CN108017301B - Method for grinding cement admixture and cement admixture grinding aid - Google Patents

Method for grinding cement admixture and cement admixture grinding aid Download PDF

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CN108017301B
CN108017301B CN201610967135.4A CN201610967135A CN108017301B CN 108017301 B CN108017301 B CN 108017301B CN 201610967135 A CN201610967135 A CN 201610967135A CN 108017301 B CN108017301 B CN 108017301B
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grinding aid
sodium
cyclohexanone
grinding
caprolactam
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CN108017301A (en
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钱文斌
蒋卫和
屈铠甲
刘佑君
王兆祥
杨浴
钱泽萱
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Hunan Changde Environment Technology Co ltd
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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B7/00Hydraulic cements
    • C04B7/36Manufacture of hydraulic cements in general
    • C04B7/48Clinker treatment
    • C04B7/52Grinding ; After-treatment of ground cement
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/001Waste organic materials
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039Premixtures of ingredients
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/52Grinding aids; Additives added during grinding

Abstract

The invention provides a method for grinding cement admixture and a cement admixture grinding aid, and the method comprises the following steps: grinding the cement mixture to be ground and the cement mixture grinding aid together; wherein the cement admixture grinding aid contains waste liquid from the preparation of caprolactam from cyclohexanone. The method for grinding the cement admixture can be used for grinding the cement admixture by taking the waste liquid of caprolactam prepared by cyclohexanone as a grinding aid.

Description

Method for grinding cement admixture and cement admixture grinding aid
Technical Field
The invention relates to a method for grinding cement admixture and a cement admixture grinding aid.
Background
Artificial or natural mineral materials, called cement admixtures, are incorporated in order to improve cement properties, adjust cement strength levels, increase cement production, etc. Most of the currently used cement admixture is industrial waste residue. The mixed materials are generally classified into two major groups, active mixed materials and inactive mixed materials, depending on their properties, wherein the active mixed material is used in the largest amount. The active mixed materials are commonly used granulated blast furnace slag, pozzolanic mixed materials, fly ash and the like, and the inactive mixed materials comprise fine powders ground from quartzite, sandstone and the like. In the production process, the grinding process consumes high energy, the utilization rate of the energy is extremely low, and the production energy consumption is very high. The grinding aid can improve the grinding efficiency in production, reduce the power consumption of grinding and is one of effective measures for reducing the production cost.
The process for preparing caprolactam by oximation and rearrangement reaction of cyclohexanone also comprises a plurality of product refining steps such as extraction, back extraction, ion exchange, rectification and the like besides the two-step main reaction due to inorganic salts such as ammonium phosphate, ammonium sulfate, sodium nitrate and the like which are byproducts, and when the products are refined, respective waste liquid can be generated, for example, caprolactam and ammonium sulfate are refined by an extraction method, the extraction waste liquid can bring waste liquid containing chemical components of caprolactam and ammonium sulfate, the waste liquid is collectively called the waste liquid for preparing caprolactam from cyclohexanone, the national total amount of the waste liquid is about 50 ten thousand tons/year (with a concentration of 50 weight percent), COD is high, and biochemical treatment cannot be directly carried out. The currently widely adopted incineration method has the disadvantages of large investment, large energy consumption, certain environmental influence and resource waste.
Disclosure of Invention
The invention aims to provide a cement admixture grinding method and a cement admixture grinding aid.
In order to achieve the above object, the present invention provides a method for grinding cement admixture, comprising: grinding the cement mixture to be ground and the cement mixture grinding aid together; wherein the cement admixture grinding aid contains waste liquid from the preparation of caprolactam from cyclohexanone.
Preferably, the waste liquid from the production of caprolactam from cyclohexanone contains waste liquid from the production of cyclohexanone oxime from the oximation of cyclohexanone and/or waste liquid from the production of caprolactam from the rearrangement of cyclohexanone oxime.
Preferably, the waste liquid from the production of caprolactam from cyclohexanone contains 0.1-15 wt% of caprolactam, preferably 1-15 wt% of caprolactam.
