose temperature Degree advantages of higher.
The performance study of a kind of grinding aid for cement of test example gained of the present invention (embodiment 5):
1, test raw material and method
Raw material: grog and Gypsum Fibrosum (purchasing in Xing Baixing commerce and trade at sunshine company limited);A kind of helping for cement of gained of the present invention Grinding agent A;Cement grinding aid B(purchases in Laiwu film new material company limited).
This test is divided into three groups, experimental group, matched group and blank group.Its proportioning is grog: Gypsum Fibrosum=95:5.By ripe Material and Gypsum Fibrosum are broken for the material of 0.5-3mm, mixing respectively, are added by grinding aid in material, and wherein experimental group adds the present invention Gained grinding aid A(addition content is 0.02%), it is 0.04% that matched group adds grinding aid B(addition content), blank group is not spiked with grinding aid Agent;By the grinding 30min in test grinding machine of the material after admixture grinding aid, after grinding, after 0.08mm sieve crossed by material, respectively Carry out mensuration and the cement performance test of powder characteristics.Wherein test the distribution of its particle diameter with LS-C (I) type laser particle analyzer. Result is as shown in table 1.Specific area measuring test basis GBT8074-2008 is measured, and uses angle of repose contour injection method to survey Fixed, strength of cement mortar is measured according to GBT17671-1999.Result is as shown in table 2.
2, result of the test and analysis
Table 1 cement powder particle size distribution
Substantially diminish, wherein from the data in table 1, it can be seen that filled the most blank group of cement powder mean particle size after grinding aid Experimental group mean particle size is significantly less than matched group, makes the mean diameter of cement be reduced to 18.1 μm by 26.9 μm, it is seen that to help Mill effect is fairly obvious;The 3-30 μm particle diameter in experimental group played a major role cement character, content is notable compared with matched group Increase, improve 18.1%, be indicated above the grinding that a kind of grinding aid for cement of gained of the present invention significantly improves cement thin Degree, improves the distribution of particles of cement.
The impact of the different Grinding Aids On Cement Properties of table 2
From the data in table 2, it can be seen that the cement specific surface area adding grinding aid all increases relative to the cement not filling grinding aid; Experimental group and matched group cement screen over-size are below blank group, and experimental group screen over-size reduces by 38.7% than matched group;Show this Bright gained grinding aid significantly reduces coarse grained content compared with matched group, hence it is evident that improve cement fineness effect;Angle of repose is used for Weigh and evaluate the mobility of powder body.Knowable to table 2 data, compared with blank group that is not added with grinding aid, after adding grinding aid Experimental group and matched group reduce 7.1 ° and 3.2 ° angle of repose respectively, and experimental group is significantly greater than matched group more by a small margin.Thus Visible, gained cement grinding aid of the present invention makes the mobility of cement be significantly improved, and changed dramatically between powder granule Contact angle and decrease frictional resistance.Cement is improve the most to some extent from intensity data, experimental group and matched group Early, later stage anti-folding/comprcssive strength, and experimental group is substantially better than matched group improving in strength of cement, and its reinforced effects ten is clearly demarcated Aobvious.
It should be pointed out that, the detailed description of the invention more representational example that is the present invention, it is clear that the skill of the present invention Art scheme is not limited to above-described embodiment, it is also possible to have many variations.Those of ordinary skill in the art, the most public with present invention institute What what that open or according to file written description was undoubted obtained, all it is considered as this patent scope of the claimed.

Claims (10)

