CN109867467B - Retarding enhanced efficient grinding aid and preparation method thereof - Google Patents
Retarding enhanced efficient grinding aid and preparation method thereof Download PDFInfo
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- CN109867467B CN109867467B CN201910303042.5A CN201910303042A CN109867467B CN 109867467 B CN109867467 B CN 109867467B CN 201910303042 A CN201910303042 A CN 201910303042A CN 109867467 B CN109867467 B CN 109867467B
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Abstract
The application discloses a retarding enhanced high-efficiency grinding aid and a preparation method thereof, wherein the retarding enhanced high-efficiency grinding aid comprises zinc blende powder, copper oxide, ethylene glycol and mannan oligosaccharide; according to the mass, the using ratio of the zinc blende powder to the copper oxide to the glycol to the manno-oligosaccharide is 1: 0.09-0.11: 1.8-2.2: 0.45-0.55, and the method has the advantage of delaying the setting time of the cement paste.
Description
Technical Field
The invention relates to a retarding enhanced efficient grinding aid and a preparation method thereof.
Background
With the rapid development of the construction industry, the quality of cement is more and more important to be concerned by people. As is well known, the production of cement is largely divided into "two mills with one firing", i.e. the preparation of raw meal, the calcination of clinker and the grinding of cement, the importance of which in the cement production process is self evident. However, when the cement is ground to a certain fineness, the cement can be agglomerated, because the cement generates charges in the grinding process, and the positive charges and the negative charges on the surfaces of cement particles are attracted to each other, and the cement grinding aid can well avoid the phenomenon. The cement grinding aid has the effects of reducing the fineness of cement, improving the specific surface area, optimizing the particle composition of cement particles, reducing the power consumption of grinding, improving the yield and the like, and is widely used in the cement industry.
Chinese patent with publication number CN102372454B, publication date of 11 and 27 in 2013, discloses a cement grinding aid, which comprises 20-40 wt% of polyalcohol amine, 5-10 wt% of polyalcohol, 10-30 wt% of lignosulfonate and 20-65 wt% of water.
The defects of the prior art are that polyalcohol amine and polyalcohol can be mixed with cementAl of (2)3+Complexing, accelerating C3The formation of A ettringite and the crystal form conversion rate thereof consume a large amount of mixing water, have certain coagulation acceleration effect and obviously shorten the setting time of cement slurry.
Disclosure of Invention
The invention aims to provide a retarding and enhancing type high-efficiency grinding aid which has the advantage of delaying the setting time of cement paste.
The technical purpose of the invention is realized by the following technical scheme:
a retarding enhanced high-efficiency grinding aid, which comprises zinc blende powder, copper oxide, glycol and mannan-oligosaccharide; according to the mass, the using amount ratio of the zinc blende powder to the copper oxide to the glycol to the mannan oligosaccharide is 1: 0.09-0.11: 1.8-2.2: 0.45-0.55.
By adopting the technical scheme, when grinding, the ethylene glycol is adsorbed on the surface of the cement particles and among microcracks, so that the free energy on the surface of the cement particles can be reduced, the unsaturated charges generated after the Ca-O ionic bonds and the Si-O covalent bonds at the cracks are neutralized, and the Ca is prevented2+And O2-The method has the advantages that the fine particles are recombined, the dispersity of the fine particles is improved, the flowability of materials in a mill is improved, the grinding efficiency is improved, meanwhile, the sphalerite (sulfide minerals with chemical components of ZnS and crystal belonging to an isometric crystal system) powder and copper oxide enter broken crystal fracture positions to influence a system to enable the ground particles to be moderate, the problems of static electricity and the like caused by excessive refining are reduced, and researches show that more than 80% of the obtained particles are 3-30 mu m, so that the phenomenon is kept unchanged even if the grinding time is prolonged, the construction operation is facilitated, and the cement strength is increased. The combined use of the glycol and the mannanoligosaccharide ensures that a small amount of grinding aid can achieve the effect and is high in efficiency.