Preferably, the waste liquid from the cyclohexanone production of caprolactam contains 2-60 wt% of inorganic salt, preferably 5-60 wt% of inorganic salt, wherein the inorganic salt comprises at least one selected from sodium nitrate, sodium sulfate, sodium thiocyanate, sodium chloride, sodium carbonate, ammonium nitrate and ammonium sulfate.
Preferably, the grinding aid also contains a pH value regulator, and the addition amount of the pH value regulator is based on the regulation of the pH value of the grinding aid to 7-14.
Preferably, the pH adjustor is at least one selected from the group consisting of lithium oxide, sodium oxide, potassium oxide, calcium oxide, magnesium oxide, aluminum oxide, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, calcium carbonate, magnesium carbonate, and trisodium phosphate.
Preferably, the grinding aid also contains saponification waste lye generated by preparing cyclohexanone through oxidizing cyclohexane; wherein the weight ratio of the saponified waste lye to the waste liquid from the preparation of caprolactam from cyclohexanone is 100: (0-1000).
Preferably, the saponified spent lye contains 30 to 90% by weight of water, based on the weight of the saponified spent lye.
Preferably, the saponified spent lye contains 0.3 to 5% by weight of sodium hydroxide, based on the weight of the saponified spent lye.
Preferably, the process for preparing cyclohexanone by oxidizing cyclohexane is at least one selected from a cobalt salt catalytic oxidation method, a boric acid catalytic oxidation method, a titanium silicalite molecular sieve catalytic oxidation method and a catalyst-free oxidation method.
Preferably, the grinding aid further comprises a cement enhancing agent comprising at least one member selected from the group consisting of an alcamines additive, a sodium and/or calcium salt additive, a cyanamide additive, and a polyol ether additive.
Preferably, the alkanolamine additive accounts for 10-90 wt% of the grinding aid by weight, and is at least one selected from the group consisting of triethanolamine, triisopropanolamine, tricyclohexanolamine, diethanol monoisopropanolamine, diethanol monocyclohexanolamine, diisopropanol monoethanolamine, diisopropanol monocyclohexanolamine, dicyclohexylalcohol monoethanolamine and dicyclohexylalcohol monoisopropanolamine.
Preferably, the sodium salt and/or calcium salt additive accounts for 1-90 wt% of the grinding aid by weight, and the sodium salt and/or calcium salt additive is at least one selected from sodium thiocyanate, sodium phosphate, sodium chloride, calcium sulfate, calcium chloride, sodium fluorosilicate, sodium sulfate and sodium nitrate.
Preferably, the polyol ether additive comprises at least one selected from the group consisting of polyols, polyol ethers and sugars, the polyols comprise at least one selected from the group consisting of ethylene glycol, propylene glycol, glycerol, polyethylene glycol, triglycerol and polypropylene glycol, the polyol ethers comprise polyethylene glycol ethers and/or polypropylene glycol ethers, and the sugars comprise at least one selected from the group consisting of white sugar, glucose and molasses, in a proportion of 1 to 90% by weight, preferably 1 to 50% by weight, of the grinding aid.
Preferably, the cyanamide additive accounts for 10-90 wt% of the grinding aid, and the cyanamide additive comprises at least one selected from melamine, sulfonated melamine, cyanamide and tricyanamide.
Preferably, the grinding aid further comprises a defoamer; the defoaming agent accounts for 0.01-0.5 wt% of the grinding aid by weight, and comprises an organic silicon defoaming agent and/or a polyether modified silicon additive.
Preferably, the grinding aid further comprises a cement accelerator which is at least one selected from the group consisting of aluminum salts, magnesium salts, carbonates, and silica salts.
Preferably, the grinding aid for the cement admixture accounts for 0.01 to 0.3 weight percent of the total weight of the grinding aid for the cement admixture and the material to be ground.
Preferably, the cement admixture to be ground is at least one selected from the group consisting of fly ash, slag, volcanic ash, sandstone, quartz sand, clay, shale, iron ore powder, kaolin, and bauxite.
The invention also provides a cement admixture grinding aid which contains the waste liquid from the preparation of caprolactam from cyclohexanone.
