CN103274632A - Reinforced cement grinding aid and preparation method thereof - Google Patents
Reinforced cement grinding aid and preparation method thereof Download PDFInfo
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- CN103274632A CN103274632A CN2013101950702A CN201310195070A CN103274632A CN 103274632 A CN103274632 A CN 103274632A CN 2013101950702 A CN2013101950702 A CN 2013101950702A CN 201310195070 A CN201310195070 A CN 201310195070A CN 103274632 A CN103274632 A CN 103274632A
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- grinding aid
- cement grinding
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- cement
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- 239000004568 cement Substances 0.000 title claims abstract description 98
- 238000000227 grinding Methods 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims abstract description 35
- 238000002156 mixing Methods 0.000 claims abstract description 31
- 229940006186 sodium polystyrene sulfonate Drugs 0.000 claims abstract description 31
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000004793 Polystyrene Substances 0.000 claims abstract description 19
- 229920002223 polystyrene Polymers 0.000 claims abstract description 19
- 239000002699 waste material Substances 0.000 claims abstract description 14
- 150000001720 carbohydrates Chemical class 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 229920003023 plastic Polymers 0.000 claims abstract description 10
- 239000004033 plastic Substances 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- 239000013530 defoamer Substances 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical group O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 6
- 238000006277 sulfonation reaction Methods 0.000 claims description 6
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 5
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 5
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 5
- 239000004567 concrete Substances 0.000 claims description 5
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 4
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 4
- 229930006000 Sucrose Natural products 0.000 claims description 4
- 240000008042 Zea mays Species 0.000 claims description 4
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 claims description 4
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 4
- 235000009973 maize Nutrition 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 3
- 235000013379 molasses Nutrition 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical group C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 239000000174 gluconic acid Substances 0.000 claims description 2
- 235000012208 gluconic acid Nutrition 0.000 claims description 2
- 150000002301 glucosamine derivatives Chemical class 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims description 2
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 17
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 abstract description 6
- 239000012744 reinforcing agent Substances 0.000 abstract description 5
- 239000002351 wastewater Substances 0.000 abstract description 5
- 239000003638 chemical reducing agent Substances 0.000 abstract description 4
- 239000011398 Portland cement Substances 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 3
- 239000002270 dispersing agent Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000003014 reinforcing effect Effects 0.000 abstract description 3
- 239000002518 antifoaming agent Substances 0.000 abstract 2
- 239000011259 mixed solution Substances 0.000 abstract 2
- 150000005846 sugar alcohols Polymers 0.000 abstract 2
- 229920002521 macromolecule Polymers 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- 239000011850 water-based material Substances 0.000 abstract 1
- 239000010881 fly ash Substances 0.000 description 18
- 239000011401 Portland-fly ash cement Substances 0.000 description 17
- 230000000694 effects Effects 0.000 description 16
- 238000004519 manufacturing process Methods 0.000 description 11
- 239000002893 slag Substances 0.000 description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 6
- 239000004202 carbamide Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- 229960004418 trolamine Drugs 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000010883 coal ash Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000010440 gypsum Substances 0.000 description 3
- 229910052602 gypsum Inorganic materials 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 229920001732 Lignosulfonate Polymers 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000002956 ash Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 235000019357 lignosulphonate Nutrition 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920006327 polystyrene foam Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 239000012745 toughening agent Substances 0.000 description 2
