CN108017297A - The method and cement grinding aid of a kind of cement grinding - Google Patents
The method and cement grinding aid of a kind of cement grinding Download PDFInfo
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- CN108017297A CN108017297A CN201610964504.4A CN201610964504A CN108017297A CN 108017297 A CN108017297 A CN 108017297A CN 201610964504 A CN201610964504 A CN 201610964504A CN 108017297 A CN108017297 A CN 108017297A
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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
- C04B7/00—Hydraulic cements
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/48—Clinker treatment
- C04B7/52—Grinding ; After-treatment of ground cement
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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
- C04B24/001—Waste organic materials
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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
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The present invention provides the method and cement grinding aid of a kind of cement grinding, this method includes：Cement is treated that abrasive material and cement grinding aid carry out grinding processing together；Wherein, the cement grinding aid contains the saponification waste lye of cyclohexane oxidation preparing cyclohexanone.The method of cement grinding provided by the invention can carry out cement grinding using the saponification waste lye of cyclohexane oxidation preparing cyclohexanone as grinding aid.
Description
Technical field
The present invention relates to the method and cement grinding aid of a kind of cement grinding.
Background technology
Building materials are the important foundation raw and semifinished materials industries for supporting social and economic development, and wherein cement and concrete is building work
Journey and the indispensable basic material of various structures, its purposes is wide, dosage is big, performance is stable and durable.Using manufacture of cement as
Example, existing cement production process are " two mill one burn ", the i.e. grinding of raw material, are calcined and cement finish grinding.For setting for grinding
For as roll squeezer, vertical mill and ball mill, the energy that powder-grinding process consumes in cement production process is very high, and the utilization of energy
Rate is again extremely low, causes the energy consumption of annual manufacture of cement very big.In modern cement industry, cement grinding aid has become cement etc.
Grinding output efficiency is improved in production, grinding pow consumption is reduced, improves strength of cement, improve building materials performance, reduce production cost
One of effective measures.Grinding aid is added in the powder-grinding process of cement can prevent powder reuniting, effectively weaken or prevent " bag
Ball ", improves cement grinding efficiency；Cement quality can be improved, improve product specification.
Cyclohexanone is the basic material for producing nylon, a large amount of waste water is produced in its production process, industry is interior, and referred to as " saponification is given up
Lye ".The waste water whole nation total amount about 800,000 tons/year (with 50% densimeters), COD high, can not directly carry out biochemical treatment.At present
The burning method generally used, not only investment is big, energy consumption is big, also has certain environment to influence, while is also the waste of resource.Cause
This, the processing of saponification waste lye is a great problem of current nylon raw material industry.
The content of the invention
The object of the present invention is to provide the method and cement grinding aid of a kind of cement grinding, cement grinding provided by the invention
Method can using the saponification waste lye of cyclohexane oxidation preparing cyclohexanone as grinding aid carry out cement grinding.
To achieve these goals, the present invention provides a kind of method of cement grinding, and this method includes：Cement is treated into abrasive material
Grinding processing is carried out together with cement grinding aid；Wherein, the cement grinding aid contains the saponification of cyclohexane oxidation preparing cyclohexanone
Spent lye.
Preferably, by weight and on the basis of the weight of the saponification waste lye of the cyclohexane oxidation preparing cyclohexanone, institute
The saponification waste lye for stating cyclohexane oxidation preparing cyclohexanone contains the water of 30-90 weight %.
Preferably, by weight and on the basis of the weight of the saponification waste lye of the cyclohexane oxidation preparing cyclohexanone, institute
The saponification waste lye for stating cyclohexane oxidation preparing cyclohexanone contains the sodium hydroxide of 0.3-5 weight %.
Preferably, the technique of the cyclohexane oxidation preparing cyclohexanone is to be aoxidized selected from cobalt salt catalytic oxidation, boric acid catalysis
Method, titanium molecular sieve catalysis oxidizing process and without at least one of catalyst oxidizing process.
Preferably, the grinding aid also contains pH adjusting agent, and the addition of the pH adjusting agent is to adjust described help
The pH value of grinding agent is subject to 7-14.
Preferably, the pH adjusting agent is selected from hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, carbonic acid, formic acid, acetic acid, oxalic acid, third
At least one in acid, malonic acid, butyric acid, succinic acid, valeric acid, glutaric acid, caproic acid, adipic acid, hydroxycaproic acid, polycarboxylic acids and sulfonic acid
Kind.