The method of the invention uses the waste liquid of caprolactam prepared by cyclohexanone as cement admixture grinding aid to grind cement admixture, which not only can solve the problem of reasonable treatment of the waste liquid of caprolactam prepared by cyclohexanone, achieve the purposes of cleanness, environmental protection, low cost and comprehensive utilization of resources, but also has good grinding aid effect, improves material fluidity in the grinding process, reduces 45 micron screen residue, improves the specific surface area of the product obtained by grinding, and does not influence the final construction performance and mechanical performance of cement.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The invention provides a method for grinding cement admixture, which comprises the following steps: grinding the cement mixture to be ground and the cement mixture grinding aid together; wherein the cement admixture grinding aid contains waste liquid from the preparation of caprolactam from cyclohexanone.
The invention also provides a cement admixture grinding aid which contains the waste liquid from the preparation of caprolactam from cyclohexanone.
According to the invention, the waste liquid from the production of caprolactam from cyclohexanone can contain the waste liquid from the production of cyclohexanone oxime from the oximation of cyclohexanone and/or the waste liquid from the production of caprolactam from rearrangement of cyclohexanone oxime, preferably, the weight ratio of the waste liquid from the production of cyclohexanone oxime from the oximation of cyclohexanone to the waste liquid from the production of caprolactam from rearrangement of cyclohexanone oxime in the waste liquid from the production of caprolactam from cyclohexanone is (0-30): (70-100).
According to the present invention, cyclohexanone may be oximated with hydroxylamine or the like to produce cyclohexanone oxime, and the process may include at least one selected from the group consisting of raschig method (HSO method), nitric oxide method (NO method), hydroxylamine phosphate method (HPO method), and ammoximation method (HAO method), and for example, the specific process steps of ammoximation method may be represented by the following formula:
Figure BDA0001145939590000051
in the process of preparing cyclohexanone oxime by oximating cyclohexanone, acid-base salt wastewater is generated by a water phase and a cleaning filter, the wastewater is called waste liquid for preparing cyclohexanone oxime by oximating cyclohexanone, and the main components of the waste liquid are water and ammonium salts such as ammonium phosphate, sodium nitrate, sodium phosphate and the like.
According to the present invention, cyclohexanone oxime may be subjected to intramolecular rearrangement in the presence of sulfuric acid or oleum or a catalyst (e.g., a titanium silicalite molecular sieve) to obtain caprolactam, which is referred to as beckmann transposition rearrangement reaction. When fuming sulfuric acid is used, the fuming sulfuric acid is generally neutralized with ammonia water after rearrangement, and a large amount of ammonium sulfate is produced as a by-product. In order to improve the yield of caprolactam and ensure the quality, ammonium sulfate solution is extracted subsequently, and the caprolactam crude product generated by rearrangement is extracted and back-extracted, wherein solvents such as benzene and toluene are generally adopted for extraction. In addition, after extraction, the caprolactam is subjected to anion-cation exchange process to remove residual inorganic salts such as ammonium sulfate and the like. The waste liquid after extraction, the waste liquid after back extraction and the waste liquid after ion exchange, which are generated in the product refining steps, are called the waste liquid for preparing caprolactam through cyclohexanone-oxime rearrangement, and are called the waste liquid for oxime rearrangement for short. The waste liquid from caprolactam rearrangement production comprises main organic components such as caprolactam, o-cyclohexanediol, o-hydroxycyclohexanone, hexanal and the like, and main inorganic components such as sodium nitrate, ammonium sulfate, sodium thiocyanate and the like. The specific reaction process steps can be shown as follows:
Figure BDA0001145939590000061
according to the invention, the waste liquid from the production of caprolactam from cyclohexanone preferably contains 0.1-15 wt.% of caprolactam, 30-80 wt.% of water and 2-60 wt.% of inorganic salts, more preferably contains 1-15 wt.% of caprolactam, 30-80 wt.% of water and 5-60 wt.% of inorganic salts. The caprolactam contributes to the strength of the cement product, and the inorganic salt may include at least one selected from the group consisting of sodium nitrate, sodium sulfate, sodium thiocyanate, sodium chloride, sodium carbonate, ammonium nitrate, and ammonium sulfate.