- -1 vitriol Chemical compound 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000004021 humic acid Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000013074 reference sample Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000003469 silicate cement Substances 0.000 description 1
- XDNDXYZWMMAEPS-UHFFFAOYSA-N silver sulfuric acid Chemical compound [Ag].OS(O)(=O)=O XDNDXYZWMMAEPS-UHFFFAOYSA-N 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- SOBHUZYZLFQYFK-UHFFFAOYSA-K trisodium;hydroxy-[[phosphonatomethyl(phosphonomethyl)amino]methyl]phosphinate Chemical compound [Na+].[Na+].[Na+].OP(O)(=O)CN(CP(O)([O-])=O)CP([O-])([O-])=O SOBHUZYZLFQYFK-UHFFFAOYSA-K 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
Abstract
The invention relates to a reinforced cement grinding aid and a preparation method thereof. The reinforced cement grinding aid is characterized by comprising the following materials in parts by weight: 20-65 parts of mixed solution of sodium polystyrene sulfonate (SPS) and aluminum sulfate, 5-25 parts of alkanolamine, 5-20 parts of polyhydric alcohol, 3-15 parts of saccharides, 0.1-1 part of antifoaming agent and 15-45 parts of water. The reinforced cement grinding aid is prepared by mixing and stirring the mixed solution, alkanolamine, polyhydric alcohol, saccharides, an antifoaming agent and water. Preferably, the sodium polystyrene sulfonate (SPS) is prepared by taking waste polystyrene as the raw material, serves as a long-chain linear macromolecule water-based material and is a surface active agent and a cement dispersing agent as well as an early strength agent and a water reducing agent; the aluminum sulfate is an effective reinforcing agent of Portland cement; and the prepared reinforced cement grinding aid has good grinding aid and reinforcing effects, and the cost is lower than that of the conventional triethanolamine cement grinding aid. According to the method, waste polystyrene plastics are recycled, and no waste acid, waste water and waste residue are discharged. Therefore, the method is environment-friendly and low in cost.
Description
Technical field
The invention belongs to the cement grinding technical field, relate to a kind of enhanced cement grinding aid and preparation method thereof, relate in particular in the cement that with flyash is main blended material (with flyash be the composite Portland cement P.C of main blended material as Portland fly ash cement P.F and part) grinding is produced, can reduce the cement grinding power consumption, improve cement and reach a kind of cement grinding aid reinforcing agent of later strength and preparation method thereof in early days.
Background technology
In manufacture of cement, in order to improve mill efficiency, reduce the grinding machine power consumption, improve cement quality, in grinding process, usually add a small amount of grinding aid.Cement grinding aid be conducive to reduce material in the grinding process surface energy, eliminate static between the material micro powder granule, improve the flowability of material in the mill, thereby improve mill efficiency, improve the cement granules grating.
In recent years, along with the rise of coal price, the production cost of cement clinker increases severely, and blended material is cheap, cement production enterprise all attempts to reduce by the addition content of raising blended material in cement proportion the usage quantity of cement clinker, thereby reduces the comprehensive production cost of ton cement.Blended material mainly comprises blast-furnace slag, flyash, slag, natural volcanic ash, slag, Wingdale etc., wherein based on blast-furnace slag and flyash.Traditional cement grinding aid or toughener mostly are by composite forming such as trolamine and various villaumite, urea, and villaumite and urea have the effect that improves strength of cement.For example, application number is that 200510047822.6 Chinese patent has been reported a kind of multifunctional cement grinding aid, is made up of flyash, sodium-chlor, trolamine, water glass, zinc ore stone flour, benzene first trisodium, gypsum, Diethylene Glycol.Because cement grinding aid of the prior art is directly by trolamine with villaumite is composite forms, being adapted to mix slag is during main cement grinding is produced, and it is not obvious to the pulverized fuel ash cement reinforced effects, and, this cement grinding aid makes and introduces a large amount of chlorions in the cement, thereby make cement in use cause the corrosion of reinforcing bar, it is unfavorable that the buildings life-span is produced.Slag most of area has at home become rare starting material, and price is far above flyash.If increase flyash proportioning in cement grinding, easily cause the obviously increase of standard consistency water requirement, cement early strength and the later strength of cement to descend obviously.Therefore, the market requirement is a kind of can effectively to improve cement grinding efficient, improves the early stage enhanced cement grinding aid that reaches later strength of the cement of a large amount of adding coal ashes simultaneously.