Preferably, waste liquid of the grinding aid also containing cyclohexanone caprolactam, the cyclohexanone caprolactam
Waste liquid contains the waste liquid of cyclohexanone oximate preparing cyclohexanone oxime and/or the waste liquid of rearrangement of cyclohexanone-oxime caprolactam；Wherein, it is described
The weight ratio of saponification waste lye and the waste liquid of the cyclohexanone caprolactam is 100：(0-1000).
Preferably, by weight, the waste liquid of the cyclohexanone caprolactam contains 0.1-15 weight % caprolactams, excellent
Select the caprolactam containing 1-15 weight %.
Preferably, the grinding aid also contains cement intensifier, the cement intensifier include selected from alcamines additive,
At least one of sodium salt and/or calcium salt additive, cyanogen amines additives and polyol ethers additive.
Preferably, by weight, the ratio that the alcamines additive accounts for the grinding aid is 10-90 weight %, described
Alcamines additive is monocyclic selected from triethanolamine, triisopropanolamine, three cyclohexanol amine, diethanol monoisopropanolamine, diethanol
The monocyclic hexanol amine of hexanol amine, diisopropanol monoethanolamine, diisopropanol, dicyclohexano monoethanolamine and dicyclohexano list isopropanol
At least one of amine.
Preferably, by weight, the ratio that sodium salt and/or the calcium salt additive accounts for the grinding aid is 1-90 weights
% is measured, sodium salt and/or the calcium salt additive is selected from sodium sulfocyanate, sodium phosphate, sodium chloride, calcium sulfate, calcium chloride, fluosilicic acid
At least one of sodium, sodium sulphate and sodium nitrate.
Preferably, by weight, the ratio that the polyol ethers additive accounts for the grinding aid is 1-90 weight %, preferably
For 1-50 weight %, the polyol ethers additive is included selected from least one of polyalcohol, polyol ethers and carbohydrate, described
Polyalcohol is included selected from least one of ethylene glycol, propane diols, glycerine, polyethylene glycol, three polyglycereol and polypropylene glycol, institute
Stating polyol ethers includes polyglycol ether and/or polypropylene glycol ether, and the carbohydrate is included in white sugar, glucose and molasses
It is at least one.
Preferably, by weight, the ratio that the cyanogen amines additives account for the grinding aid is 10-90 weight %, described
Cyanogen amines additives are included selected from least one of melamine, sulfonated melamine, cyanamide and three cyanamides.
Preferably, the grinding aid also contains defoamer；By weight, the ratio that the defoamer accounts for the grinding aid is
0.01-0.5 weight %, the defoamer include organic silicon defoamer and/or polyether-modified silicon class additive.
Preferably, the grinding aid also contains accelerator for cement slurry, and the accelerator for cement slurry is selected from aluminium salt, magnesium salts, carbonic acid
At least one of salt and silicon salt.
Preferably, by weight, the cement grinding aid accounts for the cement and treats abrasive material and cement grinding aid gross weight
0.01-0.3 weight %.
Preferably, the cement treats that abrasive material includes clinker, including or does not include building materials；The clinker is lime
The calcined product of matter raw material, the calcareous raw material are at least one in lime stone, marl, chalk, shell and coral
Kind；The building materials are selected from flyash, slag, clinker, volcanic ash, sandstone, quartz sand, clay, shale, gypsum, Iron Ore Powder, height
At least one of ridge soil and bauxite.
The present invention also provides a kind of cement grinding aid, the saponification which contains cyclohexane oxidation preparing cyclohexanone is given up
Lye.
The saponification waste lye of cyclohexane oxidation preparing cyclohexanone is carried out cement powder by the method for the present invention
Mill, can both solve the problems, such as that the saponification waste lye of cyclohexane oxidation preparing cyclohexanone is rationally handled, and reached clean environment firendly, low cost
And realize the purpose of comprehensive utilization of resources, there can also be good grinding-aid effect, improve material fluidity in grinding process, drop
Low 45 tm screen is remaining and improves the specific surface area of grinding products therefrom, and does not influence the workability and mechanical property of final cement
Energy.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The present invention provides a kind of method of cement grinding, and this method includes：Cement is treated into abrasive material and cement grinding aid together
Carry out grinding processing；Wherein, the cement grinding aid contains the saponification waste lye of cyclohexane oxidation preparing cyclohexanone.
