CN109824284B - Cement raw material additive, application thereof and cement production process - Google Patents
Cement raw material additive, application thereof and cement production process Download PDFInfo
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Abstract
The present invention relates to a cement raw material additive, its application and cement production process. The cement raw material additive provided by the disclosure can recycle industrial waste alkali liquor in cement raw material grinding and cement production, and has good comprehensive effects of increasing yield, reducing coal consumption, improving raw material burnability, desulfurizing and the like.
Description
Technical Field
The present invention relates to a cement raw material additive and its application and cement production process.
Background
The cement production is an industry with low energy utilization rate and high energy consumption, and the annual output of 2016 cement in China is 23 hundred million tons, which accounts for more than half of the global output. The cement production process is divided into three stages, namely, a calcareous raw material, a clayey raw material and a small amount of correction raw material (a certain amount of coal is added in the vertical kiln production) are crushed or dried, then are matched and ground according to a certain proportion, and are prepared into raw materials with proper components and uniform quality, which is called as a first stage: grinding the raw materials; then adding the ground raw materials into a cement kiln, calcining until the ground raw materials are partially melted to obtain cement clinker taking calcium silicate as a main component, and referring to a second stage: calcining the raw material; the clinker is added with a proper amount of gypsum and sometimes some mixed materials, and ground into cement together, which is called as a third stage: and (5) grinding the clinker. The cement production process may be referred to simply as: 'two grinding and one burning'.
Because the energy consumption of cement production is high, the reduction of the energy consumption of cement production is an important research direction, people adopt a plurality of methods to improve the utilization efficiency of the energy of cement production and reduce the energy consumption, wherein, a large amount of cement grinding aids are applied in the cement clinker grinding process, thereby obtaining wide social benefits and economic benefits. However, the important raw meal grinding process in the cement production process is less researched. For example, Chuifeng (influence of rate value and mineralizer or crystal seed on the easy-to-burn property of cement raw material; cement; 1999, 09) found that the easy-to-burn property of raw material is obviously improved after adding a proper amount of composite mineralizer, crystal seed and fluorite mineralizer, and the K1400 ℃ after external addition is averagely improved by 2-5% compared with the K1400 ℃ without addition. The researches of Mabaoguo and the like (research on the influence of a phosphorus slag-based composite mineralizer on the easy-to-burn property of a cement raw material, silicate report, 2007 year 01) find that the influence of the phosphorus slag, fluorite and steel slag composite on the easy-to-burn property of the cement raw material is researched, the adaptability of the composite mineralizer of the phosphorus slag, the steel slag and the fluorite to the calcining temperature is good, and the easy-to-burn property can be effectively improved. Chenyilan, Weishi etc. (research experiment using grinding aid in raw material grinding, cement; 1996 year 09) found that the proper addition amount can make the material obtain higher fineness, larger specific surface area and good dispersion degree, and the particle structure tends to be uniform. Thereby improving the yield of the mill and reducing the unit powder electricity consumption. However, the above studies show that the effect of the additive used in the raw meal is relatively single, and no report of using industrial waste lye, particularly saponified waste lye of cyclohexanone, as a raw meal additive is found, and no some research reports of obtaining very good application effect are found.
Cyclohexanone is a basic raw material for producing nylon, and a large amount of organic wastewater is generated in the production process of cyclohexanone. Wherein, the device for preparing cyclohexanone by cyclohexane oxidation method has the generation of organic acid and organic acid ester due to deep oxidation, alkali is needed to be added to neutralize the organic acid in the refining process of the cyclohexanone product, and the treated waste water is called 'saponification waste lye' in the industry. The total amount of the wastewater in the country is about 100 million tons/year (40% concentration meter), the COD is high, the biochemical treatment cannot be directly carried out, and the currently generally adopted incineration method has the disadvantages of large investment, large energy consumption, certain environmental influence and resource waste. The sulfite waste liquid and the soap waste liquid in the paper mill are industrial waste alkali liquid with high yield, and need to be treated as waste water, and the environmental pressure is high. The comprehensive utilization of the resources of the industrial alkaline waste lye is reported particularly as an additive in cement raw meal and the application thereof.
