CN110240426B - 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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- CN110240426B CN110240426B CN201910502484.2A CN201910502484A CN110240426B CN 110240426 B CN110240426 B CN 110240426B CN 201910502484 A CN201910502484 A CN 201910502484A CN 110240426 B CN110240426 B CN 110240426B
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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
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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
- C04B7/38—Preparing or treating the raw materials individually or as batches, e.g. mixing with fuel
- C04B7/42—Active ingredients added before, or during, the burning process
- C04B7/421—Inorganic materials
- C04B7/424—Oxides, Hydroxides
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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
- C04B7/38—Preparing or treating the raw materials individually or as batches, e.g. mixing with fuel
- C04B7/42—Active ingredients added before, or during, the burning process
- C04B7/421—Inorganic materials
- C04B7/425—Acids or salts thereof
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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
- C04B7/38—Preparing or treating the raw materials individually or as batches, e.g. mixing with fuel
- C04B7/42—Active ingredients added before, or during, the burning process
- C04B7/428—Organic materials
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Abstract
The invention relates to a cement raw material additive, application thereof and a cement production process, wherein the cement raw material additive contains depolymerization reaction liquid of waste polyester and/or waste material after fractionation of the depolymerization reaction liquid, and an optional alkalinity improver. The cement raw material additive provided by the disclosure can recycle depolymerization reaction liquid of waste polyester and/or waste material after fractionation of the depolymerization reaction liquid 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 adjuvant used in the raw meal is relatively single, and there is no report of using polyester waste, particularly polyester depolymerization reaction liquid, as the adjuvant of the raw meal, and there are no reports of some studies on obtaining very good application effect.
The polyester is a general term for a polymer obtained by polycondensation of a polyhydric alcohol such as ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, cyclohexanediol, diethylene glycol, glycerin (glycerol), pentaerythritol and the like, and a polyhydric acid such as terephthalic acid, phthalic acid, adipic acid, succinic acid, glutaric acid, oxalic acid (oxalic acid), malonic acid, butenedioic acid and the like, which are commonly used in polyesters. Polyesters include, but are not limited to, mainly, polyethylene terephthalate and polyadipates, such as polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), a depolymerization reaction liquid of polybutylene terephthalate, a depolymerization reaction liquid of polyhexamethylene terephthalate, a depolymerization reaction liquid of polycyclohexylene terephthalate, a depolymerization reaction liquid of polyethylene terephthalate, polyethylene glycol adipate (PEGA), depolymerization reaction liquid of polybutylene adipate, depolymerization reaction liquid of polycyclohexanediolate, depolymerization reaction liquid of polydiethylene adipate, depolymerization reaction liquid of polyethylene glycol succinate, depolymerization reaction liquid of polybutylene succinate and the like, wherein one PET product accounts for the majority of markets.
Taking PET as an example, the PET is mainly applied to packaging materials (such as beverage bottles), filament fibers, staple fibers, films, engineering plastics, foaming materials and the like, and the consumption amount is 6000 million tons in the current year. With the increasing popularization of polyester products in production and life, the yield of polyester is rapidly increased, but end products such as beverage bottles, films, clothes, fishing nets and the like made of polyester are mostly disposable, so that environmental pollution and resource waste are caused. How to recycle and treat the waste polyester becomes a key research of scientific researchers in various countries. In the prior art, both the chemical treatment of leftover materials in the polyester processing process and the recovery chemical treatment of waste polyester and the chemical treatment of acid and alkali in the polyester product process are the chemical depolymerization treatment of polyester essentially. For example, CN101993164A "method for treating and recovering waste water generated during sharpening polybutylene terephthalate brush hair" and CN104829030A "method for treating and recovering waste water containing sodium terephthalate and 1, 4-butanediol" all disclose that toothbrush hair produced by polybutylene terephthalate (PBT) needs to be sharpened by strong alkali solution, and 0.2-0.4 kg of toothbrush hair raw material with 1 kg of PBT is lost after sharpening. Aiming at the waste water generated after the brush wires are treated by the alkaline solution, the document adopts related process technology to realize the recovery treatment of terephthalic acid and 1, 4-butanediol. For example, CN102070234A "method for separating sodium terephthalate and alkali solution from alkali weight reduction waste liquid" discloses that "in order to improve the hand feeling and soft feeling of polyester fabric, an alkali weight reduction process is performed during a printing and dyeing process, wherein the alkali weight reduction process is intermittent and continuous, and is used for alkali stripping of a part of polyester in polyester fabric (PET). Namely: PET + NaOH + sodium terephthalate + ethylene glycol. Therefore, this process produces a large amount of high COD, high alkalinity lye wastewater. This document provides a low running cost, acid-free process for separating sodium terephthalate and an alkaline solution from a waste stream, specifically a conditioned waste stream separated by a nanoporous ceramic filter.