Application number is that 200910034779.8 Chinese patent literature has been reported a kind of chlorine-free powdery cement grinding aid that is applicable to flyash and preparation method thereof, be the mixture of alkanolamine, polyvalent alcohol, vitriol, acetate, sulfonated lignin, carbohydrate organism, bassanite, urea, inorganic carrier material, the weight ratio of this mixture is: 2 parts of alkanolamines, 3.5 parts of polyvalent alcohols, 37.5 parts in vitriol, 12 parts of acetate, 1 part of sulfonated lignin, 4 parts of carbohydrate organism, 15 parts of bassanite, 10 parts in urea, 15 parts of inorganic carrier materials.This grinding aid contains urea, and is powder body material, and consumption is higher, and incorporation is 0.5%, is unfavorable for using on a large scale in the manufacture of cement.
Application number is the preparation method that 201010585447.1 Chinese patent literature has been reported a kind of enhancement type water of coal ash cement grinding aids, comprise: be catalyzer with the vitriol oil, with alcamine compound such as trolamine or tri-isopropanolamine, react down at 130～140 ℃ with organic acid, obtain organic ammonium salt; The type water of coal ash cement grinding aids that is enhanced is stirred in described organic ammonium salt, water, Sodium salts humic acids, wooden calcium and Sodium Nitrite mixing.This invention is to be main raw material with the alcamine compound, and production cost is higher.
In addition, prior art and research mostly adopt traditional cement grinding aid component such as trolamine, urea etc. as the enhanced type grinding aids of Portland fly ash cement, DeGrain in the practical application, and production cost is higher.
Summary of the invention
Technical problem to be solved by this invention provides a kind of enhanced cement grinding aid, this cement grinding aid reinforcing agent is the composite Portland cement of main blended material for Portland fly ash cement with flyash, have better grinding aid and reinforced effects, production cost further reduces.The present invention provides the preparation method of above-mentioned enhanced cement grinding aid simultaneously.
Technical scheme of the present invention is: a kind of enhanced cement grinding aid is characterized in that its feed composition and the shared weight part of each component are respectively: sodium polystyrene sulfonate is called for short mixing solutions 20～65 weight parts, alkanolamine 5～25 weight parts, polyvalent alcohol 5～20 weight parts, carbohydrate 3～15 weight parts, defoamer 0.1～1 weight part, water 15～45 weight parts of SPS and Tai-Ace S 150; Wherein the mass concentration of the mixing solutions of SPS and Tai-Ace S 150 is that the mass ratio of 20%～50%, SPS and Tai-Ace S 150 is 1:(2～5).Mixing solutions 25～55 weight parts, alkanolamine 5～20 weight parts, polyvalent alcohol 5～15 weight parts, carbohydrate 5～10 weight parts, defoamer 0.2～0.5 weight part, water 20～40 weight parts of preferred SPS and Tai-Ace S 150.
The mixing solutions of preferred described SPS and Tai-Ace S 150 is prepared by following method: be sulphonating agent with the vitriol oil, waste polystyrene plastic is dissolved in the organic solvent in advance, and sulfonation reaction makes sulfonated polystyrene under catalyst action; Add water and stir the back and separate organic solvent and reclaim standbyly, with in waste alumina or the low taste aluminium vanadine and superfluous sulfuric acid and impurity screening, again with NaOH solution and sulfonated polystyrene reaction generation sodium polystyrene sulfonate, get the mixing solutions of SPS and Tai-Ace S 150 then.The massfraction of the preferred above-mentioned vitriol oil is 95～97%, the mass ratio 2:1～10:1 of the described vitriol oil and deposed polystyrene; Described organic solvent is hexanaphthene or 1,2-ethylene dichloride, and the mass ratio of described organic solvent and deposed polystyrene is 2:1～10:1; Described catalyzer is Vanadium Pentoxide in FLAKES or Sulfuric acid disilver salt, and the mass ratio of catalyzer and deposed polystyrene is 0.5%～2%; Described NaOH solution quality concentration is 20%～50%.Preferred sulfonation reaction temperature is 40～80 ℃; The sulfonation reaction time is 2～8 hours.
