CN110218017A - A kind of new modified cement grinding aid and preparation method thereof - Google Patents
A kind of new modified cement grinding aid and preparation method thereof Download PDFInfo
- Publication number
- CN110218017A CN110218017A CN201910456959.9A CN201910456959A CN110218017A CN 110218017 A CN110218017 A CN 110218017A CN 201910456959 A CN201910456959 A CN 201910456959A CN 110218017 A CN110218017 A CN 110218017A
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- Prior art keywords
- modified
- triethanolamine
- grinding aid
- cement grinding
- triisopropanolamine
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Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/12—Nitrogen containing compounds organic derivatives of hydrazine
- C04B24/122—Hydroxy amines
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/06—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton from hydroxy amines by reactions involving the etherification or esterification of hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/52—Grinding aids; Additives added during grinding
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses a kind of new modified cement grinding aids and preparation method thereof, the cement grinding aid is prepared by following raw material: modified triethanolamine 6~28%, dispersing agent 0.5~1%, crude glycerine 15 ~ 34%, molasses 3 ~ 8%, sodium thiosulfate 13~20%, modified triisopropanolamine 0~12%, surplus is water, total amount 100%；The percentage is mass percent.It has used that dispersing agent its chemical stability added according to demand is good, halide ion without containing corrosion equipment, has significantly improved the early strength and later strength of cement, the participation of modified hydramine can significantly improve mill efficiency, the water-retaining property after improving cement grinding.
Description
Technical field
The invention belongs to technical field of cement production, and in particular to a kind of new modified cement grinding aid and its preparation side
Method.
Background technique
In cement production process, main processes may be simply referred to as two mills one burning, i.e. mill raw material, overburnt material, mill cement,
A small amount of cement grinding aid is added before cement grinding, under early strength agent electron screening and surface active properties double action, cement
The surface nature of particle is improved, and high mill efficiency is improved.At present triethanolamine as cement early strength agent it is effective at
Part at home and abroad uses, and the Electrostatic Absorption bag ball phenomenon formed in grinding process can be greatly lowered than wide cement grinding aid,
And the coalescence trend again of the ultra-fine grain formed in grinding process can be reduced.Cement grinding aid can also significantly improve cement stream
Dynamic property, improves the grinding effect of grinding machine and the grinding efficiency of powder concentrator, as a kind of chemical addition agent, grinding aid can improve cement
Distribution of particles simultaneously excites aquation power, to improve cement early strength and later strength.
The component of liquid cement grinding additive currently on the market often has: triethanolamine, polymerized polyalcohol, polyalcohol amine, three
Isopropanolamine, ethylene glycol, propylene glycol, glycerine, sodium soap, calcium chloride, sodium chloride, sodium acetate, aluminum sulfate, calcium formate, wood
Calcium, wooden sodium etc..
Common liq grinding aid is applied to seriously affect the service performance of grinding aid in high temperature grinding machine, reduces the grinding of grinding machine
Efficiency declines the grindability of cement material, the mill efficiency decline of grinding machine, this is because liter of the grindability of material with temperature
It is high and caused by declining, simultaneously as the raising of temperature, fine dust are easy to assemble because of electrostatic attraction, cause slimeball phenomenon,
The mill efficiency of grinding machine is also reduced, cement mill unit-hour output is caused to decline.
Summary of the invention
Purpose: to solve the deficiencies in the prior art, the present invention provides a kind of new modified cement grinding aid.
Technical solution: in order to solve the above technical problems, the technical solution adopted by the present invention are as follows:
A kind of new modified cement grinding aid, which is characterized in that the cement grinding aid is prepared by following raw material: modified
Triethanolamine 6~18%, dispersing agent 0.5~1%, crude glycerine 15~34%, molasses 3~8%, sodium thiosulfate 13~20%,
Modified triisopropanolamine 0.001~12%, surplus is water, total amount 100%；The percentage is mass percent；
According to formula rate, by modified triethanolamine, dispersing agent, crude glycerine, molasses, sodium thiosulfate, modified three isopropyls
Hydramine is dissolved in water, be uniformly mixed to get.