The present invention also provides a kind of cement grinding aid, the saponification which contains cyclohexane oxidation preparing cyclohexanone is given up
Lye.
According to the present invention, the technique of cyclohexane oxidation preparing cyclohexanone, since 1961 industrialize, research is more, development
Comparatively fast.It is different according to catalyst, including cobalt salt catalytic oxidation, boric acid catalysis oxidizing process, titanium molecular sieve catalysis oxidizing process and
Without catalyst oxidizing process, though technical process respectively has feature, basic principle and reaction process are identical, and specific reaction process can
To be shown below：
In the first step, hexamethylene under catalyst existence condition or without under catalyst existence condition with oxidant (such as
Oxygen) oxidation generation cyclohexyl hydroperoxide.For example, 160 DEG C of reaction temperature, pressure about 1.08MPa, 5 kettle cascade reaction 1h, with
Air contact controls cyclohexane conversion in about 5 weight %, the about 95 weight % of selectivity of cyclohexyl hydroperoxide.
In second step, alkali, such as sodium hydroxide solution will be added in first step products therefrom, its effect is to peroxidating
Thing is decomposed, and the cobalt naphthenate catalysed promoted cyclohexyl mistake of relative response liquid weight 0-10ppm can be added depending on process condition
The decomposition of hydrogen oxide, obtains with cyclohexanoneAnd cyclohexanolBased on organic phase with
And water phase saponification waste lye.The saponification waste lye is generally black liquor or is generally 1.05- containing fraction solids, relative density
1.25 grams per milliliters, by weight and on the basis of the weight of the saponification waste lye, the saponification waste lye can contain 30-
The water of 90 weight %, the sodium hydroxide of 0.3-5 weight % and salt and organic matter etc..
According to the present invention, the saponification waste lye of cyclohexane oxidation preparing cyclohexanone can directly be made without any pretreatment
Grinding is carried out for grinding aid, adds and adjusts the better of additive.Adjusting additive, which refers to be added in grinding aid, to be contributed to
Grinding, the component of enhancing effect are improved, it is formed and additive amount is of the invention and is not limited, and can be added with one-component,
Can also be that conventional grinding aid is added in the form of additive.For example, it is described adjusting additive can include selected from pH adjusting agent,
At least one of cement intensifier, defoamer and accelerator for cement slurry, can also include in urea, lignin salt and calcium formate
At least one, and it is other it is known in those skilled in the art can addO-on therapy.The soap of the cyclohexane oxidation preparing cyclohexanone
The weight ratio for changing spent lye and adjusting additive can be 100：(0-1000), is preferably 100：(1-400).
According to the present invention, since saponification waste lye is containing excessive alkali, to avoid causing the construction intensity of the building materials such as cement
Harmful effect and in order to improve grinding effect, can add the pH value that pH adjusting agent adjusts grinding aid in saponification waste lye,
Its addition present invention does not have concrete restriction, can be to adjust the pH value of the grinding aid as 7-14.The pH value tune
The present invention that forms of section agent is also not specifically limited, such as can be selected from hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, carbonic acid, formic acid, second
Acid, oxalic acid, propionic acid, malonic acid, butyric acid, succinic acid, valeric acid, glutaric acid, caproic acid, adipic acid, hydroxycaproic acid, polycarboxylic acids and sulfonic acid
At least one of.
According to the present invention, cyclohexanone carries out oximate and the technique of rearrangement reaction caprolactam, due to phosphoric acid byproduct ammonium, sulphur
The inorganic salts such as sour ammonium, sodium nitrate, further include multiple productions such as extraction, back extraction, ion exchange, rectifying in addition to above-mentioned two steps main reaction
Product purification step, these steps obtain refining at the same time, can produce respective waste liquid, such as refine acyl in oneself by extracting process in product
Amine, ammonium sulfate, can bring the waste liquid including caprolactam, ammonium sulfate chemical constituent into abstraction waste liquor, these waste liquids are referred to as ring
The waste liquid of hexanone caprolactam, about 500,000 tons/year of waste liquid whole nation total amount (with 50 weight % densimeters), COD high, Wu Fazhi
Tap into row biochemical treatment.The burning method generally used at present, not only investment is big, energy consumption is big, also has certain environment to influence, at the same time
And the waste of resource.