Disclosure of Invention
The cement raw material additive can recycle industrial waste alkali liquid such as saponified waste alkali liquid, paper mill sulfite waste liquid, soap waste liquid and the like which are used for preparing cyclohexanone by oxidizing cyclohexane in cement raw material grinding and cement production, and has good comprehensive effects of improving yield, reducing coal consumption, improving raw material burnability and desulfurizing.
In order to achieve the above objects, the present disclosure provides a cement raw meal additive comprising an industrial waste lye and an alkalinity enhancing agent.
Optionally, the industrial waste lye is at least one selected from saponified waste lye of cyclohexanone production by cyclohexane oxidation, paper mill sulfite waste liquor and soap waste liquor.
Optionally, the saponified waste lye of the cyclohexanone production by cyclohexane oxidation contains 30-90 wt% of water, 5-60 wt% of sodium carboxylate and 0.3-10 wt% of sodium hydroxide, based on the weight of the saponified waste lye of the cyclohexanone production by cyclohexane oxidation;
the paper mill sulfite waste liquor contains 30-80 wt% of water, 5-40 wt% of lignosulfonate and 3-30 wt% of sodium sulfite based on the total weight of the paper mill sulfite waste liquor;
the soap waste liquid contains 30-85 wt% of water, 5-60 wt% of glycerin and 1-10 wt% of sodium chloride based on the total weight of the soap waste liquid.
Optionally, 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.
Optionally, the alkali enhancer accounts for 0-80 wt% of the cement raw material additive; the alkalinity improver is at least one selected from sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, calcium oxide, magnesium oxide, sodium methoxide, sodium ethoxide and potassium ethoxide.
Optionally, the cement raw material additive contains an alcohol amine additive; the proportion of the alcamines additive in the cement raw material additive is 0-99 wt%; the alkanolamine additive is at least one selected from triethanolamine, triisopropanolamine, tricyclohexylamine, diethanolisopropanolamine, diethanolisocyclolamine, diisopropanolamine, dicyclohexylamine, and dicyclohexylamine monoisopropanolamine.
Optionally, the cement raw material additive contains a polyhydric ether alcohol additive; the proportion of the polyhydric ether alcohol additive in the cement raw material additive is 0-50 wt%; the polyol ether additive includes at least one selected from the group consisting of a polyol including at least one selected from the group consisting of ethylene glycol, propylene glycol, glycerin, polyethylene glycol, triglycerol, and polypropylene glycol, a polyol ether including at least one selected from the group consisting of polyethylene glycol ether and/or polypropylene glycol ether, and a sugar including white sugar and/or molasses.
The present disclosure also provides an application of a cement raw material additive in cement raw material grinding, the application including: grinding the cement raw material to be ground and the cement raw material additive together to obtain a raw material grinding product; wherein the cement raw meal additive is the cement raw meal additive provided by the disclosure or the industrial waste lye provided by the disclosure.
Optionally, the cement raw meal additive provided by the present disclosure accounts for 0.03-0.5 wt% of the total weight of the cement raw meal to be ground and the cement raw meal additive provided by the present disclosure; the industrial waste alkali liquor accounts for 0.03 to 0.5 weight percent of the total weight of the raw material to be ground of the cement and the industrial waste alkali liquor; the raw material to be ground for the cement comprises a calcareous raw material, a clayey raw material and a correction raw material; the calcareous raw material is at least one selected from limestone, marl, chalk, shells and coral; the clayey raw material is at least one selected from loess, clay, shale, mudstone, siltstone and silt; the correcting raw material is at least one selected from iron ore, copper slag, sandstone and river sand.
The present disclosure also provides a cement production process, comprising: roasting the raw material grinding product obtained by the application of the method in a rotary kiln to obtain cement clinker to be ground; and grinding the cement clinker to be ground to obtain a clinker ground product.