Another program, a kind of new modified cement grinding aid, which is characterized in that the cement grinding aid is prepared by following raw material
It obtains: modified triethanolamine 6~18%, dispersing agent 0.5~1%, crude glycerine 15~34%, molasses 3~8%, sodium thiosulfate
13~20%, surplus is water, total amount 100%；The percentage is mass percent；
According to formula rate, modified triethanolamine, dispersing agent, crude glycerine, molasses, sodium thiosulfate are dissolved in water,
Be uniformly mixed to get.
Preferably, the new modified cement grinding aid, which is characterized in that the dispersing agent is polycarboxylic acids
One or more of salt, lauryl sodium sulfate or polycarboxylate water-reducer.
Further, the modified triethanolamine is that triethanolamine and glacial acetic acid reaction are made, and preparation method includes:
Triethanolamine and glacial acetic acid are added in the reaction vessel, stirs and evenly mixs, the concentrated sulfuric acid is added as catalysis in dropwise addition mode
Agent, then heating is heated to 110~120 DEG C of reflux, and after reaction, cooling obtains triethanolamine glacial acetic acid modifier, that is, changes
Property triethanolamine.
More preferably, in the modified triethanolamine preparation process, the triethanolamine of addition and the molar ratio of glacial acetic acid
For 1:1；
The amount that the catalyst concentrated sulfuric acid is added is the 1%~5% of reactant triethanolamine and glacial acetic acid gross mass.
Further, the modified triisopropanolamine is that triisopropanolamine and glacial acetic acid reaction are made, and preparation includes:
Triisopropanolamine and glacial acetic acid are added in the reaction vessel, stirs and evenly mixs, catalyst is added before heating up, mode is added dropwise
The concentrated sulfuric acid is added as catalyst, then heating is heated to 130~140 DEG C of reflux, and after reaction, cooling obtains three isopropanols
Amine glacial acetic acid modifier, i.e., modified triisopropanolamine.
More preferably, in the modified triisopropanolamine preparation process, the triisopropanolamine of addition and rubbing for glacial acetic acid
You are than being 1:1；
The amount that the catalyst concentrated sulfuric acid is added is the 1%~5% of reactant triisopropanolamine and glacial acetic acid gross mass.
The present invention provides a kind of new modified cement grinding aid and preparation method thereof, the participation of modified hydramine can be significant
Mill efficiency is improved, the water-retaining property after improving cement grinding；Modified triethanolamine is adsorbed in the form of " film " by levigate
Powder granule surface reduces the intensity and hardness of powder granule, particle is made to be easy to levigate；After breakage of particles, the modification of absorption
Triethanolamine plays the role of preventing the coincidence of section again；Modified triethanolamine has neutralized the unsaturated electrovalent bond of particle surface,
Mill internal electric field environment is improved, the mobility of cement is improved, prevents powder from assembling and pastes mill, to improve mill efficiency.
New modified cement grinding aid can reduce the surface energy of material, weaken and gather effect caused by molecular attraction, help external force
The acceleration extension of particle crackle realizes high-quality, energy saving, high yield the purpose of ball mill to improve mill efficiency when work done；This
Outside, new modified cement grinding aid is mentioned using modified triethanolamine, the hydration activity of polycarboxylate excitation latent hydraulicity material
High cement early strength improves cement fluidity, shortens setting time, and reduction water requirement catalyst is added again, suction can be improved
It produces effects rate, addition content is low, economical and practical.
The utility model has the advantages that new modified cement grinding aid provided by the invention, chemical stability is good, and addition content is low, nontoxic
Pollution-free, the halide ion without containing corrosion equipment significantly improves the early strength and later strength of cement, modified hydramine
Participation can significantly improve mill efficiency, the water-retaining property after improving cement grinding.It has the advantage that
1) actual amount is less than common grinding aid.
2) chemical stability is preferable, and dispersing agent is added and improves grinding aid activity.
3) nontoxic and pollution-free, it can be improved grinding aid efficiency, increase unit-hour output, it is non-corrosive, it is "dead", it is not belonging to endanger
Dangerous chemicals.
Specific embodiment
Illustrate below with reference to example to the present invention: percentage is mass percent in the present invention.