According to the present invention, the waste liquid of the cyclohexanone caprolactam can contain the useless of cyclohexanone oximate preparing cyclohexanone oxime
The waste liquid of liquid and/or rearrangement of cyclohexanone-oxime caprolactam, it is preferable that ring described in the waste liquid of the cyclohexanone caprolactam
The waste liquid of hexanone oximate preparing cyclohexanone oxime and the weight ratio of the waste liquid of the rearrangement of cyclohexanone-oxime caprolactam are (0-30)：
(70-100)。
According to the present invention, cyclohexanone can include choosing with progress oximation reaction preparing cyclohexanone oxime, its techniques such as azanols
At least one from Raschig process (HSO methods), nitric oxide method (NO methods), phosphatic hydroxylamine method (HPO methods) and oximes method (HAO methods)
Kind, such as the concrete technology step of oximes method can be shown below：
During cyclohexanone oximate preparing cyclohexanone oxime
Water phase and cleaning filter can produce acid-alkali salt waste water, which is known as the waste liquid of cyclohexanone oximate preparing cyclohexanone oxime, mainly into
It is divided into water, ammonium salt such as ammonium phosphate, sodium nitrate, sodium phosphate etc..
According to the present invention, cyclohexanone oxime can exist in sulfuric acid or oleum or catalyst (such as Titanium Sieve Molecular Sieve)
Lower carry out intramolecular rearrangement, obtains caprolactam, this reaction is known as beckmann rearrangement rearrangement reaction.If use oleum, weight
After row generally use ammonium hydroxide in and oleum, a large amount of ammonium sulfate of by-product.Ensure quality at the same time to improve caprolactam yield, subsequently
Ammonium sulfate is extracted, the caprolactam crude product for resetting generation is extracted and is stripped, extraction is generally using molten
Agent such as benzene, toluene.In addition, caprolactam removes the inorganic salts such as remaining ammonium sulfate by cation and anion exchange technique after extraction.
Such as concentrating spent liquor after concentrating spent liquor, back extraction after extracting and the waste liquid after ion exchange caused by these product purification steps,
The referred to as waste liquid of rearrangement of cyclohexanone-oxime caprolactam, the waste liquid of abbreviation oxime rearrangement.The rearrangement of cyclohexanone-oxime caprolactam
Main organic component such as caprolactam, adjacent cyclohexanediol, adjacent hydroxy-cyclohexanone, hexanal etc., primary non-organic component such as nitre in waste liquid
Sour sodium, ammonium sulfate, sodium sulfocyanate etc..Specific reaction process step can be shown below：
According to the present invention, the waste liquid of the cyclohexanone caprolactam preferably comprises 0.1-15 weight % caprolactams, 30-
The water of 80 weight % and the inorganic salts of 2-60 weight %, further preferably 1-15 weight % caprolactams, the water of 30-80 weight %
With the inorganic salts of 5-60 weight %.Caprolactam helps to improve the intensity of cement products, and the inorganic salts can include being selected from
At least one of sodium nitrate, sodium sulphate, sodium sulfocyanate, sodium chloride, sodium carbonate, ammonium nitrate and ammonium sulfate.The saponification salkali waste
The weight ratio of liquid and the waste liquid of the cyclohexanone caprolactam can be 100：(0-1000), is preferably 100：(1-400).
According to the present invention, the cement intensifier can be included selected from alcamines additive, sodium salt and/or calcium salt addition
At least one of agent, cyanogen amines additives and polyol ethers additive.
According to the present invention, alcamines additive helps to eliminate electrostatic, improves grinding effect and improves product strength, described
The ratio that alcamines additive accounts for the grinding aid can be 10-90 weight %, and the alcamines additive can be selected from three
Monoethanolamine, triisopropanolamine, three cyclohexanol amine, diethanol monoisopropanolamine, the monocyclic hexanol amine of diethanol, diisopropanol monoethanol
At least one of the monocyclic hexanol amine of amine, diisopropanol, dicyclohexano monoethanolamine and dicyclohexano monoisopropanolamine.
According to the present invention, sodium salt and/or the calcium salt additive can improve grindability and mobility that cement treats abrasive material,
And improve the intensity of cement products.By weight, the ratio that sodium salt and/or the calcium salt additive accounts for the grinding aid can be
1-90 weight %, sodium salt and/or the calcium salt additive can be selected from sodium sulfocyanate, sodium phosphate, sodium chloride, calcium sulfate, chlorine
Change at least one of calcium, prodan, sodium sulphate and sodium nitrate.