According to the invention, the waste liquid from the preparation of caprolactam from cyclohexanone can be directly used as a grinding aid for grinding without any pretreatment, and the effect of adding the adjusting additive is better. The adjusting additive refers to a component which is added into the grinding aid and is helpful for improving grinding and enhancing effects, and the composition and the addition amount of the adjusting additive are not limited in the invention, and the adjusting additive can be added as a single component or a conventional grinding aid in the form of an additive. For example, the conditioning additive may include at least one selected from a pH adjuster, a cement enhancer, a defoamer, and a cement accelerator, and may further include at least one of urea, a lignin salt, and calcium formate, and other addable components known to those skilled in the art. The weight ratio of the waste liquid of caprolactam prepared from cyclohexanone to the regulating additive can be 100: (0-1000), preferably 100: (1-400).
According to the invention, because the waste liquid from the preparation of caprolactam from cyclohexanone contains excessive acid, in order to avoid adverse effects on the construction strength of building materials such as cement and to improve the grinding effect, a pH value regulator can be added into the waste liquid from the preparation of caprolactam from cyclohexanone to regulate the pH value of a grinding aid, the addition amount of the pH value regulator is not particularly limited, and the pH value of the grinding aid can be regulated to 7-14. The composition of the pH adjuster is not particularly limited in the present invention, and may be, for example, oxides and hydroxides corresponding to alkali metals and alkaline earth metals, and salts of weak acids such as carbonic acid, phosphoric acid, and acetic acid, and is preferably at least one selected from the group consisting of lithium oxide, sodium oxide, potassium oxide, calcium oxide, magnesium oxide, aluminum oxide, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, calcium carbonate, magnesium carbonate, and trisodium phosphate.
According to the invention, the process for preparing cyclohexanone by oxidizing cyclohexane is researched more since the industrialization in 1961. According to different catalysts, including cobalt salt catalytic oxidation, boric acid catalytic oxidation, titanium silicalite catalytic oxidation and catalyst-free oxidation, although the technological processes have various characteristics, the basic principle and the reaction flow are the same, and the specific reaction flow can be shown as the following formula:
Figure BDA0001145939590000071
in the first step, cyclohexane is oxidized with an oxidizing agent (e.g., oxygen) in the presence or absence of a catalyst to form cyclohexyl hydroperoxide. For example, the reaction temperature is 160 ℃, the pressure is about 1.08MPa, 5 kettles are connected in series for reaction for 1h, the conversion rate of cyclohexane is controlled to be about 5 weight percent by contacting with air, and the selectivity of cyclohexyl hydroperoxide is about 95 weight percent.
In the second step, alkali, such as sodium hydroxide solution, is added into the product obtained in the first step, the function of the alkali is to decompose peroxide, and cobalt naphthenate with the weight of 0-10ppm relative to the weight of the reaction liquid can be added to catalyze and promote the decomposition of cyclohexyl hydroperoxide according to the process condition, so that cyclohexanone is obtained
Figure BDA0001145939590000072
And cyclohexanol
Figure BDA0001145939590000073
Mainly organic phase and water phase, namely saponification waste lye.
The saponified waste lye is generally a black liquid or a liquid containing a portion of solids, and has a density of generally 1.05 to 1.25 g/ml, and may contain 30 to 90% by weight of water, 0.3 to 5% by weight of sodium hydroxide, salts, organic substances, etc., based on the weight of the saponified waste lye. The grinding aid can also contain saponified waste lye; wherein the weight ratio of the saponification waste lye to the waste liquid of the caprolactam preparation from cyclohexanone can be 100: (0-1000), preferably 100: (1-400).
According to the present invention, the cement reinforcing agent may include at least one selected from the group consisting of an alcamines additive, a sodium and/or calcium salt additive, a cyanamide additive, and a polyol ether additive.
According to the invention, the alcohol amine additive is helpful for eliminating static electricity, improving grinding effect and improving product strength, the proportion of the alcohol amine additive in the grinding aid can be 10-90 wt%, and the alcohol amine additive can be at least one selected from triethanolamine, triisopropanolamine, tricyclohexylamine, diethanol monoisopropanolamine, diethanol monocyclohexanolamine, diisopropanol monoethanolamine, diisopropanol monocyclohexanolamine, dicyclohexylethanolamine and dicyclohexylalcohol monoisopropanolamine.