The invention discloses a cement raw material additive which takes industrial waste alkali liquid such as saponified waste alkali liquid, paper mill sulfite waste liquid, soap waste liquid and the like in the process of preparing cyclohexanone by oxidizing cyclohexane as main components, and the cement raw material additive can be used for grinding cement raw materials, so that the problem of reasonable treatment of the saponified waste alkali liquid, the paper mill sulfite waste liquid, the soap waste liquid and other industrial waste alkali liquid in the process of preparing cyclohexanone by oxidizing cyclohexane can be solved, the purposes of cleanness, environmental protection, low cost and resource comprehensive utilization can be achieved, a good grinding-aiding effect can be achieved, the yield can be improved, the material flowability in the grinding process can be improved, the coal consumption and the sulfur dioxide discharge amount can be reduced, and the mechanical property of final cement can not be influenced.
Additional features and advantages of the disclosure will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present disclosure. It should be understood that the detailed description and specific examples, while indicating the present disclosure, are given by way of illustration and explanation only, not limitation.
The present disclosure provides a cement raw meal additive comprising an industrial waste lye and an alkalinity enhancer. The industrial waste lye refers to waste liquor discharged by industrial production and having a pH value of more than 7, preferably more than 9, the industrial waste lye is preferably at least one of saponification waste lye of cyclohexanone prepared by cyclohexane oxidation, paper mill sulfite waste liquor and soap waste liquor, more preferably saponification waste lye of cyclohexanone prepared by cyclohexane oxidation, further preferably saponification waste lye containing cyclohexanone prepared by cyclohexane oxidation, and optionally other two industrial waste lye.
The cement raw material additive (or industrial waste alkali liquor) provided by the disclosure can be used for grinding the raw material to be ground of the cement in an internal mixing amount of 0.03-0.5 wt% (namely, the cement raw material additive (or industrial waste alkali liquor) provided by the disclosure accounts for 0.03-0.5 wt% of the total weight of the raw material to be ground of the cement and the cement raw material additive (or industrial waste alkali liquor)), so that the effects of yield increase and desulfurization are achieved.
The cement raw material to be ground is well known to those skilled in the art, and refers to a cement raw material before primary grinding in a preparation process of cement double-grinding and single-burning, and can comprise a calcareous raw material, a clayey raw material and a correcting raw material; the calcareous material may be at least one selected from limestone, marl, chalk, shells and coral; the clayey raw material may be at least one selected from loess, clay, shale, mudstone, siltstone and silt; the calibration raw material may be at least one selected from the group consisting of iron ore, copper slag, sandstone, and river sand.
In 2016, the total cement output reaches 23 hundred million tons, the cement raw material amount is calculated by 1.6 times of the cement output, calculated by 0.08 percent of the dosage of a cement raw material additive, about 294 million tons of cement raw material additives are required, the cement raw material is different from the cement clinker, and a grinding aid capable of being used for the cement clinker is generally difficult to be used in the cement raw material for reducing coal consumption and sulfur dioxide discharge.
According to the disclosure, the process for preparing cyclohexanone by oxidizing cyclohexane has more research and faster development 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 characteristics, the basic principle and the reaction flow are the same, and the specific reaction flow is shown as the following formula:
in the first step, cyclohexane is oxidized in the presence or absence of a catalyst to form cyclohexanone, cyclohexanol and by-products. Taking cobalt naphthenate as an example as a catalyst, the reaction temperature is 160 ℃, the pressure is about 1.08MPa, 5 kettles are connected in series for reaction for 1h, the conversion rate is controlled to be about 5 weight percent by contacting with air, and the selectivity of the cyclohexanol ketone is about 80 weight percent.
In the second step, the product obtained in the first step is subjected to alkaline washing with sodium hydroxide solution to obtain an organic phase containing cyclohexanone and cyclohexanol and an aqueous phase saponification waste lye, which can be used as such, preferably after suitable concentration, and which is generally a black liquid or a partially solid, with a relative density of generally 1.05-1.25 g/ml, and which may contain 30-90 wt% of water, 5-60 wt% of sodium carboxylate and 0.3-10 wt% of sodium hydroxide, other salts and organic substances, etc., based on the weight of the saponification waste lye of cyclohexanone produced by oxidation of cyclohexane.
According to the disclosure, the saponified waste lye from the oxidation of cyclohexane to prepare cyclohexanone can be directly used as an additive for grinding without any pretreatment, and the effect of adding the adjusting additive is better. The regulating additive is used for improving the performances of grinding aid, desulfurization and the like of the saponified waste alkali solution, and the weight ratio of the saponified waste alkali solution for preparing cyclohexanone by cyclohexane oxidation to the regulating additive can be 100: (0-1000), preferably 100: (1-600).
