CN106277894A - A kind of environmental protection early-strength graphene oxide cement grinding aid and preparation method thereof - Google Patents
A kind of environmental protection early-strength graphene oxide cement grinding aid and preparation method thereof Download PDFInfo
- Publication number
- CN106277894A CN106277894A CN201610803883.9A CN201610803883A CN106277894A CN 106277894 A CN106277894 A CN 106277894A CN 201610803883 A CN201610803883 A CN 201610803883A CN 106277894 A CN106277894 A CN 106277894A
- Authority
- CN
- China
- Prior art keywords
- grinding aid
- graphene oxide
- cement
- water
- cement grinding
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- 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
- 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
Abstract
The present invention relates to a kind of environmental protection early-strength graphene oxide cement grinding aid, it is made up of following mass percent: polymerized polyalcohol 35 55%, acrylate 2 5%, diethylene glycol 3 6%, tetraisopropyl titanate 1 3%, polycarboxylate water-reducer 3 8%, calcium dodecyl benzene sulfonate 1 2%, polyoxyethylenated alcohol sodium sulfate 1 2%, diethanolamine 5 10%, triisopropanolamine 5 10%, graphene oxide water solution 1 5%, surplus is industrial wastewater.Also relate to the preparation method of this grinding aid.The present invention utilizes environmental protection early-strength graphene oxide cement grinding aid, and graphene oxide just can significantly improve mill efficiency when volume is less, and the cement granules of grinding has bigger specific surface area and less tailing over；Significantly enhance the early strength of cement；After mill, cement is excellent with water reducer adaptability；Efficiently utilizing industrial wastewater, product is environmentally friendly, pollution-free.
Description
Technical field
The invention belongs to the technical field of construction material, be specifically related to a kind of environmental protection early-strength graphene oxide cement
Agent and preparation method thereof.
Background technology
Since 21 century, China's economic development is rapid, which also promotes the development of building industry and related industry thereof, and China becomes
For manufacture of cement the first big country.There is substantial amounts of power consumption in cement production process, wherein to account for manufacture of cement total for grinding pow consumption
2/3rds of power consumption, energy utilization rate is low, serious waste of resources.Therefore, improving mill efficiency is manufacture of cement energy-conservation of consumption reduction
Key.Cement grinding aid is a kind of raising grinding efficiency, improves material grindability energy in manufacture of cement, and addition content is little
A kind of chemical addition agent of organic or inorganic.During finished ground cement, grinding aid can significantly improve mill efficiency, is substantially reduced
Grinding pow consumption, improves fineness and the specific surface area of cement.Meanwhile, grinding aid can also improve the early strength of cement, is not damaging
On the basis of cement self performance, reduce manufacture of cement cost, improve manufacture of cement efficiency.Clinker and other mixing materials exist
In grinding machine powder process, with grain refine, cement granules specific surface area increases electrically charged because of scission of link, mutually adsorbs between granule
Produce and reunite, make mill efficiency be greatly reduced.Grinding aid acts between the granule of cement material, reduces the surface energy of particle,
Its principle is to prevent particle aggregation, improves its mobility, raising mill efficiency, thus energy-saving and emission-reduction.At present, used by cement plant
Grinding aid is generally alcohol-based liquid grinding aid.Currently, nearly 7,000,000 tons of the annual discharge of wastewater of China, centralized pollution control waste water
Discharge capacity is only 0.4 hundred million tons, accounts for the 0.1% of wastewater emission amount, still has substantial amounts of waste water not processed, brings to environmental improvement
Immense pressure.Textile industry discharge of wastewater accounts for the 9.1% of total discharge of wastewater, mainly contains oils and fats, salt and the course of processing in sewage
In the inorganic matter such as additional various slurries, dyestuff, surfactant, auxiliary agent and soda acid, sulfide, all kinds of salt compounds,
Wherein alkali, sulfide, all kinds of salt compounds environmental pollution are very big, and affect its own existence of the mankind.Textile industry is raw
The water reuse that product is produced, in manufacture of cement, can effectively solve textile industry waste water handling problem, and wrap in waste water
The surfactant contained can promote again the grinding of cement, and the solution not only improving waste water handling problem achieves again refuse profit
With.Graphene is the material that the intensity found up to now is the highest, toughness is best, specific surface area is maximum.Graphene oxide (GO)
It is the oxidized reaction of graphite and the later product of ultrasonic disperse, there is the spy that specific surface area is relatively big, surface functional group type is abundant
Point, stable dispersion in aqueous and can have the good compatibility with macromolecule.Graphene oxide is applied to polymer
Organic material and mineral-type materials are the focuses of contemporary scientific research, and having obtained confirmation in the applied research of cement-based material can
Effectively to reduce the porosity of hardened paste, improve microstructure, thus be favorably improved the mechanical property of cement.