When the cement is hydrated, on one hand, Ca can be selectively absorbed by the surface of the sphalerite powder2+Activation centers that contribute to C-S-H formation and calcium hydroxide crystallization, accelerate C3S hydration, and on the other hand, Zn in zinc blende powder2+Dissolving out and increasing Zn in the solution2+With Ca in solution2+、SO4 2-Formation of sparingly soluble complex salts with reduced formation of complex saltsCa in solution2+And part of Ca is adsorbed on the surface of the sphalerite powder2+Thus Ca in solution2+In which case the formation of C-S-H and the crystallization of calcium hydroxide are delayed, delaying C3S hydration. The two aspects are mutually contradictory in the hydration process, copper oxide and mannanoligosaccharide are added into the formula, and the copper oxide and the mannanoligosaccharide are added on the surface of the sphalerite powder and Ca2+The bonding part of the zinc oxide forms a protective film, reduces the activation rate and accelerates Zn2+With Ca in solution2+、SO4 2-The process of forming the indissolvable composite salt is carried out, the composite salt is dispersed through the mannanoligosaccharide and the ethylene glycol, and the retarding enhancement type efficient grinding aid has a good retarding effect when the mass ratio of the retarding enhancement type efficient grinding aid to cement is 0.025-0.05 wt% to 1, so that the construction performance of the slurry is improved. In the hydration process, zinc blende powder, copper oxide and mannan-oligosaccharide enter the crystal along with ethylene glycol to fill and improve the strength of cement.
Preferably, the using amount ratio of the zinc blende powder, the copper oxide, the glycol and the manno-oligosaccharide is 1:0.10:2.0:0.50 by mass.
Preferably, the feed also comprises zeolite powder, D-sodium gluconate, catechin and vanadium pentoxide; according to the mass ratio of the zinc blende powder, the copper oxide, the ethylene glycol, the mannan oligosaccharide, the zeolite powder, the D-sodium gluconate, the catechin and the vanadium pentoxide is 1:0.10:2.0:0.50: 0.14-0.16: 0.05-0.07: 0.04-0.06: 0.02-0.04.
By adopting the technical scheme, the zeolite powder provides a reaction interface during grinding, and the catechin and the vanadium pentoxide can further neutralize unsaturated charges by combining, so that the flowability and high-flowability area of the powder are increased, and the grinding speed is accelerated; when cement is hydrated, D-sodium gluconate can play a certain retarding role, but the retarding effect is almost negligible if only D-sodium gluconate is additionally added or the combination proportion is not in the range of the application in the system of the application, but the retarding effect is obvious when the D-sodium gluconate and catechin act together.
Preferably, the using amount ratio of the zinc blende powder, the copper oxide, the glycol, the mannan oligosaccharide, the zeolite powder, the sodium D-gluconate, the catechin and the vanadium pentoxide is 1:0.10:2.0:0.50:0.15:0.06:0.05:0.03 by mass.
Preferably, the application mode of the retarding and enhancing type efficient grinding aid is as follows: adding the delayed coagulation enhanced high-efficiency grinding aid into cement, mixing and grinding; the mass ratio of the retarding reinforced efficient grinding aid to the cement is 0.025-0.05: 1.
The second purpose of the invention is to provide a preparation method of the retarding and reinforcing high-efficiency grinding aid.
A preparation method of a retarding enhanced efficient grinding aid comprises the following steps: adding zinc blende powder, copper oxide, ethylene glycol and mannan-oligosaccharide into water, stirring and dispersing uniformly, concentrating to remove the solvent, and crushing to obtain the zinc blende; according to the mass, the using amount ratio of the zinc blende powder to the copper oxide to the glycol to the mannan oligosaccharide is 1: 0.09-0.11: 1.8-2.2: 0.45-0.55.