In the present disclosure, the waste liquid of sulfite in paper mill and the waste liquid of soap are well known to those skilled in the art, the waste liquid of sulfite in paper mill refers to waste water from acid pulping, the waste liquid of sulfite in paper mill generally contains 30-80 wt% of water, 5-40 wt% of lignosulfonate and 3-30 wt% of sodium sulfite based on the total weight of the waste liquid of sulfite in paper mill, the waste liquid of soap refers to waste liquid obtained from soap mill and can be used for preparing glycerin, and the waste liquid of soap generally contains 30-85 wt% of water, 5-60 wt% of glycerin and 1-10 wt% of sodium chloride based on the total weight of the waste liquid of soap.
According to the disclosure, the addition of the above-mentioned conditioning additives to the spent sulfite liquor and the spent soap liquor of a paper mill also provides good results. The weight ratio of the sulfite waste liquid and the regulating additive in the paper mill and the weight ratio of the soap waste liquid and the regulating additive in the paper mill are both 100: (0-1000), preferably 100: (10-600), the proportion of the saponified waste lye of cyclohexanone prepared by oxidizing cyclohexane, the waste sulfite liquor and the waste soap liquor of paper mill in the cement raw material additive can be any proportion.
According to the present disclosure, the alkalinity enhancer is a substance capable of enhancing the alkalinity of the industrial waste lye, for example, an alkaline compound can be used, and can reduce the emission of sulfur dioxide, and the alkalinity enhancer accounts for 0 to 80 wt%, preferably 1 to 75 wt%, more preferably 3 to 70 wt%, and still more preferably 10 to 60 wt% of the cement raw meal additive; the alkalinity enhancer may be at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, calcium oxide, magnesium oxide, sodium methoxide, sodium ethoxide and potassium ethoxide, and other alkali substances may also be used as the alkalinity enhancer.
In accordance with the present disclosure, the cement raw meal additive may contain optional conditioning additives, which may include at least one selected from the group consisting of alcamines and polyol ether additives.
According to the present disclosure, the proportion of the alkanolamine additive to the cement raw material additive, which may be at least one selected from the group consisting of triethanolamine, triisopropanolamine, tricyclohexylamine, diethanol monoisopropanolamine, diethanol monocyclohexanolamine, diisopropanol monoethanolamine, diisopropanol monocyclohexanolamine, dicyclohexylamine monoethanolamine, and dicyclohexylalcohol monoisopropanolamine, helps to eliminate static electricity and improve grinding effect, may be 0 to 99% by weight, preferably 1 to 95% by weight, more preferably 3 to 90% by weight, and still more preferably 10 to 80% by weight.
According to the present disclosure, the polyol ether additive helps to eliminate static electricity and improve grinding effect. The proportion of the polyol ether additive to the cement raw material additive by weight may be 0 to 50% by weight, preferably 1 to 45% by weight, more preferably 3 to 40% by weight, and still more preferably 10 to 30% by weight, the polyol ether additive may include at least one selected from the group consisting of a polyol, a polyol ether, and a saccharide, the polyol may include at least one selected from the group consisting of ethylene glycol, propylene glycol, glycerol, polyethylene glycol, triglycerol, and polypropylene glycol, the polyol ether may include a polyethylene glycol ether and/or a polypropylene glycol ether, and the saccharide may include white sugar and/or molasses.
The present disclosure also provides an application of a cement raw material additive in cement raw material grinding, the application including: grinding the cement raw material to be ground and the cement raw material additive together to obtain a raw material grinding product; wherein the cement raw meal additive is the cement raw meal additive provided by the disclosure or the industrial waste lye provided by the disclosure. In the present disclosure, the industrial waste alkali solution may be directly used for grinding cement raw meal, or may be optionally blended and then used as cement raw meal.
The present disclosure also provides a cement production process, comprising: roasting the raw material grinding product obtained by the application of the method in a rotary kiln to obtain cement clinker to be ground; and grinding the cement clinker to be ground to obtain a clinker ground product.