Summary of the invention
For solving the problems referred to above, the present invention provides a kind of environmental protection early-strength graphene oxide cement grinding aid, this grinding aid
Mill efficiency is high, and after mill, cement is excellent with water reducer adaptability, effectively utilizes industrial wastewater, protects environment.
Present invention simultaneously provides the preparation method of this cement grinding aid.
The present invention is achieved through the following technical solutions:
A kind of environmental protection early-strength graphene oxide cement grinding aid, is made up of following mass percent: polymerized polyalcohol 35-55%,
Acrylate 2-5%, diethylene glycol 3-6%, tetraisopropyl titanate 1-3%, polycarboxylate water-reducer 3-8%, calcium dodecyl benzene sulfonate
1-2%, polyoxyethylenated alcohol sodium sulfate 1-2%, diethanolamine 5-10%, triisopropanolamine 5-10%, graphene oxide is water-soluble
Liquid 1-5%, surplus is industrial wastewater.
Preferably, grinding aid is made up of following materials in percentage by mass: polymerized polyalcohol 44%, acrylate 2%, diethyl two
Alcohol 3%, tetraisopropyl titanate 1%, polycarboxylate water-reducer 5%, calcium dodecyl benzene sulfonate 2%, polyoxyethylenated alcohol sodium sulfate
1%, diethanolamine 10%, triisopropanolamine 10%, graphene oxide water solution 2%, industrial wastewater 20%.
Preferably, the concentration of graphene oxide described above is 1-5mg/ml, and described industrial wastewater is that textile industry is given up
Water.
The preparation method of this cement grinding aid, comprises the following steps:
(1) by polymerized polyalcohol, acrylate and diethylene glycol heating in water bath to 70 DEG C～100 DEG C, tetraisopropyl titanate is added,
Stir 10-20 minute, ultrasonic disperse 10-20min, react 1-3h；
(2) maintain bath temperature 70 DEG C～100 DEG C, add industrial wastewater, mix homogeneously；
(3) be sequentially added into calcium dodecyl benzene sulfonate, polyoxyethylenated alcohol sodium sulfate, diethanolamine, triisopropanolamine and
Polycarboxylate water-reducer, stirs to all dissolving；
(4) graphene oxide solution being added, heating in water bath, to 60-90 DEG C, stands 10-24h after ultrasonic disperse 10-30min,
Cement grinding aid.
The useful achievement of the present invention is:
The present invention utilizes environmental protection early-strength graphene oxide cement grinding aid, and graphene oxide just can be more notable when volume is less
Improving mill efficiency, the cement granules of grinding has bigger specific surface area and less tailing over；Significantly enhance the morning of cement
Phase intensity；After mill, cement is excellent with water reducer adaptability；Efficiently utilizing industrial wastewater, product is environmentally friendly, pollution-free.
In the cement pulverizing course of equal time, this product relatively blank sample label PC42.5 cement 0.045mm tails over
Reducing 8%-12%, 0.08mm and tail over reduction 10%-20%, specific surface area improves 8%-10%, and 3 days intensity improves 4-6Mpa, and 28 days strong
Degree improves 4-8Mpa.After the mill of relatively commercially available prod, cement has had certain improvement with the adaptability of water reducer, and liquidity value added reduces,
Be effectively improved adaptability bad cause bleeding, be layered, take off end phenomenon, water-reducing rate improves 3-5%.
Detailed description of the invention
In order to be more fully understood that the essence of the present invention, below by specific embodiment, technical scheme is entered
The elaboration of one step.
Embodiment 1
The preparation method of a kind of type environmental protection early-strength graphene oxide cement grinding aid, comprises the following steps, and following percentage ratio is equal
For mass percent:
(1) take 35% polymerized polyalcohol, 2% acrylate and 3% diethylene glycol heating in water bath 70 DEG C, add metatitanic acid four isopropyl of 1%
Ester, mechanical agitation 10min, then ultrasonic disperse 10min is to after uniformly, and water-bath 1h obtains alkanolamine ester compounds.
(2) maintain bath temperature 70 DEG C, alkanolamine ester compounds adds 34% textile waste, mix homogeneously, joins
Become solution.