According to the present invention, polyol ethers additive helps to eliminate electrostatic, improves grinding effect, and improve cement products
Intensity.By weight, the ratio that the polyol ethers additive accounts for the grinding aid can be 1-90 weight %, be preferably 1-50
Weight %, the polyol ethers additive can be included selected from least one of polyalcohol, polyol ethers and carbohydrate, described more
First alcohol can be included selected from least one of ethylene glycol, propane diols, glycerine, polyethylene glycol, three polyglycereol and polypropylene glycol,
The polyol ethers can include polyglycol ether and/or polypropylene glycol ether, and the carbohydrate can be included selected from white sugar, glucose
At least one of with molasses.
According to the present invention, cyanogen amines additives help to eliminate electrostatic, improve grinding effect, and can improve cement products
Intensity, by weight, the ratio that the cyanogen amines additives account for the grinding aid can be 10-90 weight %, the cyanamide
Class additive can be included selected from least one of melamine, sulfonated melamine, cyanamide and three cyanamides.
According to the present invention, defoamer can be used for the surface tension for reducing grinding aid, suppress foam generation or eliminate to have produced
Raw foam, so as to improve grinding-aid effect.By weight, the ratio that the defoamer accounts for the grinding aid can be 0.01-0.5
Weight %, the defoamer can include organic silicon defoamer and/or polyether-modified silicon class additive, the organic silicon disappear
Infusion can be selected from least one of dimethyl silicone polymer, fluorosilicone and ethylene glycol siloxanes, commercially available can also mix
The solidifying special defoamer of soil, such as Dongguan De Feng defoamers Co., Ltd building materials industry class defoamer, product type " DF-179 " and
“DF-175”。
According to the present invention, the grinding aid can also contain accelerator for cement slurry, and the accelerator for cement slurry can be selected from aluminium
At least one of salt, magnesium salts, carbonate and silicon salt.
According to the present invention, grinding aid can be used for the grinding that cement treats abrasive material with the interior volume of 0.01-0.3 weight %, with
Improve the efficiency of grinding and the performance of gained ground prod.
Cement treats that abrasive material refers generally to clinker, and clinker refers to using calcium carbonate as the calcareous raw material of main component
Calcined product, for preparing cement finish powder after grinding, the cement finish powder refers to that clinker and the mixing of other mixed materials are laggard
The product of row grinding, that is, form the component of cement, and method of the invention can be used for the cement for preparing the various trades mark, such as
It can be used for the cement finish powder for preparing PO 42.5, PI 42.5 or PC32.5R cement.The calcareous raw material can be selected from stone
Lime stone, marl, chalk, shell and alcyonarian raw material.Wherein, the essential mineral of lime stone is calcite, and carbonate-free lime stone contains CaO
About 56%, loss on ignition is about 44%；Marl is the mixed uniformly sedimentary rock that calcium carbonate and clay deposit formation at the same time, it is led
It is calcite to want mineral, the malmy CaO content of high calcium >=45 weight %, the malmy 45 weight % of CaO content ＜ of low calcium；In vain
The material that chalk is sea hydrobiont shell to be formed with shell accumulation, its main component are calcium carbonate, content 80-90%；The shellfish
The calcium carbonate content of shell and alcyonarian raw material is 90% or so.
In cement grinding, in order to improve cement performance, adjust strength of cement grade, increase cement output etc., and mix
Artificial or natural mineral material, is known as cement mixture, the cement mixture can include flyash, slag, clinker,
One or more in volcanic ash, sandstone, quartz sand, clay, shale, gypsum, Iron Ore Powder, kaolin and bauxite.
China is a building materials consumption big country, and by taking cement as an example, cement total output has reached 1,800,000,000 tons within 2011, by grinding aid
Agent dosage accounts for 0.05 weight % of cement products calculating, about needs 900,000 tons of grinding aid, grinding aid of the invention both rationally make use of
Chemical products waste liquid, it may have significantly more economic benefit and environmental benefit.
According to the present invention, this area conventional technical means can be used by adding the operation of grinding aid progress grinding, for example with
Ball mill, roll squeezer or vertical mill grinding 20-40min.
The present invention will be further illustrated by embodiment below, but the present invention is not therefore subject to any restriction.