Calcination of the raw meal mill product is well known to those skilled in the art in light of this disclosure and refers to feeding the raw meal mill product into a cement rotary kiln for calcination to partial fusion to produce calcium silicate cement clinker (granular or block) having calcium silicate as a major component. In order to increase the roasting temperature, combustion improver such as coal can be added for roasting together, so that the coal consumption can be reduced, and the energy utilization rate can be increased.
The present disclosure is further illustrated by the following examples, but is not to be construed as being limited thereby.
The embodiment of the disclosure uses the saponified waste alkali solution to be taken from the saponified waste alkali solution generated in a cyclohexane oxidation device of caprolactam division of the creeling division, a petrochemical group, in 2017, 8 and 1, wherein the process for preparing cyclohexanone by cyclohexane oxidation is a catalyst-free oxidation method, which is marked as solution a, and the properties of the solution a are as follows: the relative density was 1.197 g/cc, the water content was 42 wt% and the sodium hydroxide content was 2 wt%.
The paper mill sulfite waste liquid and the soap waste liquid are respectively sampled in Yueyang paper mill in 2016 (6 months) and Yue-Yan paper mill in 2017 (8 months) and 6 days in Hunan, and the properties of the paper mill sulfite waste liquid are as follows: the relative density was 1.052 g/cc, and the water content was 40% by weight. The properties of the soap waste liquid are as follows: the relative density was 1.098 g/cc and the water content was 40 wt%.
The conditioning additives used in the examples were: ethylene glycol, glycerol, molasses, triglycerol, triethanolamine and diethanol monoisopropanolamine are all commercially available, and the alkaline enhancers used in the examples are: sodium hydroxide, calcium hydroxide, magnesium oxide, products of different brands, do not influence the use.
In the examples, the mixing ratio of the cement raw material additive is cement raw material additive/(cement grinding raw material + cement raw material additive).
In the examples, the proportion of the industrial waste alkali solution is industrial waste alkali solution/(industrial waste alkali solution + cement raw material to be ground).
First, industrial experimental effect
Examples SA1-SA5 and comparative example DA1 illustrate the effect of the presence or absence of additives to cement raw meal or industrial waste lye on the grinding effect of the raw meal.
The experiment is carried out in Huaibei mining bureau-phase mountain cement plant, and the specific operation steps are as follows: feeding cement raw materials to be ground into a vertical mill separately or together with a cement raw material additive (industrial waste alkali liquor) for raw material grinding, wherein the raw material grinding condition is that the fineness is controlled (0.08mm) to be less than 18 weight percent, the statistical mill main current is 190-210 amperes, the grinding pressure is 1.1MPa, the mill outlet temperature is 75-85 ℃, and the circulating fan current is 250 amperes; the raw material grinding product is sent into a kiln system for decomposition and calcination, the calcination condition ensures that the clinker quality is qualified, the kiln current is 600-plus-700 amperes, the kiln rotating speed is 3.8 r/min, and the decomposition temperature is 860-plus-890 ℃, so that the cement clinker to be ground is obtained; during the period, the average yield of the raw meal mill, the fineness of the obtained raw meal (the ratio of the sieved weight), the decomposition rate of calcium carbonate during calcination, the average coal consumption and SO were measured2Discharge amount, etc.
Comparative example DA1
The raw materials to be ground of the cement are independently subjected to raw material grinding treatment, and specific conditions and results are shown in table 1.
Example SA1
The liquid A (100 parts by weight) is mixed with cement in a proportion of 0.03 weight percent to be ground to carry out raw material grinding treatment and calcination, and specific conditions and results are shown in Table 1.
Example SA2
The liquid A (100 parts by weight) is mixed with cement in the proportion of 0.1 percent by weight to be ground, and the raw materials are ground and calcined, and the specific conditions and results are shown in table 1.
Example SA3
After adding 70 parts by weight of an alkaline enhancer (sodium hydroxide) into 100 parts by weight of the solution A, the solution A is used as a cement raw material additive, cement is added into the cement raw material to be ground in a proportion of 0.2 percent by weight for grinding and calcining the raw material, and specific conditions and results are shown in Table 1.