(3) in the solution configured, it is proportionally added into the calcium dodecyl benzene sulfonate 1% of metering, aliphatic alcohol polyethenoxy
Ether sodium sulfate 1%, diethanolamine 10%, triisopropanolamine 9%, polycarboxylate water-reducer 3%, it is evenly stirred until all dissolvings；
(4) graphene oxide solution 1% (concentration is 1mg/ml) of metering, heating in water bath to 60 DEG C, ultrasonic disperse 10min are added；
Last solution left standstill 10h, after standing, the most i.e. obtains cement grinding aid.Have no irritating odor after testing, solid content closes
Lattice, pH value are qualified, chloride ion content is qualified, comply fully with the requirement of GB/T26748-2011.
Embodiment 2
The preparation method of a kind of type environmental protection early-strength graphene oxide cement grinding aid, comprises the following steps, and following percentage ratio is equal
For mass percent:
(1) take 55% polymerized polyalcohol, 5% acrylate and 6% diethylene glycol heating in water bath 100 DEG C, add tetraisopropyl titanate
3%, mechanical agitation 20min, then ultrasonic disperse 20min is to after uniformly, and water-bath 2h obtains alkanolamine ester compounds.
(2) maintain bath temperature 100 DEG C, add in alkanolamine ester compounds, 4% textile waste, mix homogeneously,
Wiring solution-forming.
(3) in the solution configured, it is proportionally added into the calcium dodecyl benzene sulfonate 2% of metering, aliphatic alcohol polyethenoxy
Ether sodium sulfate 2%, diethanolamine 5%, triisopropanolamine 5%, polycarboxylate water-reducer 8%, it is evenly stirred until all dissolvings；
(4) graphene oxide solution 5% (concentration is 5mg/ml) of metering, heating in water bath to 90 DEG C, ultrasonic disperse 30min are added；
Last solution left standstill 24h, after standing, the most i.e. obtains cement grinding aid.Have no irritating odor after testing, solid content closes
Lattice, pH value are qualified, chloride ion content is qualified, comply fully with the requirement of GB/T26748-2011.
Embodiment 3
The preparation method of a kind of type environmental protection early-strength graphene oxide cement grinding aid, comprises the following steps, and following percentage ratio is
Mass percent:
(1) take 44% polymerized polyalcohol, 2% acrylate and 3% diethylene glycol heating in water bath 90 DEG C, add tetraisopropyl titanate 1%,
Mechanical agitation 20min, then ultrasonic disperse 20min is to after uniformly, and water-bath 3h obtains alkanolamine ester compounds.
(2) maintain bath temperature 90 DEG C, alkanolamine ester compounds adds 20% textile waste, mix homogeneously, joins
Become solution.
(3) in the solution configured, it is proportionally added into the calcium dodecyl benzene sulfonate 2% of metering, aliphatic alcohol polyethenoxy
Ether sodium sulfate 1%, diethanolamine 10%, triisopropanolamine 10%, polycarboxylate water-reducer 5%, it is evenly stirred until all dissolvings；
(4) graphene oxide solution 2% (concentration is 2mg/ml) of metering, heating in water bath to 90 DEG C, ultrasonic disperse 20min are added；
Last solution left standstill 24h, after standing, the most i.e. obtains cement grinding aid.Have no irritating odor after testing, solid content closes
Lattice, pH value are qualified, chloride ion content is qualified, comply fully with the requirement of GB/T26748-2011.It is designated as grinding aid D.
Comparative example 1
The grinding aid that a kind of commercially available shared market share is bigger, it is mainly composed of diethanolamine and polyalcohols grinding aid, remembers
For grinding aid A.
Comparative example 2
The preparation method of a kind of environmental protection early-strength graphene oxide cement grinding aid, step is identical with embodiment 3, and difference exists
In, the addition of non-oxidation Graphene in system, i.e. without step (4), other steps, all with embodiment 3, are designated as grinding aid B.
Comparative example 3
A kind of environmental protection early-strength graphene oxide cement grinding aid and preparation method thereof, step is identical with embodiment 3, difference
Being, the addition of fat-free polyoxyethylenated alcohol sodium sulfate in system, other steps, all with embodiment 3, are designated as grinding aid C.
Above-mentioned 4 kinds of grinding aids are used for PC 42.5 cement ball-milling, and each proportioning such as table 1, the chemical component table of clinker is shown in
Table 2.Gypsum Fibrosum is the natural gypsum.Ball-milling technology: mill feed material 5kg every time, uses the Ceramic Balls of a diameter of 5cm, the filling of abrading-ball
Amount is 100kg, and the rotating speed of grinding machine is 50r/min, and grinding time is 30min.Under identical grinding time, mixing of each grinding aid
Dosage is 0.03%.