Preferably, the method comprises the following steps: adding zinc blende powder, copper oxide, ethylene glycol, mannan-oligosaccharide, zeolite powder, D-sodium gluconate, catechin and vanadium pentoxide into water, stirring, dispersing, concentrating to remove solvent, and pulverizing; according to the mass ratio of the zinc blende powder, the copper oxide, the ethylene glycol, the mannan oligosaccharide, the zeolite powder, the D-sodium gluconate, the catechin and the vanadium pentoxide is 1:0.10:2.0:0.50: 0.14-0.16: 0.05-0.07: 0.04-0.06: 0.02-0.04.
The technical effects of the invention are mainly reflected in the following aspects: after the grinding aid is added for grinding, the fineness of cement is reduced, more than 80% of the cement falls into the range of 3-30 mu m, the fineness of the cement is rarely changed after grinding for a certain time, the controllability is good, the strength of the cement is enhanced, the hydration is delayed, a good retarding effect is achieved, and the construction performance of slurry is improved.
Detailed Description
Example 1: the retarding enhanced efficient grinding aid is prepared by the following method: adding zinc blende powder, copper oxide, ethylene glycol and mannooligosaccharide into water, stirring and dispersing uniformly, concentrating to remove the solvent, and crushing to obtain the zinc blende. In the preparation process, the water consumption is 3 times of the zinc blende powder by mass.
In the formula, the mass ratio of the zinc blende powder, the copper oxide, the glycol and the mannanoligosaccharide is 1:0.10:2.0: 0.50.
Example 2: the retarding and strengthening type efficient grinding aid is different from the grinding aid in example 1 in that in the formula, the mass ratio of zinc blende powder, copper oxide, glycol and mannan-oligosaccharide is 1:0.09:1.8: 0.45.
Example 3: the retarding and strengthening type efficient grinding aid is different from the grinding aid in example 1 in that in the formula, the mass ratio of zinc blende powder, copper oxide, glycol and mannan-oligosaccharide is 1:0.11:2.2: 0.55.
Example 4: the retarding enhanced efficient grinding aid is prepared by the following method: adding zinc blende powder, copper oxide, ethylene glycol, mannan-oligosaccharide, zeolite powder, D-sodium gluconate, catechin and vanadium pentoxide into water, stirring, dispersing, concentrating to remove solvent, and pulverizing. In the preparation process, the water consumption is 3 times of the zinc blende powder by mass.
In the formula, the mass ratio of zinc blende powder, copper oxide, glycol, mannan oligosaccharide, zeolite powder, D-sodium gluconate, catechin and vanadium pentoxide is 1:0.10:2.0:0.50:0.15:0.06:0.05: 0.03.
Example 5: the retarding and strengthening efficient grinding aid is different from the grinding aid in example 4 in that in the formula, the mass ratio of zinc blende powder, copper oxide, glycol, mannan oligosaccharide, zeolite powder, D-sodium gluconate, catechin and vanadium pentoxide is 1:0.10:2.0:0.50:0.14:0.05:0.04: 0.02.
Example 6: the retarding and strengthening efficient grinding aid is different from the grinding aid in example 4 in that in the formula, the mass ratio of zinc blende powder, copper oxide, glycol, mannan oligosaccharide, zeolite powder, D-sodium gluconate, catechin and vanadium pentoxide is 1:0.10:2.0:0.50:0.16:0.07:0.06: 0.04.
Example 7: the retarding and strengthening type efficient grinding aid is different from that in the embodiment 4 in that the mass ratio of zinc blende powder, copper oxide, glycol, mannan oligosaccharide, zeolite powder, D-sodium gluconate, catechin and vanadium pentoxide is 1:0.10:2.0:0.50:0.12:0.03:0.02: 0.01.
Example 8: the retarding and strengthening efficient grinding aid is different from the grinding aid in example 4 in that in the formula, the mass ratio of zinc blende powder, copper oxide, glycol, mannan oligosaccharide, zeolite powder, D-sodium gluconate, catechin and vanadium pentoxide is 1:0.10:2.0:0.50:0.18:0.09:0.08: 0.06.