Preferred described alkanolamine is at least di-alcohol monoisopropanolamine (DEIPA), N, N, N', the mixing of any one or a few in N'-four (2-hydroxyethyl) quadrol (THEEA) or the N methyldiethanol amine (MEDA).Preferred described polyvalent alcohol is in the aliphatic dibasic alcohol of C2～C5 or the trivalent alcohol, as any one or a few the mixing in propylene glycol, glycerol, ethylene glycol or the Diethylene Glycol.Preferred described carbohydrate organism is at least at least a or several mixing in molasses, maize treacle, glucose, sucrose, gluconic acid or the glucosamine salt.Preferred described defoamer be at least in tributyl phosphate (TNBP) or the three iso-butyl ester of phosphoric acid (TIBP) a kind of.
The present invention also provides the method for preparing above-mentioned enhanced cement grinding aid, and its concrete steps are: mixing solutions, water, alkanolamine, polyvalent alcohol, carbohydrate, the defoamer of SPS and Tai-Ace S 150 are mixed in proportion, stir, get the enhanced cement grinding aid.
Enhanced cement grinding aid its incorporation in use is 0.05%～0.15% of cement weight, preferably adopts volume pump to add on the mill cement material.This enhanced cement grinding aid can effectively improve the intensity of silicate cement in grinding aid.
Polystyrene foamed plastics (PS) is called polystyrene foamed again, because having advantages such as easy-formation, price is low, use properties is good, it is widely used in new packaging material, building material which can retain moisture, acousticing heat-insulating material etc., but the polystyrene foamed plastics after using goes out of use in a large number, adds that it is difficult to degrade voluntarily and has caused well-known " white pollution ".Phenyl ring has greater activity in the polystyrene molecule, can be by chemical modification other functional group that induces one in the phenyl ring, as sulfonic group, carboxylic acid group, hydroxyl etc., it is transformed into has the functional macromolecular material of purpose, as as water treatment auxiliary agent, sizing agent, or catalytic pyrolysis prepares styrene monomer, fuel etc.The aqueous high molecular material is because application performance excellence, widespread use in the cement concrete industry in recent years.After waste polystyrene foam plastic is sulphur-modified, can prepare cement water reducing agent and oil well cement additive etc.
Most critical is separating and processing of remaining sulfuric acid and waste water in the method for sulfonating of polystyrene and the technology, the prior art employing is separated or adopts calcium hydroxide, calcium oxide or lime neutralization to remove for the calcium sulfate after-filtration, pollute greatlyyer, intractability is high and influence its technology and use and promote.Compared with prior art, low, pollution-free, the no spent acid waste water and dregs discharging of cost of the present invention.The present invention with deposed polystyrene and strong sulfuric acid response after, at first with the superfluous sulfuric acid of neutralization such as waste alumina or low-grade aluminium vanadine, obtain Tai-Ace S 150, this is known cement early strength agent; Then with the NaOH neutralization, obtain the mixing solutions of sodium polystyrene sulfonate (SPS) and Tai-Ace S 150, sodium polystyrene sulfonate (SPS) is known cement dispersants and water reducer; Mixing solutions with sodium polystyrene sulfonate (SPS) and Tai-Ace S 150 mixes with water, alkanolamine, polyvalent alcohol, carbohydrate, defoamer etc. again, prepares the enhanced cement grinding aid.Employed waste alumina or cheap being easy to get of low-grade aluminium vanadine.Production technique among the present invention does not need to consider the processing of residual sulfuric acid and waste water, but is translated into effective cement early strength agent-Tai-Ace S 150; In addition, the mixing solutions with sodium polystyrene sulfonate (SPS) and Tai-Ace S 150 also is what not appear in the newspapers as cement grinding aid reinforcing agent.