According to the invention, the sodium salt and/or calcium salt additive can improve the grindability and fluidity of the cement admixture and improve the strength of the cement product. The grinding aid comprises a grinding aid, a sodium salt and/or calcium salt additive and a grinding aid, wherein the sodium salt and/or calcium salt additive accounts for 1-90 wt% of the grinding aid by weight, and the sodium salt and/or calcium salt additive can be at least one selected from sodium thiocyanate, sodium phosphate, sodium chloride, calcium sulfate, calcium chloride, sodium fluosilicate, sodium sulfate and sodium nitrate.
According to the invention, the polyol ether additive is helpful for eliminating static electricity, improving the grinding effect and improving the strength of cement products. The proportion of the grinding aid additive by weight may be 1-90 wt%, preferably 1-50 wt%, based on the grinding aid, and the polyol ether additive may include at least one selected from the group consisting of polyols, polyol ethers, and sugars, the polyols may include at least one selected from the group consisting of ethylene glycol, propylene glycol, glycerol, polyethylene glycol, triglycerol, and polypropylene glycol, the polyol ethers may include polyethylene glycol ethers and/or polypropylene glycol ethers, and the sugars may include at least one selected from the group consisting of white sugar, glucose, and molasses.
According to the invention, the cyanamide additive is helpful for eliminating static electricity, improving grinding effect and improving the strength of cement products, the proportion of the cyanamide additive in the grinding aid can be 10-90 wt%, and the cyanamide additive can comprise at least one selected from melamine, sulfonated melamine, cyanamide and tricyanamide.
According to the invention, the defoaming agent can be used for reducing the surface tension of the grinding aid, inhibiting the generation of foam or eliminating the generated foam, thereby improving the grinding aid effect. The defoaming agent accounts for 0.01-0.5 wt% of the grinding aid, the defoaming agent can comprise a silicone defoaming agent and/or a polyether modified silicone additive, the silicone defoaming agent can be at least one selected from polydimethylsiloxane, fluorosilicone and ethylene glycol siloxane, and can also be a special defoaming agent for commercially available concrete, such as building material industry defoaming agents of Dongguan Defeng defoaming agent company Limited, and product models of 'DF-179' and 'DF-175'.
According to the invention, the grinding aid may also contain a cement accelerator, which may be at least one selected from the group consisting of aluminum salts, magnesium salts, carbonates, and silica salts.
According to the invention, the grinding aid can be used for grinding the cement admixture to be ground in an internal mixing amount of 0.01-0.3 wt% so as to improve the grinding efficiency and the performance of the obtained ground product.
According to the invention, the cement admixture to be ground can be added into the cement final powder as a part of a cement product after being ground, and the cement admixture to be ground can be one or more selected from fly ash, slag, volcanic ash, sandstone, quartz sand, clay, shale, gypsum, iron ore powder, kaolin and bauxite.
According to the invention, grinding operation by adding grinding aid can be carried out by conventional technical means in the field, such as grinding for 20-40min by using a ball mill, a roller press or a vertical mill.
The invention will be further illustrated by the following examples, but is not to be construed as being limited thereto.
In the embodiment of the invention, the waste liquid obtained by preparing caprolactam from cyclohexanone is marked as liquid C, which is obtained from a corresponding production device of caprolactam division of Barring division of petrochemical group of China, and comprises 10 wt% of waste liquid (marked as liquid C1) obtained by oximation of cyclohexanone to prepare cyclohexanone oxime and 90 wt% of waste liquid (marked as liquid C2) obtained by rearrangement of cyclohexanone oxime to prepare caprolactam. The specific properties of the liquid C are as follows: the relative density is 1.16 g/cubic centimeter, the content of ammonium nitrate is 14 weight percent, the content of ammonium sulfate is 10 weight percent, the content of sodium thiocyanate is 11 weight percent, the content of caprolactam is 6 weight percent, the content of water is 55 weight percent, and the balance is impurities such as sodium fatty acid, paraffin oil, organosilicon and the like.