Example SA4
After adding 40 parts by weight of an alkaline enhancer (calcium hydroxide) to 100 parts by weight of the solution A, 40 parts by weight of triglycerol is added to serve as a cement raw material additive, and cement is added to the cement raw material to be ground in a proportion of 0.3% by weight to perform raw material grinding treatment and calcination, wherein specific conditions and results are shown in Table 1.
Example SA5
After adding 10 parts by weight of an alkaline enhancer (sodium hydroxide) to 100 parts by weight of the solution A, 30 parts by weight of triglycerol and 20 parts by weight of triethanolamine were added as a cement raw material additive, and cement was added to the cement raw material in an amount of 0.5% by weight to perform raw material grinding and calcination, and the specific conditions and results are shown in Table 1.
TABLE 1
As can be seen from the above table, the comprehensive performance optimization is more obvious with the increase of the internal mixing proportion and the addition of the adjusting additive. In the example SA5, when the addition amount of cement raw material additive is 0.5%, the fineness of 30t/h, 0.08mm and 0.2mm of raw material yield is reduced by 0.4% and 1.5%, respectively, the decomposition rate is increased by 3.6%, the coal consumption is reduced by 2.8t/h, and in addition, the discharge amount of sulfur dioxide is reduced by 44.6%. Overall, the cement raw material additive has good effects in the aspects of yield improvement, coal saving and sulfur reduction.
Examples SB1-SB3 and comparative example DA1 illustrate the effect of three industrial waste alkali stocks on the effect of raw meal grinding.
Example SB1
After adding 10 parts by weight of an alkaline enhancer (sodium hydroxide) to 100 parts by weight of the solution A, 20 parts by weight of ethylene glycol and 60 parts by weight of triethanolamine were added as a cement raw material additive, and cement was added to the cement raw material in an amount of 0.3% by weight to grind and calcine the raw material, and the specific conditions and results are shown in Table 2.
Example SB2
The method comprises the steps of adding 10 parts by weight of an alkaline enhancer (sodium hydroxide) into 100 parts by weight of sulfite waste liquor of a paper mill, adding 20 parts by weight of glycerol and 40 parts by weight of diethanol monoisopropanolamine to serve as a cement raw material additive, and adding cement to be ground into raw materials in a proportion of 0.3 wt% to perform raw material grinding treatment and calcination, wherein specific conditions and results are shown in Table 2.
Example SB3
After adding 10 parts by weight of an alkaline enhancer (sodium hydroxide) to 100 parts by weight of the soap waste liquid, 20 parts by weight of molasses and 40 parts by weight of diethanol monoisopropanolamine were added as an additive to cement raw materials, and cement raw materials to be ground were added in a proportion of 0.3% by weight to perform grinding treatment and calcination of the raw materials, and specific conditions and results are shown in table 2.
TABLE 2
As can be seen from the above table, the three industrial wastes and the alkalinity improver have the functions of yield improvement, coal saving and desulfurization after being compounded. The difference of the application effects of the three materials is not large, but the effect of the embodiment SB1 compounded by the material A is the most obvious, when the internal mixing proportion is 0.3%, the fineness of 25t/h, 0.08mm and 0.2mm of the raw material is respectively reduced by 0.3% and 1.2%, the decomposition rate is improved by 2.3%, and the coal consumption is reduced by 2.3 t/h.
Secondly, the influence of the additive on the mechanical property of the fired clinker
Examples SC1-SC8 and a comparative example DC1 illustrate the influence of cement raw material additives on mechanical properties of ground raw material burned clinker, and the specific test method is shown in the national standard GB/T50081-2002 Standard for testing mechanical properties of ordinary concrete of the people's republic of China, which is shown in Table 3.
TABLE 3
The addition of the raw material additive can reduce the fineness of the raw material and improve the easy-burning property of the raw material, so that the strength of the corresponding cement is promoted to a certain extent, and the strength is improved to a certain extent after the addition of the raw material additive, as can be seen from the table above, in the embodiment with better effect, the strength is improved by about 9% in 1 day and 3 days, and the strength is improved by about 5% in 28 days.