Comparative example 1: a grinding aid, referred to CN102372454B, example 1, comprises the following components in percentage by weight: 15% of triethanolamine, 10% of triisopropanolamine, 8% of diethylene glycol, 20% of modified sodium lignosulfonate and 47% of water.
Comparative example 2: a grinding aid prepared by the following method: adding zinc blende powder, copper oxide and ethylene glycol into water, stirring, dispersing, concentrating to remove solvent, and pulverizing. In the preparation process, the water consumption is 3 times of the zinc blende powder by mass.
In the formula, the mass ratio of the zinc blende powder, the copper oxide and the ethylene glycol is 1:0.10: 2.0.
Comparative example 3: a grinding aid prepared by the following method: adding zinc blende powder, ethylene glycol and mannooligosaccharide into water, stirring and dispersing uniformly, concentrating to remove solvent, and pulverizing. In the preparation process, the water consumption is 3 times of the zinc blende powder by mass.
In the formula, the mass ratio of the zinc blende powder, the glycol and the mannanoligosaccharide is 1:2.0: 0.50.
Comparative example 4: a grinding aid prepared by the following method: adding zinc blende powder, copper oxide, ethylene glycol and mannooligosaccharide into water, stirring and dispersing uniformly, concentrating to remove the solvent, and crushing to obtain the zinc blende. In the preparation process, the water consumption is 3 times of the zinc blende powder by mass.
In the formula, the mass ratio of the zinc blende powder, the copper oxide, the glycol and the mannanoligosaccharide is 1:0.07:1.5: 0.40.
Comparative example 5: a grinding aid prepared by the following method: adding zinc blende powder, copper oxide, ethylene glycol and mannooligosaccharide into water, stirring and dispersing uniformly, concentrating to remove the solvent, and crushing to obtain the zinc blende. In the preparation process, the water consumption is 3 times of the zinc blende powder by mass.
In the formula, the mass ratio of the zinc blende powder, the copper oxide, the glycol and the mannanoligosaccharide is 1:0.13:2.5: 0.60.
Comparative example 6: a grinding aid which differs from example 1 in that the ethylene glycol is replaced by triethanolamine.
Performance testing
The cement of P.042.5 variety is used as a sample to be ground, a test group is added, the mixed material and pure cement material (blank group) are respectively put into a phi 500 x 500 test mill, the grinding is carried out for a period of time, the fineness is measured according to national standard, and the adding amount of the test group is respectively controlled to be 0.04wt% (adding amount) of the cement during testing. And (5) testing the physical properties of the sample after grinding for 30 minutes. The parallel test is carried out for 5 times, and the average value is taken. The test results are shown in tables 3 and 4.
Table 3 shows: compared with a blank group, the particles ground in the embodiments 1-8 are smaller and more intensively distributed in 3-30 μm, and the particle distribution is less changed after 30 minutes and 120 minutes of grinding, so that the method is suitable for industrial application (individual difference of grinding time exists); compared with a control group, the particle distribution of the powder ground in the embodiments 1-8 is more concentrated in 3-30 μm, the change of the distribution can be ignored even if the grinding time is prolonged, and meanwhile, the grinding speed is high and the efficiency is high.
Table 4 shows: compared with the blank group and the control group, the samples of examples 1 to 8 have higher flexural and compressive strength, slower initial setting and better retardation effect.
Table 1 compositions and proportions of cement materials of the P.042.5 variety
Table 2 main chemical composition and mass percentage of raw material of cement material of p.042.5 variety
TABLE 3 particle distribution after grinding (0.04 wt%)
TABLE 4 physical Properties measurement (0.04 wt% in addition)
The cement of P.042.5 variety is used as a sample to be ground, a test group is added, the mixed materials are respectively put into a phi 500 x 500 test mill, ground for 30 minutes, and tested for physical properties. When tested, the addition amounts of the test groups were respectively controlled to be 0.025, 0.04, 0.05 and 0.15wt% (addition amount) of the cement. The parallel test is carried out for 5 times, and the average value is taken. The test results are shown in table 5.