In addition, different depolymerization and separation processes generate 3-30% of waste liquid after the fractionation of depolymerization reaction liquid, about 30% of the depolymerization reaction liquid is recycled by a chemical method in the polyester industry, the fractionated waste accounts for 10% of the depolymerized materials, and nearly 200 million tons of waste needs to be incinerated or biochemically treated every year. The comprehensive utilization of the waste polyester resources, particularly the use of the waste polyester as an additive in cement raw materials and the application thereof are rarely reported.
Disclosure of Invention
The cement raw meal additive can recycle depolymerization reaction liquid of waste polyester and/or waste materials obtained after fractionation of the depolymerization reaction liquid in cement raw meal grinding and cement production, and has good comprehensive effects of improving yield, reducing coal consumption, improving raw meal burnability and desulfurizing.
To achieve the above object, a first aspect of the present disclosure: provided is a cement raw meal additive comprising a depolymerization reaction liquid of waste polyester and/or a waste material after fractionation of the depolymerization reaction liquid, and optionally an alkali improver.
Alternatively, the depolymerization reaction liquid of the waste polyester is a depolymerization reaction liquid of a polyethylene terephthalate, preferably at least one of a depolymerization reaction liquid of a polyethylene terephthalate, a depolymerization reaction liquid of a polypropylene terephthalate, a depolymerization reaction liquid of a polybutylene terephthalate, a depolymerization reaction liquid of a polyhexamethylene terephthalate, a depolymerization reaction liquid of a polycyclohexylene terephthalate, and a depolymerization reaction liquid of a polyethylene terephthalate, and more preferably a depolymerization reaction liquid of a polyethylene terephthalate and/or a depolymerization reaction liquid of a polybutylene terephthalate.
Optionally, the depolymerization reaction liquid of the polyester contains 30-99 wt% of polybasic acid salt, 0-65 wt% of polyhydric alcohol and 0-10 wt% of inorganic base by weight and based on the total weight of the depolymerization reaction liquid of the polyester, or the depolymerization reaction liquid of the polyester contains 30-70 wt% of polybasic acid, 0-50 wt% of polyhydric alcohol and 5-70 wt% of inorganic acid salt;
the waste material after the fractionation of the depolymerization reaction solution contains 30-99 wt% of polybasic acid salt, 0-65 wt% of polyhydric alcohol and 0-10 wt% of inorganic base, or the waste material after the fractionation of the depolymerization reaction solution contains 30-70 wt% of polybasic acid, 0-50 wt% of polyhydric alcohol and 5-70 wt% of inorganic acid salt, based on the total weight of the waste material after the fractionation of the depolymerization reaction solution;
wherein the polybasic acid is at least one of terephthalic acid, phthalic acid, adipic acid, succinic acid, glutaric acid, oxalic acid, malonic acid and butenedioic acid; the polybasic acid salt is at least one of sodium salt, potassium salt, lithium salt, calcium salt and magnesium salt of the polybasic acid; the polyhydric alcohol is at least one of ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, cyclohexanediol and diethylene glycol; the inorganic base is at least one of sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, magnesium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, calcium carbonate, magnesium carbonate, sodium bicarbonate, potassium bicarbonate and trisodium phosphate; the inorganic acid salt is at least one of sodium salt, potassium salt, lithium salt, calcium salt and magnesium salt corresponding to hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, methanesulfonic acid, p-benzenesulfonic acid and sodium bisulfate.