Embodiment 1
A kind of new modified cement grinding aid, raw material composition are as follows: modified triethanolamine 8%, dispersant polycarboxylate
0.7%, crude glycerine 23%, molasses 5%, sodium thiosulfate 15%, modified triisopropanolamine 0%, surplus is water, total amount 100%；
The modified triethanolamine its preparation the following steps are included:
Reacted with the triethanolamine and glacial acetic acid of mole 1:1: be added in three neck round bottom flask triethanolamine (55g,
It 0.36mol) is stirred with glacial acetic acid (20g, 0.36mol), catalyst is added before heating up, the catalyst concentrated sulfuric acid is added, and (reactant is total
The 3% of quality) 2.25g is slowly added dropwise, 110~120 DEG C of reflux are heated to, after reaction, cooling obtains triethanolamine ice to 4h
Acetic acid modifier.
The percentage is mass percent, according to formula rate, by modified triethanolamine, dispersing agent, crude glycerine, sugar
Honey, sodium thiosulfate are dissolved in water, and are uniformly mixed to get product 1.
Embodiment 2
A kind of new modified cement grinding aid, raw material composition are as follows: modified triethanolamine 7%, dispersant polycarboxylate
0.5%, crude glycerine 13%, molasses 3%, sodium thiosulfate 16%, modified triisopropanolamine 3%, surplus is water, total amount 100%；
The modified triethanolamine its preparation the following steps are included:
Reacted with the triethanolamine and glacial acetic acid of mole 1:1: be added in three neck round bottom flask triethanolamine (55g,
It 0.36mol) is stirred with glacial acetic acid (20g, 0.36mol), catalyst is added before heating up, the catalyst concentrated sulfuric acid is added, and (reactant is total
The 1% of quality) 0.75g is slowly added dropwise, 110~120 DEG C of reflux are heated to, after reaction, cooling obtains triethanolamine ice to 5h
Acetic acid modifier.
The modified triisopropanolamine, preparation the following steps are included:
It is reacted with the triisopropanolamine of mole 1:1 and glacial acetic acid: triisopropanolamine being added in three neck round bottom flask
Catalyst is added before heating up in the stirring of (69g, 0.36mol) and glacial acetic acid (20g, 0.36mol), and (the reaction of the catalyst concentrated sulfuric acid is added
The 3% of object gross mass) 2.67g is slowly added dropwise, 130~140 DEG C are heated to, after reaction, cooling obtains triisopropanolamine to 4h
Glacial acetic acid modifier.
The percentage is mass percent, according to formula rate, by modified triethanolamine, dispersing agent, crude glycerine, sugar
Honey, sodium thiosulfate, modified triisopropanolamine are dissolved in water, and are uniformly mixed to get product 2.
Embodiment 3
A kind of new modified cement grinding aid, raw material composition are as follows: modified triethanolamine 18%, dispersant polycarboxylate
1%, crude glycerine 34%, molasses 8%, sodium thiosulfate 20%, modified triisopropanolamine 12%, surplus is water, total amount 100%；
The modified triethanolamine its preparation the following steps are included:
Reacted with the triethanolamine and glacial acetic acid of mole 1:1: be added in three neck round bottom flask triethanolamine (55g,
It 0.36mol) is stirred with glacial acetic acid (20g, 0.36mol), catalyst is added before heating up, the catalyst concentrated sulfuric acid is added, and (reactant is total
The 5% of quality) 3.75g is slowly added dropwise, 110~120 DEG C of reflux are heated to, after reaction, cooling obtains triethanolamine ice to 4h
Acetic acid modifier.
The modified triisopropanolamine, preparation the following steps are included:
It is reacted with the triisopropanolamine of mole 1:1 and glacial acetic acid: triisopropanolamine being added in three neck round bottom flask
Catalyst is added before heating up in the stirring of (69g, 0.36mol) and glacial acetic acid (20g, 0.36mol), and (the reaction of the catalyst concentrated sulfuric acid is added
The 5% of object gross mass) 4.45g is slowly added dropwise, 130~140 DEG C are heated to, after reaction, cooling obtains triisopropanolamine to 3h
Glacial acetic acid modifier.