Table 5 shows: compared with the blank group, the strength of the examples 1 to 8 is higher and the retardation effect is good; the retardation effect and the strength are influenced by the doping amount, and the retardation effect is good when the doping amount of the examples 1 to 8 is 0.025wt% -0.05 wt%.
TABLE 5 physical Property measurements (different doping levels)
The above are only typical examples of the present invention, and besides, the present invention may have other embodiments, and all the technical solutions formed by equivalent substitutions or equivalent changes are within the scope of the present invention as claimed.
Claims (4)
1. A retarding enhanced high-efficiency grinding aid is characterized by comprising zinc blende powder, copper oxide, ethylene glycol, mannan oligosaccharide, zeolite powder, D-sodium gluconate, catechin and vanadium pentoxide; according to the mass ratio of the zinc blende powder, the copper oxide, the ethylene glycol, the mannan oligosaccharide, the zeolite powder, the D-sodium gluconate, the catechin and the vanadium pentoxide is 1:0.10:2.0:0.50: 0.14-0.16: 0.05-0.07: 0.04-0.06: 0.02-0.04.
2. The retarding and enhancing type efficient grinding aid as claimed in claim 1, which is characterized in that the usage ratio of zinc blende powder, copper oxide, ethylene glycol, mannan oligosaccharide, zeolite powder, D-sodium gluconate, catechin and vanadium pentoxide is 1:0.10:2.0:0.50:0.15:0.06:0.05:0.03 by mass.
3. The retarding and enhancing type high-efficiency grinding aid as claimed in claim 1 or 2, which is applied in the following manner: adding the delayed coagulation enhanced high-efficiency grinding aid into cement, mixing and grinding; the mass ratio of the retarding reinforced efficient grinding aid to the cement is 0.025-0.05% to 1.
4. A preparation method of a retarding enhanced efficient grinding aid is characterized by comprising the following steps: adding zinc blende powder, copper oxide, ethylene glycol, mannan-oligosaccharide, zeolite powder, D-sodium gluconate, catechin and vanadium pentoxide into water, stirring, dispersing, concentrating to remove solvent, and pulverizing; according to the mass ratio of the zinc blende powder, the copper oxide, the ethylene glycol, the mannan oligosaccharide, the zeolite powder, the D-sodium gluconate, the catechin and the vanadium pentoxide is 1:0.10:2.0:0.50: 0.14-0.16: 0.05-0.07: 0.04-0.06: 0.02-0.04.
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| KR100650175B1 (en) * | 2005-04-02 | 2006-11-27 | 케이지케미칼 주식회사 | Grinding aid for minuteness shatter of mineral |
| CN100434385C (en) * | 2005-11-11 | 2008-11-19 | 同济大学 | Method for consolidating heavy metal zinc of cement base material and suppressing its slow coagulation effect |
| CN102173632B (en) * | 2011-02-16 | 2013-01-02 | 蒋元海 | Composite plastic-retaining grinding aid for cement and use method |
| CN103755198A (en) * | 2013-12-20 | 2014-04-30 | 沈阳洪达信息科技有限公司 | Cement grinding enhancer |
| CN106277909A (en) * | 2016-08-19 | 2017-01-04 | 桂林华越环保科技有限公司 | Concrete retarder |
| US20200055775A1 (en) * | 2017-02-13 | 2020-02-20 | Gcp Applied Technologies Inc. | Early strength enhancement of cements |
| CN109321204A (en) * | 2018-10-24 | 2019-02-12 | 河南省力量钻石股份有限公司 | A kind of more particle agglomeration type abrasive grain bodies, preparation method and applications |
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