Optionally, the depolymerization reaction liquid of the waste polyester is a reaction liquid obtained by depolymerizing the waste polyester by a hydrolysis method or a reaction liquid obtained by depolymerizing the waste polyester by an alcohol-base combination method.
Optionally, the alkalinity enhancer comprises 0-80% by weight of the cement raw meal additive; the alkalinity enhancer is at least one selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, magnesium hydroxide, calcium oxide, magnesium oxide, sodium carbonate, potassium carbonate, sodium methoxide, sodium ethoxide, potassium methoxide and potassium ethoxide.
Optionally, the cement raw meal additive contains 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.
Optionally, the cement raw meal additive contains 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.
In a second aspect of the present disclosure: the application of the cement raw meal additive in cement raw meal grinding is provided, and the application comprises the following steps:
mixing a cement raw material to be ground with a cement raw additive, and then grinding to obtain a cement raw product mixed with the cement raw additive;
or, the cement raw material is ground while being mixed with the cement raw material additive to obtain a cement raw material product mixed with the cement raw material additive;
or mixing the ground cement raw material with a cement raw additive to obtain a cement raw product mixed with the cement raw additive;
the cement raw material additive is the cement raw material additive of the first aspect of the disclosure, or the cement raw material additive is the depolymerization reaction liquid of the waste polyester and/or the waste material after fractionation of the depolymerization reaction liquid of the disclosure.
Alternatively, the cement raw material additive of the present disclosure accounts for 0.03 to 2% by weight of the total weight of the cement raw material and the cement raw material additive; the depolymerization reaction liquid of the waste polyester and/or the waste material after the fractionation of the depolymerization reaction liquid in the present disclosure account for 0.03 to 2 wt% of the total weight of the cement raw material and the depolymerization reaction liquid of the waste polyester and/or the waste material after the fractionation of the depolymerization reaction liquid; the raw materials of the cement raw material comprise 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.
A third aspect of the disclosure: a cement production process is provided, which comprises the following steps:
roasting the cement raw material product obtained by applying the second aspect of the disclosure 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.
By the technical scheme, the waste polyester depolymerization reaction liquid and/or the waste after fractionation of the depolymerization reaction liquid are used as the cement raw material additive or the main component of the cement raw material additive, and the cement raw material additive can be used for grinding cement raw materials, so that the problem of reasonable treatment of the waste polyester depolymerization reaction liquid and/or the waste after fractionation of the depolymerization reaction liquid can be solved, the purposes of cleanness, environmental protection, low cost and resource comprehensive utilization are achieved, a good grinding aid effect can be achieved, the yield can be improved, the material flowability in the grinding process is improved, the coal consumption and the sulfur dioxide discharge amount are reduced, and the mechanical property of the final cement is not 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 first aspect of the disclosure: provided is a cement raw meal additive comprising a depolymerization reaction liquid of waste polyester and/or a waste material after fractionation of the depolymerization reaction liquid, and optionally an alkali improver.
In the present disclosure, polyesters include, but are not limited to, primarily polyethylene terephthalate, polyadipates, polybutylenes, and the like, such as polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), and polyethylene adipate (PEGA), and the like. In the present disclosure, the depolymerization reaction liquid of the waste polyester may be a depolymerization reaction liquid of a polyethylene terephthalate, preferably at least one of a depolymerization reaction liquid of a polyethylene terephthalate, a depolymerization reaction liquid of a polypropylene terephthalate, a depolymerization reaction liquid of a polybutylene terephthalate, a depolymerization reaction liquid of a polyhexamethylene terephthalate, a depolymerization reaction liquid of a polycyclohexylene terephthalate, and a depolymerization reaction liquid of a polyethylene terephthalate, and more preferably a depolymerization reaction liquid of a polyethylene terephthalate and/or a depolymerization reaction liquid of a polybutylene terephthalate.