As can be seen from tables 1-2, the industrial waste liquid provided by the present disclosure has certain effects of increasing yield and reducing energy consumption, and after the adjustment additive and the alkalinity improver are added, the effects can be obviously increased. As can be seen from the data, the SA5 with the best effect in the embodiment increases the yield by 30 tons/h; the cement raw material additive improves the burnability of the raw material by reducing the fineness of the raw material and changing the distribution state of the raw material, thereby reducing the coal consumption, and the cement raw material additive and the industrial waste alkali liquor can promote the absorption of calcium to sulfur dioxide, thereby having certain environmental protection benefit. As can be seen from table 3, the cement raw meal additives provided by the present disclosure do not affect or even improve the mechanical properties of the final cement.
Third, the effect of improving the easy-to-burn property of raw material
The raw meal is a sample taken in a vertical mill application test in a cement plant, and a thermogravimetric analysis test of the sample is carried out on a thermogravimetric analyzer. The experimental conditions were that the carrier gas flow was 200L/min and the atmosphere was air. The heating rate is 10K/min, the temperature is increased from room temperature to 950 ℃, and TG and corresponding data are output on a computer.
TABLE 4
| Numbering | Source of raw meal | Decomposition temperature (. degree.C.) | Decomposition Rate (%) | Relative value (. degree. C.) |
| DD1 | DA1 | 760 | 20 | / |
| SD1 | SA2 | 753 | 20 | -7 |
| SD2 | SA3 | 750 | 20 | -10 |
| SD3 | SB1 | 741 | 20 | -19 |
| SD4 | SB2 | 744 | 20 | -16 |
| SD5 | SB3 | 746 | 20 | -14 |
As can be seen from Table 4, the decomposition temperatures of the raw materials added with the cement raw material additive are reduced to different degrees at the same decomposition rate (20%), on the one hand, the smaller the fineness, the more uniform the fineness, the easier it is to burn; on the other hand, the activation energy of the cement raw meal additive is reduced probably because certain alkaline substances in the cement raw meal additive act with the raw meal. The combination of the decomposition rate and other data of industrial application shows that the cement raw meal additive has the function of improving the raw meal burnability.
Although the present disclosure has been described in detail hereinabove with respect to general description, specific embodiments and experiments, it will be apparent to those skilled in the art that some modifications or improvements may be made based on the present disclosure. Accordingly, such modifications and improvements are intended to be within the scope of this disclosure, as claimed.
Claims (9)
1. A cement raw material additive, the cement raw material additive contains industrial waste lye and alkalinity improver; the industrial waste alkali liquor is saponified waste alkali liquor obtained by oxidizing cyclohexane to prepare cyclohexanone.
2. The cement raw meal additive as claimed in claim 1, wherein the saponified waste lye of cyclohexanone production by cyclohexane oxidation contains 30-90% by weight of water, 5-60% by weight of sodium carboxylate and 0.3-10% by weight of sodium hydroxide, based on the weight of the saponified waste lye of cyclohexanone production by cyclohexane oxidation.
3. The cement raw meal additive as set forth in claim 1, wherein said process for preparing cyclohexanone by oxidation of cyclohexane is at least one selected from the group consisting of a cobalt salt catalytic oxidation process, a boric acid catalytic oxidation process, a titanium silicalite catalytic oxidation process, and a catalyst-free oxidation process.
4. The cement raw meal additive according to claim 1, wherein the alkalinity enhancer comprises less than 80% by weight of the cement raw meal additive; the alkalinity improver is at least one selected from sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, calcium oxide, magnesium oxide, sodium methoxide, sodium ethoxide and potassium ethoxide.
5. The cement raw meal additive according to claim 1, wherein the cement raw meal additive comprises an alcamines additive; the proportion of the alcamines additive in the cement raw material additive is 0-99 wt%; the alkanolamine additive is at least one selected from triethanolamine, triisopropanolamine, tricyclohexylamine, diethanolisopropanolamine, diethanolisocyclolamine, diisopropanolamine, dicyclohexylamine, and dicyclohexylamine monoisopropanolamine.