Table 1 PC42.5 experimental raw formula
Table 2 raw material chemical analysis
Being analyzed the result of grinding below, table 3 and table 4 are grinding aid grinding aid performance and the cement performance survey of PC42.5 respectively
The result of examination, grinding aid A is poor with the compatibility of additive, has more serious bleeding, is layered, takes off end phenomenon, and grinding aid B is with outward
Adding the compatible general of agent, have slight bleeding, be layered, take off end phenomenon, grinding aid C is compatible general with additive, has light
Micro-bleeding, being layered, take off end phenomenon, grinding aid D is compatible good with additive, without bleeding, is layered, takes off end phenomenon.
Table 3 PC42.5 grinding aid grinding aid performance test
Table 4 PC42.5 cement performance is tested
Grinding-aid effect compares, D > B > C > A > blank, such as table 3, grinding aid D of the present invention, 0.045mm tail over reduction about 10%,
0.08mm tails over reduction about 18%, and specific surface area improves about 9%, significantly reduces and tails over, improves the specific surface area of cement.
Mechanical property compares, D > B > C > A > blank, such as table 4, grinding aid D of the present invention, 3 days intensity improves 6Mpa, and 28
It intensity improves 8Mpa.After the mill of relatively commercially available prod, cement has had certain improvement with the adaptability of water reducer, and liquidity value added drops
Low, be effectively improved adaptability bad cause bleeding, be layered, take off end phenomenon.
Above-described embodiment, only for technology design and the feature of the explanation present invention, its object is to allow person skilled in the art
Scholar will appreciate that present disclosure and implements according to this, can not limit the scope of the invention with this.All according to the present invention
The equivalence that spirit is made changes or modifies, and all should contain within protection scope of the present invention.
Claims (5)
1. an environmental protection early-strength graphene oxide cement grinding aid, it is characterised in that be made up of following mass percent: polymerization
Polyhydric alcohol 35-55%, acrylate 2-5%, diethylene glycol 3-6%, tetraisopropyl titanate 1-3%, polycarboxylate water-reducer 3-8%, 12
Alkyl benzene calcium sulfonate 1-2%, polyoxyethylenated alcohol sodium sulfate 1-2%, diethanolamine 5-10%, triisopropanolamine 5-10%, oxygen
Functionalized graphene aqueous solution 1-5%, surplus is industrial wastewater.
Cement grinding aid the most according to claim 1, it is characterised in that be made up of following materials in percentage by mass: polymerization
Polyhydric alcohol 44%, acrylate 2%, diethylene glycol 3%, tetraisopropyl titanate 1%, polycarboxylate water-reducer 5%, DBSA
Calcium 2%, polyoxyethylenated alcohol sodium sulfate 1%, diethanolamine 10%, triisopropanolamine 10%, graphene oxide water solution 2%, work
Industry waste water 20%.
Cement grinding aid the most according to claim 1, it is characterised in that the concentration of described graphene oxide is 1-5mg/
ml。
Cement grinding aid the most according to claim 1, it is characterised in that described industrial wastewater is textile industry waste water.
5. the preparation method of the cement grinding aid that one of claim 1-4 is described, it is characterised in that comprise the following steps:
(1) by polymerized polyalcohol, acrylate and diethylene glycol heating in water bath to 70 DEG C～100 DEG C, tetraisopropyl titanate is added,
Stir 10-20 minute, ultrasonic disperse 10-20min, react 1-3h；
(2) maintain bath temperature 70 DEG C～100 DEG C, add industrial wastewater, mix homogeneously；
(3) be sequentially added into calcium dodecyl benzene sulfonate, polyoxyethylenated alcohol sodium sulfate, diethanolamine, triisopropanolamine and
Polycarboxylate water-reducer, stirs to all dissolving；
(4) graphene oxide solution being added, heating in water bath, to 60-90 DEG C, stands 10-24h after ultrasonic disperse 10-30min,
Cement grinding aid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610803883.9A CN106277894A (en) | 2016-09-05 | 2016-09-05 | A kind of environmental protection early-strength graphene oxide cement grinding aid and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610803883.9A CN106277894A (en) | 2016-09-05 | 2016-09-05 | A kind of environmental protection early-strength graphene oxide cement grinding aid and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106277894A true CN106277894A (en) | 2017-01-04 |
Family
ID=57711092