The depolymerization recovery process of the waste polyester according to the present disclosure may be a conventional process in the art, and may be, for example, depolymerization by an alcoholysis process, depolymerization by a hydrolysis process, or depolymerization by a combined alcohol-base process. The common alcoholysis depolymerization processes include a methanol alcoholysis process, an ethylene glycol alcoholysis process, an isooctanol alcoholysis process, a supercritical alcoholysis process and the like, conditions such as different alcoholysis reaction temperatures and pressures are large in difference and have advantages and disadvantages, and the obtained depolymerization reaction liquid mainly comprises corresponding polybasic acid ester and polyhydric alcohol; the hydrolysis depolymerization process comprises an acid hydrolysis method, an alkaline hydrolysis method, a neutral hydrolysis method and a supercritical hydrolysis method, and the obtained depolymerization reaction liquid mainly comprises polybasic acid (sodium) and polyhydric alcohol; the alcohol-base combined depolymerization process generally adopts corresponding polyhydric alcohol and strong base, for example, taking alcohol-base combined depolymerization of PET as an example, ethylene glycol and caustic soda are usually added as reaction media, and rapid decomposition can be realized at normal pressure to obtain sodium terephthalate and ethylene glycol. In the present disclosure, the depolymerization reaction liquid of the waste polyester is preferably a reaction liquid obtained by depolymerizing the waste polyester by a hydrolysis method or a reaction liquid obtained by depolymerizing the waste polyester by an alcohol-base combination method. The methods have more documents and have more mature industrial production technologies at home and abroad, such as relatively detailed introduction seen in the zhongqiao master paper 'process research on depolymerizing waste polyester bottles by alcohol-base hydrolysis' (southern university, 2012) and introduction related to 'chemical depolymerization research progress of waste polyester materials' (2011.31(1)) published in 'chemical environmental protection' by liu fu Sheng and the like.
The depolymerization reaction liquid obtained after the polyester depolymerization process is a corresponding polybasic acid ester (salt) and a polyhydric alcohol, and taking PET as an example, the depolymerization reaction liquid is terephthalic acid ester (salt) and ethylene glycol. The waste material after fractionation of the depolymerization reaction solution refers to a purified corresponding polyol and polyacid (or polyacid ester or polyacid salt) product obtained by treating the depolymerization reaction solution by conventional technical means (including acidification but not limited to acidification) and fractionating. In the present disclosure, the fractionated waste of the depolymerization reaction solution differs depending on the depolymerization method, some waste is obtained by directly fractionating the depolymerization reaction solution, and some waste is obtained by reacting the reaction solution with an inorganic acid and then fractionating the reaction solution. Wherein the salt is preferably a sodium salt; the inorganic acid may be, for example, sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, methanesulfonic acid, p-benzenesulfonic acid, sodium hydrogensulfate, or the like.
According to the present disclosure, the depolymerization reaction liquid of the polyester may contain 30 to 99 wt% of a polybasic acid salt, 0 to 65 wt% of a polyhydric alcohol, and 0 to 10 wt% of an inorganic base, or the depolymerization reaction liquid of the polyester may contain 30 to 70 wt% of a polybasic acid, 0 to 50 wt% of a polyhydric alcohol, and 5 to 70 wt% of an inorganic acid salt, by weight and based on the total weight of the depolymerization reaction liquid of the polyester.