The percentage is mass percent, according to formula rate, by modified triethanolamine, dispersing agent, crude glycerine, sugar
Honey, sodium thiosulfate, modified triisopropanolamine are dissolved in water, and are uniformly mixed to get product 3.
Embodiment 4
A kind of new modified cement grinding aid, raw material composition are as follows: modified triethanolamine 6%, dispersant polycarboxylate
0.5%, crude glycerine 13%, molasses 3%, sodium thiosulfate 13%, modified triisopropanolamine 6%, surplus is water, total amount 100%；
The modified triethanolamine its preparation the following steps are included:
Reacted with the triethanolamine and glacial acetic acid of mole 1:1: be added in three neck round bottom flask triethanolamine (55g,
It 0.36mol) is stirred with glacial acetic acid (20g, 0.36mol), catalyst is added before heating up, the catalyst concentrated sulfuric acid is added, and (reactant is total
The 3% of quality) 2.25g is slowly added dropwise, 110~120 DEG C of reflux are heated to, after reaction, cooling obtains triethanolamine ice to 3h
Acetic acid modifier.
The modified triisopropanolamine, preparation the following steps are included:
It is reacted with the triisopropanolamine of mole 1:1 and glacial acetic acid: triisopropanolamine being added in three neck round bottom flask
Catalyst is added before heating up in the stirring of (69g, 0.36mol) and glacial acetic acid (20g, 0.36mol), and (the reaction of the catalyst concentrated sulfuric acid is added
The 1% of object gross mass) 0.89g is slowly added dropwise, 130~140 DEG C are heated to, after reaction, cooling obtains triisopropanolamine to 5h
Glacial acetic acid modifier.
The percentage is mass percent, according to formula rate, by modified triethanolamine, dispersing agent, crude glycerine, sugar
Honey, sodium thiosulfate, modified triisopropanolamine are dissolved in water, and are uniformly mixed to get product 4.
Performance test
Application method of the invention, the addition content of cement grinding aid are the one thousandth of cement ingredient.
Cement is sampled according to Sampling method of cement GB/T 12573, is surveyed according to the test method of cement performance detection
Determine the physical property of cement.Cement specific surface is tested according to GB/T 8074-2008 " Method of determination for specific surface of cement Bo Shi method "
Product；Strength of cement mortar is measured according to GB/T17671-1999 " Test method for strength of hydraulic cement mortar (ISO method) ".
As a result it see the table below:
The present invention is disclosed with preferred embodiment above, so it is not intended to limiting the invention, all to use equivalent replacement
Or equivalent transformation mode technical solution obtained, it is within the scope of the present invention.
Claims (9)
1. a kind of new modified cement grinding aid, which is characterized in that the cement grinding aid is prepared by following raw material: modified three
Ethanol amine 6~18%, dispersing agent 0.5~1%, crude glycerine 15 ~ 34%, molasses 3 ~ 8%, sodium thiosulfate 13~20%, modified three isopropyls
Hydramine 0.001~12%, surplus are water, total amount 100%；The percentage is mass percent；
According to formula rate, by modified triethanolamine, dispersing agent, crude glycerine, molasses, sodium thiosulfate, modified triisopropanolamine
Be dissolved in water, be uniformly mixed to get.
2. a kind of new modified cement grinding aid, which is characterized in that the cement grinding aid is prepared by following raw material: modified three
Ethanol amine 6~18%, dispersing agent 0.5~1%, crude glycerine 15 ~ 34%, molasses 3 ~ 8%, sodium thiosulfate 13~20%, surplus are water,
Total amount 100%；The percentage is mass percent；
According to formula rate, modified triethanolamine, dispersing agent, crude glycerine, molasses, sodium thiosulfate are dissolved in water, mixed
Uniformly to get.
3. new modified cement grinding aid according to claim 1 or 2, which is characterized in that the dispersing agent is polycarboxylic acids
One or more of salt, lauryl sodium sulfate or polycarboxylate water-reducer.
4. new modified cement grinding aid according to claim 1 or 2, which is characterized in that the modified triethanolamine is
Triethanolamine and glacial acetic acid reaction are made, and preparation method includes:
Triethanolamine and glacial acetic acid are added in the reaction vessel, stirs and evenly mixs, the concentrated sulfuric acid is added as catalyst, so in dropwise addition mode
Heating is heated to 110 ~ 120 DEG C of reflux afterwards, and after reaction, cooling obtains triethanolamine glacial acetic acid modifier, i.e., modified three second
Hydramine.