The embodiment of the present invention be derived from using saponification waste lye on June 3rd, 2016 Sinopec Group Ba Ling branch companies oneself
The saponification waste lye produced in lactams division department Cyclohexane Oxidation Unit, cyclohexane oxidation preparing cyclohexanone technique are no catalyst
Oxidizing process, is denoted as A liquid, its property is：Relative density is 1.197 grams/cc, and water content is 42 weight %, sodium hydroxide
Content is 2 weight %.
The embodiment of the present invention is denoted as C liquid using the waste liquid of cyclohexanone caprolactam, is derived from Ba Ling points of Sinopec Group
The corresponding process units of caprolactam division department of company, it contains the waste liquid and 90 weights of 10 weight % cyclohexanone oximate preparing cyclohexanone oximes
Measure the waste liquid of % rearrangement of cyclohexanone-oxime caprolactams.C liquid specific natures are：1.16 grams/cc of relative density, ammonium nitrate
Content is 14 weight %, and ammonium sulphate content is 10 weight %, and sodium sulfocyanate content is 11 weight %, and caprolactam content is 6 weights
% is measured, water content is 55 weight %, the impurity such as the aliphatic acid of 4% surplus is received, paraffin oil and organosilicon.
The adjusting additive has been used to be in embodiment：Sulfuric acid, acetic acid, adipic acid, triethanolamine and three polyglycereol, are business
Purchase.
The embodiment of the present invention and comparative example use《National Standard of the People's Republic of China's GB/T26748-2011 cements
Agent》In method be detected.
The embodiment of the present invention and comparative example the grinding grinding-aid effect in GB/T 26748-2011 standard appendix As are met are tested
Carried out in the national standard cement test small grinding of method.
Comparative example DA1 and embodiment SA1-SA5 explanations are only with A liquid as cement grinding aid to cement grog grinding effect
Influence.
Comparative example DA1
Clinker (commercial grades are PO42.5 cement) is subjected to grinding processing, actual conditions and the results are shown in Table 1.
Embodiment SA1-SA5
A liquid is subjected to grinding processing to mix clinker (commercial grades is PO42.5 cement) in different part by weight,
Actual conditions and it the results are shown in Table 1.
Table 1：The grinding condition and result of comparative example DA1 and embodiment SA1-SA5
As can be seen from Table 1：1st, after adding saponification waste lye, the mobility of all materials improves；2nd, soap is added
After changing spent lye, the remaining drop of 45 tm screens of all materials；3rd, after adding saponification waste lye, the ratio of embodiment SA1-SA5 materials
Surface area all increases, but excessive addition, can increase substantially the mobility of material, reduce between material, abrasive media
Frictional force, makes material not ground effectively, so specific surface area declines while increase is tailed over.These result tables
Bright, which has good grind -aiding effect to clinker.
Embodiment SB1-SB4 explanations use A liquid (in terms of 100 parts by weight), add and do not add conduct after adjusting additive
Influence of the cement grinding aid to cement grog grinding effect, the commercial grades of clinker are used in embodiment SB1-SB4
PO42.5。
Embodiment SB1
Using A liquid as grinding aid with mixed in the ratio of 0.05 weight % clinker carry out grinding processing, actual conditions and
It the results are shown in Table 2.
Embodiment SB2
Using A liquid addition sulfuric acid adjust to pH value be 10 after as grinding aid, it is ripe with water mixing mud in the ratio of 0.05 weight %
Material carries out grinding processing, actual conditions and the results are shown in Table 2.
Embodiment SB3
It is 10 that A liquid addition acetic acid, which is adjusted to pH value, is made after adding the triethanolamines of 40 parts by weight, 30 parts by weight C liquid
For grinding aid, grinding processing is carried out to mix clinker in the ratio of 0.05 weight %, actual conditions and the results are shown in Table 2.
Embodiment SB4
Add adipic acid to make pH to 10 A liquid, add the triethanolamine, 25 parts by weight C liquid and 15 parts by weight of 30 parts by weight
Grinding aid is used as after three polyglycereol, grinding processing, actual conditions and knot are carried out to mix clinker in the ratio of 0.05 weight %
Fruit is shown in Table 2.
Table 2：The grinding condition and result of embodiment SB1-SB4
As can be seen from Table 2：It will add and be adjusted after additive optimizes in A liquid, more than 45 tm screen of all materials
Decline and specific surface area increased, illustrate there is effect of optimization to the saponification waste lye after adding adjusting additive.