Wherein the polybasic acid can be at least one of terephthalic acid, phthalic acid, adipic acid, succinic acid, glutaric acid, oxalic acid (i.e., oxalic acid), malonic acid and butenedioic acid; the polybasic acid salt may be at least one of sodium salt, potassium salt, lithium salt, calcium salt and magnesium salt of the polybasic acid; the polyhydric alcohol can be at least one of ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, cyclohexanediol and diethylene glycol; the inorganic base may be at least one of sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, magnesium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, calcium carbonate, magnesium carbonate, sodium bicarbonate, potassium bicarbonate, and trisodium phosphate; the inorganic acid salt may be at least one of sodium salt, potassium salt, lithium salt, calcium salt and magnesium salt corresponding to hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, methanesulfonic acid, p-benzenesulfonic acid and sodium bisulfate.
Further, when the depolymerization reaction liquid of the waste polyester is a depolymerization reaction liquid of a polyterephthalate, the depolymerization reaction liquid of the polyterephthalate may contain 50 to 99 wt% of a terephthalate, 0 to 50 wt% of a polyol and 0 to 10 wt% of an inorganic base, or the depolymerization reaction liquid of the polyterephthalate may contain 30 to 70 wt% of a terephthalic acid, 0 to 40 wt% of a polyol and 15 to 40 wt% of an inorganic acid salt, based on the total weight of the depolymerization reaction liquid of the polyterephthalate.
For example, when the depolymerization reaction liquid of the waste polyester is a depolymerization reaction liquid of polyethylene terephthalate, the depolymerization reaction liquid of polyethylene terephthalate may contain 50 to 99 wt% of a terephthalate salt, 0 to 40 wt% of ethylene glycol, and 0 to 10 wt% of an inorganic base, based on the total weight of the depolymerization reaction liquid of polyethylene terephthalate, or the depolymerization reaction liquid of polyethylene terephthalate may contain 50 to 99 wt% of terephthalic acid, 0 to 40 wt% of ethylene glycol, and 15 to 40 wt% of an inorganic acid salt.
The cement raw material additive (or the depolymerization reaction liquid of the waste polyester and/or the fractionated waste of the depolymerization reaction liquid) provided by the disclosure can be used for grinding the cement raw material in an internal mixing amount of 0.03-2 wt% (namely, by weight, the cement raw material additive (or the depolymerization reaction liquid of the waste polyester and/or the fractionated waste of the depolymerization reaction liquid) provided by the disclosure accounts for 0.03-2 wt% of the total weight of the cement raw material and the cement raw material additive (or the depolymerization reaction liquid of the waste polyester and/or the fractionated waste of the depolymerization reaction liquid), so as to achieve the effects of yield improvement and desulfurization.
The raw materials of cement are well known to those skilled in the art, and refer to the raw materials of cement before the first grinding in the preparation process of cement double-grinding and single-firing, and may include calcareous raw materials, clayey raw materials and calibration raw materials; 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 yield reaches 23 hundred million tons, the cement raw material amount is calculated by 1.6 times of the cement yield, calculated by 0.08 percent of the dosage of a cement raw material additive, about 294 ten thousand tons of the cement raw material additive is needed, the cement raw material is different from cement clinker, and a grinding aid capable of being used for the cement clinker is generally difficult to be used for reducing coal consumption and sulfur dioxide emission in the cement raw material.
According to the present disclosure, the alkalinity enhancer is a substance capable of enhancing the alkalinity of the depolymerization reaction liquid of the waste polyester and/or the fractionation waste liquid of the waste after the fractionation of the depolymerization reaction liquid, and may be, for example, an alkali compound, and is capable of reducing the emission amount of sulfur dioxide, and the alkalinity enhancer may be 0 to 80% by weight, preferably 1 to 75% by weight, more preferably 3 to 70% by weight, and still more preferably 10 to 60% by weight, based on the weight of the cement raw material additive; the alkalinity enhancer may be at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, magnesium hydroxide, calcium oxide, magnesium oxide, potassium carbonate, sodium methoxide, sodium ethoxide, potassium methoxide and potassium ethoxide, and other alkaline substances may be used as the alkalinity enhancer.