The embodiment of the invention uses saponification waste lye taken from a cyclohexane oxidation device of caprolactam division of Baling division of petrochemical group in China, the process for preparing cyclohexanone by cyclohexane oxidation is a catalyst-free oxidation method, which is marked as solution A and has the following properties: the relative density was 1.197 g/cc, the water content was 42 wt% and the sodium hydroxide content was 2 wt%.
The conditioning additives used in the examples were: sodium hydroxide, potassium hydroxide, sodium carbonate, triethanolamine and triglycerol are all commercially available.
The embodiment and the comparative example of the invention adopt a method in national standard GB/T26748-.
The grinding in the embodiment and the comparative example of the invention is carried out in a national standard cement test small mill which accords with the grinding-aid effect experimental method in GB/T26748-.
The comparative example DA1 and examples SA1 to SA5 illustrate the effect of using liquid C alone as a grinding aid for cement admixtures on the grinding effect of the cement admixtures.
Comparative example DA1
Slag (a group of martensite steels) and fly ash (Anhui Liuan power plant) are respectively subjected to grinding treatment, and specific conditions and results are respectively shown in tables 1 and 2.
Example SA1-SA5
And respectively grinding the slag (the martensite steel group) and the fly ash (Anhui six-ampere power plant) mixed in the liquid C according to different weight proportions, wherein specific conditions and results are respectively shown in tables 1 and 2.
Table 1: slag milling conditions and results for comparative example DA1 and example SA1-SA5
Figure BDA0001145939590000101
Figure BDA0001145939590000111
Table 2: fly ash milling conditions and results for comparative example DA1 and examples SA1-SA5
Figure BDA0001145939590000112
As can be seen from the results of tables 1-2: 1. after the liquid C is added, the fluidity of all materials is improved; 2. after the liquid C is added, the 45 micron screen residue of all materials is reduced; 3. after the addition of the liquid C, the specific surface areas of the materials in the examples SA1-SA5 are all increased, but excessive addition of the liquid C can greatly improve the flowability of the materials, reduce the friction force between the materials and a grinding medium, prevent the materials from being effectively ground, increase the screen residue and reduce the specific surface area. These results show that the liquid C has good grinding-aiding effect on slag and fly ash.
Examples SB1-SB4 illustrate the effect of using liquor C (100 parts by weight), with and without the addition of conditioning additives, as a cement grinding aid on the grinding effect of cement admixtures, examples SB1-SB4 using slag from the Mare Steel group and fly ash from the Anhui Saian Power plant.
Example SB1
And (3) mixing the liquid C as a grinding aid with slag and fly ash in a proportion of 0.1 weight percent respectively for grinding treatment, wherein specific conditions and results are shown in tables 3-4.
Example SB2
And adding sodium hydroxide into the solution C to adjust the pH value to 10, then using the solution C as a grinding aid, and mixing slag and fly ash in a proportion of 0.1 weight percent respectively for grinding treatment, wherein specific conditions and results are shown in tables 3-4.
Example SB3
And adding potassium hydroxide into the solution C to adjust the pH value to 10, adding 40 parts by weight of triethanolamine and 30 parts by weight of the solution A to serve as grinding aids, and respectively doping slag and fly ash into the solution in a proportion of 0.1 weight percent for grinding treatment, wherein specific conditions and results are shown in tables 3-4.
Example SB4
Adding sodium carbonate into the solution C to adjust the pH value to 10, adding 30 parts by weight of triethanolamine, 25 parts by weight of the solution A and 15 parts by weight of triglycerol as grinding aids, and respectively doping slag and fly ash into the solution in a proportion of 0.1 weight percent for grinding treatment, wherein the specific conditions and results are shown in tables 3-4.
Table 3: slag milling conditions and results of examples SB1-SB4
Examples Amount of slag (g) Grinding time (min) 45 μm screen (%) Specific surface area (m)2/kg)
SB1 5000 70 7.8 531
SB2 5000 70 7.3 535
SB3 5000 70 6.8 544
SB4 5000 70 6.5 557
Table 4: fly ash milling conditions and results of examples SB1-SB4
Examples Amount of fly ash (g) Grinding time (min) 45 μm screen (%) Specific surface area (m)2/kg)
SB1 5000 35 18.3 419
SB2 5000 35 17.5 422
SB3 5000 35 16.8 431
SB4 5000 35 15.5 450
As can be seen from the results of tables 3-4: after the adjusting additive is added into the liquid C for optimization, the 45-micron screen residue of all the materials is reduced and the specific surface area is increased, which shows that the liquid C has the optimization effect after the adjusting additive is added.