6. The cement raw meal additive according to claim 1, wherein the cement raw meal additive comprises a polyhydric ether alcohol-based additive; the proportion of the polyhydric ether alcohol additive in the cement raw material additive is 0-50 wt%; the polyol ether additive includes at least one selected from the group consisting of a polyol including at least one selected from the group consisting of ethylene glycol, propylene glycol, glycerin, polyethylene glycol, triglycerol, and polypropylene glycol, a polyol ether including at least one selected from the group consisting of polyethylene glycol ether and/or polypropylene glycol ether, and a sugar including white sugar and/or molasses.
7. The application of cement raw meal additive in cement raw meal grinding comprises the following steps: grinding the cement raw material to be ground and the cement raw material additive together to obtain a raw material grinding product; wherein the cement raw material additive is the cement raw material additive as defined in any one of claims 1 to 6 or the industrial waste lye as defined in any one of claims 1 to 6.
8. The use according to claim 7, wherein the cement raw material additive as defined in any one of claims 1 to 6 is present in an amount of 0.03 to 0.5% by weight based on the total weight of the cement raw material to be ground and the cement raw material additive as defined in any one of claims 1 to 6; the industrial waste lye of any one of the claims 1 to 6, which constitutes from 0.03 to 0.5% by weight of the total weight of said raw meal for cement and said industrial waste lye of any one of the claims 1 to 6; the raw material to be ground for the cement comprises a calcareous raw material, a clayey raw material and a correction raw material; the calcareous raw material is at least one selected from limestone, marl, chalk, shells and coral; the clayey raw material is at least one selected from loess, clay, shale, mudstone, siltstone and silt; the correcting raw material is at least one selected from iron ore, copper slag, sandstone and river sand.
9. A cement production process, comprising:
roasting the raw meal grinding product obtained by the application of claim 7 or 8 in a rotary kiln to obtain cement clinker to be ground;
and grinding the cement clinker to be ground to obtain a clinker ground product.
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| CN109824285B (en) * | 2017-11-23 | 2020-08-04 | 湖南昌迪环境科技有限公司 | Cement flue gas desulfurizer and application thereof |
| CN113354311A (en) * | 2020-06-22 | 2021-09-07 | 阳新娲石水泥有限公司 | Resource-saving low-carbon cement clinker and preparation method thereof |
| CN112759289B (en) * | 2020-12-31 | 2023-03-10 | 安徽海螺新材料科技有限公司 | Cement raw material additive with grinding-aid and decomposition-promoting effects |
| CN113896439A (en) * | 2021-10-08 | 2022-01-07 | 湖南昌迪环境科技有限公司 | Cement raw material additive, application thereof and cement production process |
| CN113800796A (en) * | 2021-11-02 | 2021-12-17 | 南京永能新材料有限公司 | Cement raw material additive and preparation method thereof |
| CN114907030A (en) * | 2022-05-26 | 2022-08-16 | 昌德新材科技股份有限公司 | Cement raw material additive and application thereof and cement production process |
| CN114907031A (en) * | 2022-05-26 | 2022-08-16 | 昌德新材科技股份有限公司 | Cement raw material additive, application thereof and cement production process |
| CN116573869B (en) * | 2023-05-26 | 2024-05-28 | 安徽建筑大学 | Method for producing cement clinker by using slag waste |
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Application publication date: 20190531 Assignee: Pingdingshan Changming Technology Co.,Ltd. Assignor: HUNAN CHANGDE ENVIRONMENT TECHNOLOGY CO.,LTD. Contract record no.: X2022980015684 Denomination of invention: A cement raw meal additive and its application and cement production process Granted publication date: 20210827 License type: Common License Record date: 20220921 Application publication date: 20190531 Assignee: Hangzhou Changde Industrial Co.,Ltd. Assignor: HUNAN CHANGDE ENVIRONMENT TECHNOLOGY CO.,LTD. Contract record no.: X2022980015690 Denomination of invention: A cement raw meal additive and its application and cement production process Granted publication date: 20210827 License type: Common License Record date: 20220921 Application publication date: 20190531 Assignee: Changde Xincai Technology Co.,Ltd. Assignor: HUNAN CHANGDE ENVIRONMENT TECHNOLOGY CO.,LTD. Contract record no.: X2022980015674 Denomination of invention: A cement raw meal additive and its application and cement production process Granted publication date: 20210827 License type: Common License Record date: 20220921 |