According to the present disclosure, the depolymerization reaction liquid of the waste polyester and/or the waste material after fractionation of the depolymerization reaction liquid can be directly used as an additive for grinding without any pretreatment, and the effect of adding the adjustment additive is better. The adjusting additive is used for improving the properties of the waste polyester depolymerization reaction liquid and/or the waste material after fractionation of the depolymerization reaction liquid, such as grinding aid, desulfurization and the like, and the weight ratio of the waste polyester depolymerization reaction liquid and/or the waste material after fractionation of the depolymerization reaction liquid to the adjusting additive can be 100: (0-1000), preferably 100: (1-600).
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.
In a second aspect of the present disclosure: provides an application of a cement raw material additive in cement raw material grinding.
In one embodiment, the application comprises: mixing the raw cement material to be ground with the raw cement additive (for example, adding the raw cement additive to a conveyor belt carrying the raw cement material to be mixed with the raw cement material), and grinding to obtain the raw cement product mixed with the raw cement additive.
In a second embodiment, the application comprises: the cement raw material is ground while being mixed with the cement raw additive (i.e. the mixing is completed in the grinding treatment device), so as to obtain the cement raw product mixed with the cement raw additive.
In a third embodiment, the application comprises: mixing the ground raw cement material with the raw cement additive (such as mixing in raw cement powder selection, raw cement warehouse or bucket elevator before preheater) to obtain raw cement product mixed with the raw cement additive.
In the above embodiment, the pulverizing process may be performed in a conventional apparatus (e.g., a raw mill). The application is preferably realized in the first embodiment in which the mixing of the raw cement material and the raw cement additives is performed before the grinding process.
The cement raw material additive is the cement raw material additive of the first aspect of the disclosure, or the cement raw material additive is the depolymerization reaction liquid of the waste polyester and/or the waste material after fractionation of the depolymerization reaction liquid of the disclosure. In the present disclosure, the depolymerization reaction solution of the waste polyester and/or the waste material after fractionation of the depolymerization reaction solution may be directly ground into cement raw material, or may be optionally blended and then used as cement raw material ground.
According to the present disclosure, the cement raw material additive may account for 0.03 to 2% by weight of the total weight of the cement raw material and the cement raw material additive. Alternatively, when the depolymerization reaction solution of the waste polyester and/or the waste after fractionation of the depolymerization reaction solution are used as they are, the depolymerization reaction solution of the waste polyester and/or the waste after fractionation of the depolymerization reaction solution may account for 0.03 to 2 wt% of the total weight of the cement raw material and the depolymerization reaction solution of the waste polyester and/or the waste after fractionation of the depolymerization reaction solution. The raw materials of the cement raw materials 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.
A third aspect of the disclosure: a cement production process is provided, which comprises the following steps:
roasting the cement raw material product obtained by applying the second aspect of the disclosure 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 calcination of cement raw products is well known to those skilled in the art in light of this disclosure and refers to feeding the raw ground product into a cement rotary kiln and calcining it to a partial fusion to obtain calcium silicate cement clinker (granular or block) containing calcium silicate as a main 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 depolymerization reaction liquid of polyester or waste after fractionation of the depolymerization reaction liquid used in the examples of the present disclosure is derived from the following four cases:
a reaction liquid sample is depolymerized by a laboratory acid hydrolysis method, 192 g of polyethylene glycol terephthalate, 180 g of water and 3 g of sulfuric acid are added into a 1000ml high-pressure kettle, the hydrolysis depolymerization reaction is carried out for 5h at the temperature of 190 ℃ and under the pressure of 1MPa, potassium carbonate with equivalent of sulfuric acid is added for neutralization after the reaction is finished, the solution A is marked, the reaction liquid mainly comprises 44 wt% of terephthalic acid, 16 wt% of ethylene glycol, 1 wt% of potassium sulfate and 38 wt% of water, and the sample is uniformly stirred when in use. The waste material after the fractionation of the depolymerization reaction liquid of the polyethylene glycol terephthalate is derived from a waste material sample after the fractionation after the depolymerization by the laboratory alcohol-base combination method, for example, 192 g of the polyethylene glycol terephthalate, 88 g of sodium hydroxide and 31 g of ethylene glycol are added into a 1000ml high-pressure kettle, the reaction is carried out for 2h at the temperature of 100 ℃ and 110 ℃ and under the pressure of 0.1MPa, the reaction liquid is heated and rectified under normal pressure after the reaction is finished, the reflux ratio is controlled to be 2:1, the temperature of the top of the tower is 197 ℃, the kettle liquid after about 70 g of ethylene glycol is distilled out and is marked as liquid B, the waste material after the fractionation mainly comprises 86 weight percent of sodium terephthalate, 9 weight percent of ethylene glycol and 3 weight percent of sodium hydroxide, and the sample is stirred uniformly when in use.