Comparative example DC1
Comparative example DC1 is used《National Standard of the People's Republic of China's GB/T 50080-2002 normal concrete mix physical property
Can test method standard》The trade mark for measuring cement products is the workability of PO 42.5, specific test condition and the results are shown in Table 3.
Embodiment SC1-SC4
Embodiment SC1-SC4 illustrates A liquid and containing influence of the A liquid of additive to cement workability is adjusted, by embodiment
Grinding aid is mixed in cement products with the ratio of 0.05 weight % in SB1-SB4, and the trade mark of cement products used is PO 42.5,
Specific test method is shown in《National Standard of the People's Republic of China's GB/T 50080-2002 normal concrete mixture performance tests
Method standard》, specific test condition and the results are shown in Table 3.
Table 3：Comparative example DC1 and embodiment SC1-SC4 illustrates influence of the saponification waste lye to cement workability
As can be seen from Table 3, the addition of saponification waste lye adds the consumptive use of water normal consistence of cement, shortens solidifying
The time is tied, the influence to glue sand mobile phase is increased slightly or remains unchanged, and meets national standard.
Comparative example DD1-DD3
The comparative example DD1-DD3 measure trades mark are PI 52.5, PO 42.5, the cement mechanical property of PC 32.5R, specific to survey
Method for testing is shown in《National Standard of the People's Republic of China's GB/T 50081-2002 normal concrete mechanical test method marks
It is accurate》, specific test condition and the results are shown in Table 4.
Embodiment SD1-SD3
Embodiment SD1-SD3 illustrates influence of the saponification waste lye to cement mechanical property, by the grinding aid of embodiment SB4 with
In 0.05 weight % ratios incorporation cement, the trade mark of cement used is PI 52.5, PO 42.5, PC 32.5R, specific test side
Method is shown in《National Standard of the People's Republic of China's GB/T 50081-2002 standard for test methods of mechanical properties of ordinary concretes》, tool
Body test condition and it the results are shown in Table 4.
Table 4：Comparative example DD1-DD3 and embodiment SD1-SD3 illustrates influence of the saponification waste lye to cement workability
From the results shown in Table 4, due to the difference of cement, the strength of cement change difference after grinding aid, institute are filled
The cement mortar compression strength for having age has increased and amplitude meets the requirement of national Specification.
Although above the present invention is made to retouch in detail with general explanation, embodiment and experiment
State, but on the basis of the present invention, it can be made some modifications or improvements, or add known or even ripe grinding aid component,
Such as polycarboxylic acid salt, lignin sulfonate, polyacrylamide, this will be apparent to those skilled in the art.
Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to claimed model
Enclose.
Claims (18)
1. a kind of method of cement grinding, this method include：Cement is treated that abrasive material and cement grinding aid carry out grinding processing together；
Wherein, the cement grinding aid contains the saponification waste lye of cyclohexane oxidation preparing cyclohexanone.
2. according to the method described in claim 1, wherein, give up by weight and with the saponification of the cyclohexane oxidation preparing cyclohexanone
On the basis of the weight of lye, the saponification waste lye of the cyclohexane oxidation preparing cyclohexanone contains the water of 30-90 weight %.
3. according to the method described in claim 1, wherein, give up by weight and with the saponification of the cyclohexane oxidation preparing cyclohexanone
On the basis of the weight of lye, the saponification waste lye of the cyclohexane oxidation preparing cyclohexanone contains the sodium hydroxide of 0.3-5 weight %.
4. according to the method described in claim 1, wherein, the technique of the cyclohexane oxidation preparing cyclohexanone is to be catalyzed selected from cobalt salt
Oxidizing process, boric acid catalysis oxidizing process, titanium molecular sieve catalysis oxidizing process and without at least one of catalyst oxidizing process.
5. according to the method described in claim 1, wherein, the grinding aid also contains pH adjusting agent, the pH adjusting agent
Addition to adjust the pH value of the grinding aid as 7-14.
6. according to the method described in claim 5, wherein, the pH adjusting agent is selected from hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, carbon
It is acid, formic acid, acetic acid, oxalic acid, propionic acid, malonic acid, butyric acid, succinic acid, valeric acid, glutaric acid, caproic acid, adipic acid, hydroxycaproic acid, poly-
At least one of carboxylic acid and sulfonic acid.