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610803883.9A Withdrawn CN106277894A (en) | 2016-09-05 | 2016-09-05 | A kind of environmental protection early-strength graphene oxide cement grinding aid and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106277894A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107216058A (en) * | 2017-04-24 | 2017-09-29 | 浙江博力建材科技有限公司 | A kind of graphene cement grinding aid and preparation method thereof |
| CN108940553A (en) * | 2018-07-19 | 2018-12-07 | 佛山陵朝新材料有限公司 | A kind of ore crushing grinding aid special |
| CN109293265A (en) * | 2018-12-20 | 2019-02-01 | 四川聚创石墨烯科技有限公司 | Graphene/carbon nano-onions grinding aid and its composite material and preparation method |
| CN112142356A (en) * | 2020-09-11 | 2020-12-29 | 湖北京兰水泥集团有限公司 | Biodegradable cement grinding aid and preparation method thereof |
| CN116874211A (en) * | 2023-05-09 | 2023-10-13 | 山东诚港新材料科技有限公司 | Coal-saving sulfur-fixing agent for cement rotary kiln production |
-
2016
- 2016-09-05 CN CN201610803883.9A patent/CN106277894A/en not_active Withdrawn
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107216058A (en) * | 2017-04-24 | 2017-09-29 | 浙江博力建材科技有限公司 | A kind of graphene cement grinding aid and preparation method thereof |
| CN108940553A (en) * | 2018-07-19 | 2018-12-07 | 佛山陵朝新材料有限公司 | A kind of ore crushing grinding aid special |
| CN109293265A (en) * | 2018-12-20 | 2019-02-01 | 四川聚创石墨烯科技有限公司 | Graphene/carbon nano-onions grinding aid and its composite material and preparation method |
| CN109293265B (en) * | 2018-12-20 | 2021-09-03 | 四川聚创石墨烯科技有限公司 | Graphene/carbon nano onion grinding aid, composite material thereof and preparation method |
| CN112142356A (en) * | 2020-09-11 | 2020-12-29 | 湖北京兰水泥集团有限公司 | Biodegradable cement grinding aid and preparation method thereof |
| CN116874211A (en) * | 2023-05-09 | 2023-10-13 | 山东诚港新材料科技有限公司 | Coal-saving sulfur-fixing agent for cement rotary kiln production |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106277894A (en) | A kind of environmental protection early-strength graphene oxide cement grinding aid and preparation method thereof | |
| CN106380110B (en) | A kind of graphene oxide is modified cement grinding aid and preparation method thereof | |
| CN101337788A (en) | Modified triethanolamine, preparation method and application thereof | |
| EP3351506A1 (en) | Method for producing phosphoric acid and by-producing alpha-hemihydrate gypsum by wet-process | |
| CN103274632B (en) | Reinforced cement grinding aid and preparation method thereof | |
| CN108623196A (en) | A kind of lime excitation large dosage industrial residue low-carbon cement and preparation method thereof | |
| CN103382124B (en) | A kind of molybdenum tailings air-entrained concrete building block and preparation method thereof | |
| CN101549973A (en) | Compound concrete high efficiency water reducing agent | |
| CN106279705B (en) | A kind of anti-mud sacrifice agent of lignin and preparation method thereof and the application in concrete | |
| CN102180641A (en) | Method and process for high strength curing of drilling waste | |
| CN112047661A (en) | Recycled aggregate concrete additive | |
| CN102838197A (en) | Method for preparing novel composite flocculant PSAFS (poly-silicate aluminum ferrous sulfate) | |
| CN102503220A (en) | Composite steel slag grinding aid | |
| CN104119018A (en) | High-collapse-protection type polycarboxylic water reducer prepared by complex formulation of VC (vitamin C) waste mother liquor | |
| CN102060461A (en) | Cement composite grinding aid and preparation method thereof | |
| CN114044856A (en) | Mud-blocking type polycarboxylate superplasticizer and preparation method thereof | |
| CN109809729B (en) | Method for preparing cement grinding aid by utilizing landfill leachate | |
| CN109135852A (en) | A kind of modification of molasses waste liquid and the preparation method of coal water slurry dispersing agent | |
| CN101857391B (en) | Printing and dyeing sewage recycling method | |
| CN114685080A (en) | Preparation method of phosphogypsum-based cement additive | |
| CN104016602A (en) | Preparation method using industrial waste residue titanium gypsum as cement component | |
| CN109867494B (en) | Preparation method of wall protection slurry for mechanical rotary digging pile | |
| CN103708754B (en) | A kind of ready mixed concrete adulterant and preparation method thereof | |
| CN102614809A (en) | Method for preparing dispersing-stabilizing agent by using papermaking sludge | |
| CN101037311B (en) | Concrete reinforced abrasion-aided additive and its application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20170104 |
|
| WW01 | Invention patent application withdrawn after publication |