The depolymerization reaction liquid of the poly (butylene adipate) comes from a sample of a laboratory alkaline hydrolysis method, for example, 198 g of poly (butylene adipate), 120 g of water and 84 g of sodium hydroxide are added into a 1000ml autoclave, the hydrolysis depolymerization reaction is carried out at 230 ℃ and 2.5-3MPa, the solution is marked as solution C, the reaction liquid mainly comprises 46 wt% of disodium adipate, 22 wt% of butanediol, 29 wt% of water and 1% of sodium hydroxide, and the sample is stirred uniformly when in use.
The waste material after fractionation of the depolymerization reaction liquid of the poly (butylene adipate) comes from a sample of a laboratory alcoholysis method, for example, 198 g of poly (butylene adipate), 96 g of methanol and 1 g of methanesulfonic acid are added into a 1000ml high-pressure kettle, alcoholysis depolymerization reaction is carried out at 65-70 ℃ and 0.1-0.2MPa, sodium hydroxide equivalent to methanesulfonic acid is added for neutralization after the reaction is finished, then the neutralized reaction liquid is heated for normal-pressure rectification, the reflux ratio is controlled to be 2:1, the temperature at the top of the tower is about 65-229 ℃, 265 g of distillate (containing 30 g of methanol, 82 g of butanediol and 153 g of dimethyl adipate) is recorded as liquid D after fractionation, the liquid D mainly comprises 60% of dimethyl adipate, the content of butanediol is 31% by weight, the content of sodium methanesulfonate is 5% by weight, and the sample is uniformly stirred when in use.
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 weight/(cement raw material weight + cement raw material additive weight).
In the embodiment, the doping proportion in the waste liquid is the weight of the waste liquid/(the weight of the waste liquid + the weight of the raw material of the cement raw material), wherein the waste liquid refers to the depolymerization reaction liquid of the waste polyester and/or the waste after fractionation of the depolymerization reaction liquid.
First, application of the Experimental results
Examples SA1-SA5 and comparative example DA1 illustrate the effect of cement raw meal additives with or without depolymerized reaction fluids containing waste polyesters on the grinding effect of raw meal
Taking a cement raw material of Tianrui group Guangshan Cement Co Ltd as an experimental sample, drying and crushing the raw material, and then uniformly stirring to simulate actual cement raw material limestone of a factory: sandstone: iron ore: the shale is prepared according to the proportion of 85:6.9:4.5:3.6(W/W), 5000g of shale is taken out for small grinding each time, the shale is ground for 9 minutes, and the density is as follows: 2.73kg/m3The blank 0.08mm of screen residue is controlled according to 13.0-16.0 percent, and the 02mm of screen residue is less than 1.0 percent.
Comparative example DA1
The raw materials of the cement raw materials are independently subjected to grinding treatment, and specific conditions and results are shown in table 1.
Example SA1
The solution A (100 parts by weight) is mixed with cement raw materials in a proportion of 0.03 weight percent for grinding treatment and calcination, and specific conditions and results are shown in Table 1.