5. new modified cement grinding aid according to claim 4, which is characterized in that prepared by the modified triethanolamine
Cheng Zhong, the triethanolamine of addition and the molar ratio of glacial acetic acid are 1:1.
6. new modified cement grinding aid according to claim 4, which is characterized in that prepared by the modified triethanolamine
Cheng Zhong, the amount that the catalyst concentrated sulfuric acid is added is the 1% ~ 5% of reactant triethanolamine and glacial acetic acid gross mass.
7. new modified cement grinding aid according to claim 1, which is characterized in that the modified triisopropanolamine is three
Isopropanolamine and glacial acetic acid reaction are made, and preparation includes:
Triisopropanolamine and glacial acetic acid are added in the reaction vessel, stirs and evenly mixs, catalyst is added before heating up, dropwise addition mode is added
The concentrated sulfuric acid is as catalyst, and then heating is heated to 130 ~ 140 DEG C of reflux, and after reaction, cooling obtains triisopropanolamine ice
Acetic acid modifier, i.e., modified triisopropanolamine.
8. new modified cement grinding aid according to claim 7, which is characterized in that the modified triisopropanolamine preparation
In the process, the molar ratio of the triisopropanolamine and glacial acetic acid of addition is 1:1.
9. new modified cement grinding aid according to claim 7, which is characterized in that the modified triisopropanolamine preparation
In the process, the amount that the catalyst concentrated sulfuric acid is added is the 1% ~ 5% of reactant triisopropanolamine and glacial acetic acid gross mass.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111072304A (en) * | 2019-12-27 | 2020-04-28 | 杭州斯曼特建材科技有限公司 | Fly ash and slag curing agent and preparation method thereof |
| CN111072305A (en) * | 2019-12-25 | 2020-04-28 | 安徽成弘建新材料有限公司 | Slag activity synergist and preparation method and application thereof |
| CN111072303A (en) * | 2019-12-27 | 2020-04-28 | 杭州斯曼特建材科技有限公司 | Steel slag grinding-aid reinforcing agent and preparation method thereof |
| CN112159149A (en) * | 2020-08-26 | 2021-01-01 | 信阳市灵石科技有限公司 | Cement grinding aid and preparation method thereof |
| CN112624653A (en) * | 2020-12-31 | 2021-04-09 | 上海三瑞高分子材料股份有限公司 | Early-strength cement grinding aid |
| CN113512307A (en) * | 2021-03-26 | 2021-10-19 | 湛江宝钢新型建材科技有限公司 | Steel slag functional agent and preparation method and use method thereof |
| CN115028386A (en) * | 2022-03-28 | 2022-09-09 | 史才军 | Compound cement grinding aid containing monoethanol diisopropanolamine and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111072305A (en) * | 2019-12-25 | 2020-04-28 | 安徽成弘建新材料有限公司 | Slag activity synergist and preparation method and application thereof |
| CN111072304A (en) * | 2019-12-27 | 2020-04-28 | 杭州斯曼特建材科技有限公司 | Fly ash and slag curing agent and preparation method thereof |
| CN111072303A (en) * | 2019-12-27 | 2020-04-28 | 杭州斯曼特建材科技有限公司 | Steel slag grinding-aid reinforcing agent and preparation method thereof |
| CN112159149A (en) * | 2020-08-26 | 2021-01-01 | 信阳市灵石科技有限公司 | Cement grinding aid and preparation method thereof |
| CN112624653A (en) * | 2020-12-31 | 2021-04-09 | 上海三瑞高分子材料股份有限公司 | Early-strength cement grinding aid |
| CN113512307A (en) * | 2021-03-26 | 2021-10-19 | 湛江宝钢新型建材科技有限公司 | Steel slag functional agent and preparation method and use method thereof |
| CN115028386A (en) * | 2022-03-28 | 2022-09-09 | 史才军 | Compound cement grinding aid containing monoethanol diisopropanolamine and preparation method thereof |
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