Beneficial effect:
Raw material of the present invention is based on waste polystyrene foam plastic, and sufficient and cheap, pollution-free, the no spent acid waste water and dregs in source discharges, thereby enhanced cement grinding aid provided by the invention has a good application prospect.The present invention is that the sodium polystyrene sulfonate (SPS) of feedstock production is long-chain linear polymer waterborne material with the polystyrene, is a kind of tensio-active agent and cement dispersants, is again hardening accelerator and water reducer; Tai-Ace S 150 is effective toughener of Portland fly ash cement; Its mixing solutions has good reinforced effects to Portland fly ash cement, and, the preparation method of the enhanced cement grinding aid that is used for Portland fly ash cement of the present invention's preparation is chloride ion-containing not, thereby can not make cement in use cause the corrosion of reinforcing bar.Simultaneously, the grinding aid of the cement grinding aid reinforcing agent that is used for Portland fly ash cement of the present invention's preparation is functional, cost is lower, can increase substantially cement output and cement early strength, satisfy national standard to the requirement of cement products and cement grinding aid, concrete weather resistance is had no adverse effect.Experimental result shows, the enhanced cement grinding aid of the present invention's preparation is that volume is 0.1% o'clock in 30% the Portland fly ash cement at doping quantity of fly ash, and 3d/28d ultimate compression strength has improved 4.2Mpa and 6.8Mpa than reference sample respectively.The enhanced cement grinding aid of the present invention's preparation is applicable to various cement, especially Portland fly ash cement is had tangible reinforced effects.
Embodiment
Below the technical scheme in the embodiment of the invention is carried out clear, complete description, obviously, described embodiment only is a part of embodiment of the present invention, rather than whole embodiment; According to following embodiment, the present invention may be better understood.Yet, those skilled in the art will readily understand that the described concrete material proportion of embodiment, processing condition and result thereof only are used for explanation the present invention, and should also can not limit the present invention described in detail in claims.Based on the embodiment among the present invention, those of ordinary skills belong to the scope of protection of the invention not making all other embodiment that obtain under any creative work prerequisite.
In order to further specify technical scheme of the present invention, be described below in conjunction with the preferred embodiment of the invention of embodiment, but should be appreciated that these describe the just feature and advantage for further specifying, rather than to the restriction of claim of the present invention.
Embodiment 1:
10 weight part polystyrene foamed plasticss are dissolved in the 30 weight part organic solvent epoxy hexanes in advance, the catalyzer Vanadium Pentoxide in FLAKES that adds 0.05 weight part, the vitriol oil of 20 weight parts 95% is added dropwise to reactor, after adding 50 weight parts waters after 4 hours, reaction under 60 ℃ stirs and isolates the epoxy hexane, use in the waste alumina again and remaining sulfuric acid, remove by filter impurity and unreacted waste alumina, the NaOH solution with 20% is adjusted solution pH value 7, obtains the mixing solutions of SPS and Tai-Ace S 150;
Get mixing solutions 26 weight parts of above-mentioned SPS and Tai-Ace S 150, add water 28.5 weight parts, di-alcohol monoisopropanolamine (DEIPA) 20 weight parts, ethylene glycol 5 weight parts, Diethylene Glycol 10 weight parts, molasses 10 weight parts, the mixing of tributyl phosphate 0.5 weight part successively, stir the type that is enhanced cement grinding aid.
Be the enhanced cement grinding aid that adds 0.05% present embodiment preparation in 30% the Portland fly ash cement at doping quantity of fly ash, it carried out reinforced effects measure that measurement result is as shown in table 1.
Embodiment 2:
10 weight part polystyrene foamed plasticss are dissolved in 100 weight part organic solvents 1 in advance, in the 2-ethylene dichloride, the catalyst sulfuric acid silver that adds 0.2 weight part, the vitriol oil of 25 weight parts 97% is added dropwise to reactor, after 40 ℃ down reaction added 65 weight parts waters after 8 hours, stirs and isolate 1, the 2-ethylene dichloride, use in the aluminium vanadine again and remaining sulfuric acid, remove by filter impurity and unreacted aluminium vanadine, the NaOH solution with 40% is adjusted solution pH value 7, obtains the mixing solutions of SPS and Tai-Ace S 150;
Get mixing solutions 52.5 weight parts of above-mentioned SPS and Tai-Ace S 150, add water 20.2 weight parts, N successively, N, N', N'-four (2-hydroxyethyl) quadrol (THEEA) 3 weight parts, di-alcohol monoisopropanolamine (DEIPA) 7 weight parts, Diethylene Glycol 7 weight parts, maize treacle 5 weight parts, sucrose 5 weight parts, three iso-butyl ester of phosphoric acid 0.3 weight part mix, stir the type that is enhanced cement grinding aid.