7. according to the method described in claim 1, wherein, waste liquid of the grinding aid also containing cyclohexanone caprolactam, institute
The waste liquid and/or rearrangement of cyclohexanone-oxime system that the waste liquid for stating cyclohexanone caprolactam contains cyclohexanone oximate preparing cyclohexanone oxime are in oneself
The waste liquid of acid amides；Wherein, the weight ratio of the saponification waste lye and the waste liquid of the cyclohexanone caprolactam is 100：(0-
1000)。
8. according to the method described in claim 7, wherein, by weight, the waste liquid of the cyclohexanone caprolactam contains
0.1-15 weight % caprolactams.
9. according to the method described in claim 1, wherein, the grinding aid also contains cement intensifier, the cement intensifier
Including in alcamines additive, sodium salt and/or calcium salt additive, cyanogen amines additives and polyol ethers additive at least
It is a kind of.
10. according to the method described in claim 9, wherein, by weight, the alcamines additive accounts for the ratio of the grinding aid
Example is 10-90 weight %, and the alcamines additive is selected from triethanolamine, triisopropanolamine, three cyclohexanol amine, diethanol list
The monocyclic hexanol amine of isopropanolamine, diethanol, diisopropanol monoethanolamine, the monocyclic hexanol amine of diisopropanol, dicyclohexano monoethanol
At least one of amine and dicyclohexano monoisopropanolamine.
11. according to the method described in claim 9, wherein, by weight, sodium salt and/or the calcium salt additive accounts for described help
The ratio of grinding agent is 1-90 weight %, and sodium salt and/or the calcium salt additive is selected from sodium sulfocyanate, sodium phosphate, sodium chloride, sulphur
At least one of sour calcium, calcium chloride, prodan, sodium sulphate and sodium nitrate.
12. according to the method described in claim 9, wherein, by weight, the polyol ethers additive accounts for the grinding aid
Ratio is 1-90 weight %, and the polyol ethers additive is included selected from least one of polyalcohol, polyol ethers and carbohydrate,
The polyalcohol includes at least one in ethylene glycol, propane diols, glycerine, polyethylene glycol, three polyglycereol and polypropylene glycol
Kind, the polyol ethers include polyglycol ether and/or polypropylene glycol ether, and the carbohydrate includes being selected from white sugar, glucose and sugar
At least one of honey.
13. according to the method described in claim 9, wherein, by weight, the cyanogen amines additives account for the ratio of the grinding aid
Example is 10-90 weight %, and the cyanogen amines additives include being selected from melamine, sulfonated melamine, cyanamide and three cyanamides
At least one of.
14. according to the method described in claim 1, wherein, the grinding aid also contains defoamer；By weight, the defoaming
The ratio that agent accounts for the grinding aid is 0.01-0.5 weight %, and the defoamer includes organic silicon defoamer and/or polyethers changes
Property silicon class additive.
15. according to the method described in claim 1, wherein, the grinding aid also contains accelerator for cement slurry, the accelerator for cement slurry
For selected from least one of aluminium salt, magnesium salts, carbonate and silicon salt.
16. according to the method described in claim 1, wherein, by weight, the cement grinding aid account for the cement treat abrasive material and
The 0.01-0.3 weight % of cement grinding aid gross weight.
17. according to the method described in claim 1, wherein, the cement treats that abrasive material includes clinker, including or does not include water
Cement mixture；The clinker is the calcined product of calcareous raw material, and the calcareous raw material is selected from lime stone, plaster
At least one of rock, chalk, shell and coral；The cement mixture is selected from flyash, slag, clinker, volcanic ash, sand
At least one of rock, quartz sand, clay, shale, gypsum, Iron Ore Powder, kaolin and bauxite.
18. a kind of cement grinding aid, which contains the saponification waste lye of cyclohexane oxidation preparing cyclohexanone.
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| CN108017296A (en) * | 2016-10-28 | 2018-05-11 | 湖南昌迪环境科技有限公司 | A kind of grinding aid and its application |
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| CN108017300B (en) * | 2016-10-28 | 2020-05-15 | 湖南昌迪环境科技有限公司 | Cement grinding method and cement grinding aid |
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| CN110790524B (en) * | 2019-10-30 | 2021-09-28 | 东南大学 | Steel slag acidic vertical grinding agent and preparation and application thereof |
| CN115893907A (en) * | 2022-12-31 | 2023-04-04 | 卫辉市春江水泥有限公司 | Composite cement grinding aid and preparation method thereof |
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