Comparative example DC1
Comparative example DC1 Cement Final powder workability with a PO42.5 designation is determined by the national Standard of the people's republic of China GB/T50080-2002 Standard of the Performance test method for ordinary concrete mixtures, the material ratio of the final cement powder is shown in Table 5, and the specific test conditions and results are shown in Table 6.
Examples SC1-SC4
Examples SC1-SC4 illustrate the influence of the liquid C and the liquid C containing a regulating additive on the cement construction performance, the grinding aid in examples SB1-SB4 is doped into the cement final powder according to the proportion of 0.05 weight percent, the brand of the cement used in the cement final powder is PO42.5, the material proportion is shown in Table 5, the specific test method is shown in the national standard GB/T50080-2002 standard test method for the performance of the common concrete mixture of the people's republic of China, and the specific test conditions and results are shown in Table 6.
Table 5: proportioning of cement powder materials
Figure BDA0001145939590000131
Figure BDA0001145939590000141
Table 6: comparative example DC1 and examples SC1-SC4 demonstrate the effect of liquid C on Cement workability
Figure BDA0001145939590000142
As can be seen from the results in Table 6, the addition of the liquid C increases the water consumption for the standard consistency of the cement, shortens the setting time, slightly increases or maintains the influence on the mobile phase of the mortar, and both meet the national standard.
Comparative examples DD1-DD3
In the comparative example DD1-DD3, the mechanical properties of the cement with the brands of PI 52.5, PO42.5 and PC 32.5R are determined, the concrete composition is shown in Table 7, the concrete test method is shown in the national Standard GB/T50081-2002 Standard for testing the mechanical properties of the common concrete of the people's republic of China, and the concrete test conditions and results are shown in Table 8.
Examples SD1-SD3
Examples SD1-SD3 illustrate the influence of liquid C on the mechanical properties of cement, the grinding aid of example SB4 is added into cement in a proportion of 0.05 wt%, the brands of the used cement are PI 52.5, PO42.5 and PC 32.5R, the concrete composition is shown in Table 7, the concrete test method is shown in the national Standard GB/T50081-2002 Standard test method for the mechanical properties of ordinary concrete of the people's republic of China, and the concrete test conditions and results are shown in Table 8.
Table 7 shows the final cement powder material ratios
Cement powder Clinker Gypsum plaster Fly ash Slag of mine Limestone
PC32.5R 56% 5% 18% 9% 12%
PO42.5 77% 5% 8% 5% 5%
PI 52.5 95% 5% / / /
Table 8: comparative examples DD1-DD3 and examples SD1-SD3 demonstrate the effect of liquid C on Cement workability
Figure BDA0001145939590000151
As can be seen from the results in Table 8, the cement strength changes after the grinding aid is added are different due to different cements, so that the compressive strength of cement mortar at all ages is increased and the compressive strength meets the requirements of national standard regulations.
Example SE1-SE2
Slag (martensite steel group) is respectively mixed in the C1 liquid and the C2 liquid for grinding treatment, and the specific conditions and results are shown in Table 9.
Table 9: slag milling conditions and results for example SE1-SE2
Figure BDA0001145939590000161
As can be seen from table 9, the single use of the C1 liquid and the single use of the C2 liquid for the grinding treatment also has a good grinding effect.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and tests, it will be apparent to those skilled in the art that modifications and improvements can be made thereto or known or even established grinding aid ingredients, such as polycarboxylates, lignosulfonates, polyacrylamides, can be added based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims (17)

1. A method for grinding cement admixture, which comprises the following steps: grinding the cement mixture to be ground and the cement mixture grinding aid together; wherein the cement admixture grinding aid contains waste liquid from the preparation of caprolactam from cyclohexanone; the waste liquid from the preparation of caprolactam from cyclohexanone contains waste liquid from the preparation of cyclohexanone oxime by oximation of cyclohexanone and/or waste liquid from the preparation of caprolactam by rearrangement of cyclohexanone oxime; the waste liquid from the preparation of caprolactam from cyclohexanone contains caprolactam and inorganic salt; the inorganic salt includes at least one selected from the group consisting of sodium nitrate, sodium sulfate, sodium thiocyanate, sodium chloride, sodium carbonate, ammonium nitrate and ammonium sulfate; the material to be ground of the cement admixture is at least one selected from fly ash, slag, volcanic ash, sandstone, quartz sand, clay, shale, iron ore powder, kaolin and bauxite.