Be the enhanced cement grinding aid that adds 0.05% present embodiment preparation in 30% the Portland fly ash cement at doping quantity of fly ash, it carried out reinforced effects measure that measurement result is as shown in table 1.
Embodiment 3:
Get the prepared SPS of embodiment 2 and mixing solutions 45 weight parts of Tai-Ace S 150, add water 30 weight parts, N successively, N, N', N'-four (2-hydroxyethyl) quadrol (THEEA) 5 weight parts, methyldiethanolamine (MEDA) 2.5 weight parts, propylene glycol 5 weight parts, Diethylene Glycol 5 weight parts, sucrose 5 weight parts, Sunmorl N 60S 2.3 weight parts, tributyl phosphate 0.2 weight part mix, stir the type that is enhanced cement grinding aid.
Be the enhanced cement grinding aid that adds 0.1% present embodiment preparation in 30% the Portland fly ash cement at doping quantity of fly ash, it carried out reinforced effects measure that measurement result is as shown in table 1.
Embodiment 4:
Get the prepared SPS of embodiment 2 and mixing solutions 44.8 weight parts of Tai-Ace S 150, add water 35 weight parts, di-alcohol monoisopropanolamine (DEIPA) 1 weight part, N successively, N, N', N'-four (2-hydroxyethyl) quadrol (THEEA) 3 weight parts, methyldiethanolamine (MEDA) 1 weight part, ethylene glycol 5 weight parts, maize treacle 10 weight parts, three iso-butyl ester of phosphoric acid 0.2 weight part mix, and stir the type that is enhanced cement grinding aid.
Be the enhanced cement grinding aid that adds 0.15% present embodiment preparation in 30% the Portland fly ash cement at doping quantity of fly ash, it carried out reinforced effects measure that measurement result is as shown in table 1.
Comparative example 1
Be that 30% Portland fly ash cement carries out strength detection to doping quantity of fly ash, the result is as shown in table 1.
Comparative example 2
Be to add the powder grinding aid that 0.5% application number is embodiment 6 in 200910034779.8 the Chinese patent literature in 30% the Portland fly ash cement at doping quantity of fly ash, measure its reinforced effects, measurement result is as shown in table 1.
Table 1 doping quantity of fly ash is the reinforced effects of 30% enhanced cement grinding aid
From above-described embodiment and comparative example as can be seen, the enhanced cement grinding aid for Portland fly ash cement provided by the invention is chloride ion-containing not, and production cost is low, has better reinforced effects, and especially later strength is promoted more obvious.
Grinding-aid effect compares:
Proportional arrangement cement according to grog 55%, flyash 30%, slag 6%, Wingdale 5%, gypsum 4%.Earlier cement clinker and gypsum are crushed to below the 5mm with jaw crusher, mix with other blended material in proportion then; Mix the grinding aid of various dose respectively, grinding after 25 minutes in the experiment mill is measured 45um and the 80um screen over-size of cement sample behind the grinding respectively, as table 2.From table embodiment and comparative example as can be seen, the enhanced cement grinding aid for Portland fly ash cement provided by the invention has grinding-aid effect preferably.
The grinding-aid effect of the grinding aid component of the different volumes of table 2 and kind relatively
To the above-mentioned explanation of the disclosed embodiments, make this area professional and technical personnel can realize or use the present invention.Multiple modification to these embodiment will be apparent concerning those skilled in the art, and will be defined generally away from realizing in other embodiments under the situation that does not break away from the spirit or scope of the present invention herein.Therefore, the present invention will can not be restricted to these embodiment shown in this article, but will meet the wideest scope consistent with principle disclosed herein and features of novelty.