1. the grinding aid for cement, it is characterised in that be prepared from by following raw materials according, be weight portion: ethylenediamine tetraacetic Methylenephosphonic acid sodium 0.1-0.15;Molasses 12-14;Sodium thiosulfate 4.8-6.6;Sodium hexameta phosphate 5.6-8.3;Amino three methene phosphine Acid sodium 1.8-3.4;Useless industrial lubricant 7-13;Dodecylbenzene sodium sulfonate 15-19;α-sodium olefin sulfonate 0.65-0.95;Pyrusussuriensis Alcohol 4.6-6.5;Diethylene glycol 17-20;Dibutyl phthalate 0.06-0.42;Trioctyl trimellitate (TOTM) 0.25-0.5;Chlorination Paraffin 0.06-0.11;Dioctyl phthalate 0.16-0.32;Silicone lubricant 0.06-0.08;Fluorinated lubricant 0.07-0.09;Surface active agent tween-80 0.08-0.18.
A kind of grinding aid for cement, it is characterised in that be prepared from by following raw materials according, all For weight portion: ethylene diamine tetra methylene phosphonic acid sodium 0.12-0.13;Molasses 12.5-13.5;Sodium thiosulfate 5.4-6.0;Hexa metaphosphoric acid Sodium 6.6-7.3;ATMP sodium 2.3-2.9;Useless industrial lubricant 9-11;Dodecylbenzene sodium sulfonate 16-18;α-alkene Base sodium sulfonate 0.75-0.85;Sorbitol 5.2-5.9;Diethylene glycol 18-19;Dibutyl phthalate 0.16-0.32;Benzene partially Three sour three monooctyl ester 0.35-0.4;Chlorinated paraffin 0.08-0.09;Dioctyl phthalate 0.2-0.28;Silicone lubricant 0.065-0.075;Fluorinated lubricant 0.075-0.085;Surface active agent tween-80 0.1-0.16.
A kind of grinding aid for cement, it is characterised in that be prepared from by following raw materials according, all For weight portion: ethylene diamine tetra methylene phosphonic acid sodium 0.125;Molasses 13;Sodium thiosulfate 5.7;Sodium hexameta phosphate 7;Amino three methene Alendronate 2.6;Useless industrial lubricant 10;Dodecylbenzene sodium sulfonate 17;α-sodium olefin sulfonate 0.8;Sorbitol 5.5;Diethyl two Alcohol 18.5;Dibutyl phthalate 0.24;Trioctyl trimellitate (TOTM) 0.38;Chlorinated paraffin 0.085;Dioctyl phthalate 0.24;Silicone lubricant 0.07;Fluorinated lubricant 0.08;Surface active agent tween-80 0.13.
4. the preparation method of a kind of grinding aid for cement as described in claim 1-3 is arbitrary, it is characterised in that step is such as Under:
(1) α-sodium olefin sulfonate, dodecylbenzene sodium sulfonate, ATMP sodium and diethylene glycol are together joined instead Answer in still, add the deionized water of 1.2-1.8 times of described material quantity, be heated to 60-78 DEG C (being preferably heated to 66-72 DEG C), stir Mixing 0.8-2 hour, then add sodium hexameta phosphate, sorbitol and sodium thiosulfate in reactor, 40-60min(is preferred in stirring Stirring 45-55min), it is cooled to 30-46 DEG C (being preferably cooled to 34-42 DEG C), is stirred for 35-65min(and is preferably stirred for 45- 55min), obtain mixed solution A, standby;
(2) pouring in reactor by ethylene diamine tetra methylene phosphonic acid sodium, the deionized water adding 1.3-1.5 times amount (is preferably added to The deionized water of 1.35-1.45 times amount), stirring and dissolving, it is to slowly warm up to 80-88 DEG C (being preferably to slowly warm up to 82-86 DEG C), adds Enter chlorinated paraffin, molasses and useless industrial lubricant, stir, constant temperature 0.5-0.8 hour (preferably constant temperature 0.6-0.7 hour), Then stand and be cooled to 60 DEG C-74 DEG C, be sequentially added into dibutyl phthalate, dioctyl phthalate, tri trimellitate Monooctyl ester and surface active agent tween-80, constant temperature is refined 3-5 hour (preferably constant temperature is refined 3.5-4.5 hour), is obtained emulsion;
(3) step (2) gained emulsion is cooled to 25-45 DEG C (being preferably cooled to 30-40 DEG C), add silicone lubricant and Fluorinated lubricant is combined 35-65min(and is preferably combined 45-55min), obtain mixed solution B, standby;
(4) step (1) gained mixed solution A is joined in step (3) gained mixed solution B, mix homogeneously, regulate pH value PH value is preferably regulated for 7.6-8.8 for 7.2-9.2(), to obtain final product.
The preparation method of a kind of grinding aid for cement the most according to claim 4, it is characterised in that in step (1) Add the deionized water (being preferably added to the deionized water of 1.5 times of described material quantities) of 1.3-1.7 times of described material quantity.
The preparation method of a kind of grinding aid for cement the most according to claim 4, it is characterised in that in step (1) Stir 1.2-1.6 hour (preferably stirring 1.4 hours).
The preparation method of a kind of grinding aid for cement the most according to claim 4, it is characterised in that in step (2) It is cooled to 64 DEG C-70 DEG C (being preferably cooled to 67 DEG C).
The preparation method of a kind of grinding aid for cement the most according to claim 4, it is characterised in that in step (3) Described silicone lubricant is silicone powder.
The preparation method of a kind of grinding aid for cement the most according to claim 4, it is characterised in that in step (3) Described fluorinated lubricant is perfluoro polyether oil.
A kind of grinding aid for cement the most according to claim 4, it is characterised in that the consumption of grinding aid accounts for cement The consumption of the preferred grinding aid of 0.01%-0.03%(of total amount accounts for the 0.015%-0.025% of cement total amount, grinding aid more preferably The consumption of agent accounts for the 0.02% of cement total amount).
CN201610033550.2A 2016-01-19 2016-01-19 Grinding aid used for cement and preparation method thereof Pending CN105731870A (en)

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CN101062845A (en) * 2007-04-30 2007-10-31 上海国冶工程技术有限公司 Industrial residue activating grinding aid
CN101618955A (en) * 2009-07-30 2010-01-06 葫芦岛市辽西混凝土外加剂有限公司 High efficiency cement composite grinding additive and preparation method thereof
CN101693605A (en) * 2009-10-12 2010-04-14 东阿东昌天汇科技有限公司 Composite high-efficient liquid cement grinding aid
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CN108821628A (en) * 2018-07-12 2018-11-16 北京人众创新工贸有限公司 A kind of no chlorine high-early (strength) cement grinding aid and preparation method thereof

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