2. The process as claimed in claim 1, wherein the waste liquid from the production of caprolactam from cyclohexanone contains 0.1-15% by weight of caprolactam.
3. The process as claimed in claim 1, wherein the waste liquid from cyclohexanone to caprolactam contains 2-60 wt% of the inorganic salt.
4. The method of claim 1, wherein the grinding aid further comprises a pH adjusting agent added in an amount to adjust the pH of the grinding aid to a range of 7 to 14.
5. The method according to claim 4, wherein the pH adjustor is at least one selected from the group consisting of lithium oxide, sodium oxide, potassium oxide, calcium oxide, magnesium oxide, aluminum oxide, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, calcium carbonate, magnesium carbonate and trisodium phosphate.
6. The method of claim 1 wherein the grinding aid further comprises saponified spent lye from oxidation of cyclohexane to cyclohexanone; wherein the weight ratio of the saponified waste lye to the waste liquid from the preparation of caprolactam from cyclohexanone is 100: (0-1000).
7. The process of claim 6, wherein the saponified spent lye contains 30 to 90 weight percent of water, based on the weight of the saponified spent lye.
8. The process of claim 6, wherein the saponified spent lye contains 0.3 to 5 weight percent of sodium hydroxide, based on the weight of the saponified spent lye.
9. The method of claim 6, wherein the process for preparing cyclohexanone by oxidizing cyclohexane is at least one selected from a cobalt salt catalytic oxidation method, a boric acid catalytic oxidation method, a titanium silicalite catalytic oxidation method and a catalyst-free oxidation method.
10. The method of claim 1 wherein the grinding aid further comprises a cement enhancing agent comprising at least one selected from the group consisting of an alcamines additive, a sodium and/or calcium salt additive, a cyanamide additive, and a polyol ether additive.
11. The method of claim 10 wherein the proportion of the alkanolamine additive is 10-90% by weight of the grinding aid, the alkanolamine additive being at least one selected from the group consisting of triethanolamine, triisopropanolamine, tricyclohexylamine, diethanolisopropanolamine, diethanolisocyclolamine, diisopropanolamine, dicyclohexylamine, and dicyclohexylamine monoisopropanolamine.
12. The method of claim 10 wherein the grinding aid is present in a ratio of 1-90% by weight of sodium and/or calcium salt additive, the sodium and/or calcium salt additive being at least one selected from the group consisting of sodium thiocyanate, sodium phosphate, sodium chloride, calcium sulfate, calcium chloride, sodium fluorosilicate, sodium sulfate and sodium nitrate.
13. The method of claim 10 wherein the polyol ether additive comprises a polyol ether comprising a polyethylene glycol ether and/or a polypropylene glycol ether in a proportion of 1 to 90 percent by weight of the grinding aid.
14. The method of claim 10 wherein the cyanamide additive comprises at least one member selected from the group consisting of melamine, sulfonated melamine, mono-cyanamide, and tri-cyanamide in a weight ratio of 10 to 90 percent of the grinding aid.
15. The method of claim 1 wherein the grinding aid further comprises an antifoaming agent; the defoaming agent accounts for 0.01-0.5 wt% of the grinding aid by weight, and comprises an organic silicon defoaming agent and/or a polyether modified silicon additive.
16. The method of claim 1 wherein the grinding aid further comprises a cement accelerator which is at least one selected from the group consisting of aluminum salts, magnesium salts, carbonates, and silica salts.
17. The method as claimed in claim 1, wherein the grinding aid for cement admixture constitutes 0.01 to 0.3% by weight, based on the total weight of the grinding aid for cement admixture to be ground and the cement admixture, of the grinding aid.
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