Claims (10)
1. an enhanced cement grinding aid is characterized in that its feed composition and the shared weight part of each component are respectively: mixing solutions 20～65 weight parts, alkanolamine 5～25 weight parts, polyvalent alcohol 5～20 weight parts, carbohydrate 3～15 weight parts, defoamer 0.1～1 weight part, water 15～45 weight parts of sodium polystyrene sulfonate abbreviation SPS and Tai-Ace S 150; Wherein the mass concentration of the mixing solutions of SPS and Tai-Ace S 150 is that the mass ratio of 20%～50%, SPS and Tai-Ace S 150 is 1:(2～5).
2. enhanced cement grinding aid according to claim 1 is characterized in that its feed composition and the shared weight part of each component are respectively: mixing solutions 25～55 weight parts of SPS and Tai-Ace S 150, alkanolamine 5～20 weight parts, polyvalent alcohol 5～15 weight parts, carbohydrate 5～10 weight parts, defoamer 0.2～0.5 weight part, water 20～40 weight parts.
3. enhanced cement grinding aid according to claim 1, the mixing solutions that it is characterized in that described SPS and Tai-Ace S 150 is prepared by following method: be sulphonating agent with the vitriol oil, waste polystyrene plastic is dissolved in the organic solvent in advance, and sulfonation reaction makes sulfonated polystyrene under catalyst action; Add water and stir the back and separate organic solvent and reclaim standbyly, with in waste alumina or the low taste aluminium vanadine and superfluous sulfuric acid and impurity screening, again with NaOH solution and sulfonated polystyrene reaction generation sodium polystyrene sulfonate, get the mixing solutions of SPS and Tai-Ace S 150 then.
4. enhanced cement grinding aid according to claim 3 is characterized in that, the massfraction of the described vitriol oil is 95～97%, the mass ratio 2:1～10:1 of the described vitriol oil and deposed polystyrene; Described organic solvent is hexanaphthene or 1,2-ethylene dichloride, and the mass ratio of described organic solvent and deposed polystyrene is 2:1～10:1; Described catalyzer is Vanadium Pentoxide in FLAKES or Sulfuric acid disilver salt, and the mass ratio of catalyzer and deposed polystyrene is 0.5%～2%; Described NaOH solution quality concentration is 20%～50%.
5. enhanced cement grinding aid according to claim 3 is characterized in that, the sulfonation reaction temperature is 40～80 ℃; The sulfonation reaction time is 2～8 hours.
6. enhanced cement grinding aid according to claim 1 is characterized in that, described alkanolamine is at least di-alcohol monoisopropanolamine, N, N, N', the mixing of any one or a few in N'-four (2-hydroxyethyl) quadrol or the N methyldiethanol amine.
7. enhanced cement grinding aid according to claim 1 is characterized in that, described polyvalent alcohol is any one or a few the mixing in propylene glycol, glycerol, ethylene glycol or the Diethylene Glycol.
8. enhanced cement grinding aid according to claim 1 is characterized in that, described carbohydrate organism is at least at least a or several mixing in molasses, maize treacle, glucose, sucrose, gluconic acid or the glucosamine salt.
9. enhanced cement grinding aid according to claim 1 is characterized in that, described defoamer be at least in tributyl phosphate or the three iso-butyl ester of phosphoric acid a kind of.
10. method for preparing enhanced cement grinding aid as claimed in claim 1, its concrete steps are: mixing solutions, water, alkanolamine, polyvalent alcohol, carbohydrate, the defoamer of SPS and Tai-Ace S 150 are mixed in proportion, stir, get the enhanced cement grinding aid.
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| CN109748535B (en) * | 2019-03-29 | 2021-05-28 | 日照弗尔曼新材料科技有限公司 | Cement grinding aid and preparation method thereof |
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Application publication date: 20130904 Assignee: HUBEI XINTONGLING VIENTIANE TECHNOLOGY CO.,LTD. Assignor: Nanjing University of Technology Contract record no.: 2015420000128 Denomination of invention: Reinforced type cement grinding aid and preparation method thereof Granted publication date: 20150218 License type: Exclusive License Record date: 20150707 |
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