Example SA2
The solution A (100 parts by weight) is mixed with cement raw materials in a proportion of 0.1 percent by weight for grinding treatment and calcination, and 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, and cement raw material is mixed with 0.3% by weight of the solution A to carry out grinding treatment and calcination, wherein 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 raw material is added in a proportion of 0.8% by weight to perform 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 2 wt% of a cement raw material was added to the solution A to perform grinding and calcination, and the specific conditions and results are shown in Table 1.
TABLE 1 comparison table of grinding and calcining effects of cement raw material additives with different mixing amounts and formulas
As can be seen from Table 1, with the increase of the internal mixing proportion and the addition of the adjusting additive, the specific surface area of the raw material grinding is increased, and the sifting residue is obviously reduced; the free calcium oxide (f-CaO) content of the calcination experiments of K1450 and K1350 was significantly reduced, indicating an improved sinterability.
Examples SB1-SB4 and comparative example DA1 illustrate the effect of depolymerization reaction liquids of different waste polyesters and/or the waste after fractionation of the depolymerization reaction liquids 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 a cement raw material was added in an amount of 0.3% by weight to perform grinding treatment and calcination, and the specific conditions and results are shown in Table 2.
Example SB2
After adding 10 parts by weight of an alkaline enhancer (sodium hydroxide) to the solution B (100 parts by weight), 20 parts by weight of glycerin and 40 parts by weight of diethanol monoisopropanolamine were added as cement raw material additives, and cement raw material was added in an amount of 0.3% by weight to perform grinding treatment and calcination, and the specific conditions and results are shown in Table 2.
Example SB3
After adding 10 parts by weight of an alkaline enhancer (sodium hydroxide) to the solution C (100 parts by weight), 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 were added in an amount of 0.3% by weight to perform grinding and calcination, and the specific conditions and results are shown in Table 2.
Example SB4
After adding 10 parts by weight of an alkaline enhancer (sodium hydroxide) to the solution D (100 parts by weight), 20 parts by weight of molasses and 40 parts by weight of diethanol monoisopropanolamine were added as cement raw material additives, and cement raw material was added in an amount of 0.3% by weight to conduct grinding treatment and calcination, and the specific conditions and results are shown in Table 2.
TABLE 2 comparison of grinding and calcining effects of cement raw material additives containing different depolymerization reaction liquids
As can be seen from Table 2, the cement raw material additives containing different depolymerization reaction liquids have increased specific surface area of raw material grinding and obviously reduced screen residue; the free calcium oxide (f-CaO) content of the calcination experiments of K1450 and K1350 was significantly reduced.
Second, industrial application test
The industrial experiment is carried out by Leishui cement Co Ltd in south of Hunan, and the specific operation steps are as follows: feeding cement raw materials (DA1) alone or with depolymerization reaction liquid containing waste polyester cement raw material additive (SC1) into a vertical mill for raw material grinding under the conditions that the fineness is controlled to be less than 18 weight percent (0.08mm), 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 calculated to be 700 amperes for complement, the kiln rotating speed is 3.8 revolutions per minute, the decomposition temperature is 860 degrees for complement, and the average decomposition rate of calcium carbonate is normally controlled to be 95.5-96.5 percent, so that the clinker to be ground for cement is obtained; during the period, the average yield of raw material grinding, the fineness of the obtained raw material (the weight ratio of the sieved residue), the decomposition temperature and the decomposition rate of calcium carbonate during roasting, and the average standard coal consumption were measuredAnd flue gas SO at the outlet of the preheater2Concentration, etc. the comparison time of DA1 and SC1 is 120 h.
Example SC1
The solution A (100 parts by weight) was mixed with cement raw materials in an amount of 0.2% by weight, and subjected to milling treatment and calcination, and the specific conditions and results are shown in Table 3.
TABLE 3 trial effect table for industrial application
As can be seen from Table 3, the added cement raw meal additive reduces the coal consumption by reducing the fineness of the raw meal and the decomposition temperature of the decomposing furnace, and the cement raw meal additive can promote the absorption of calcium to sulfur dioxide and obviously reduce the SO in the outlet flue gas of the preheater2Concentration, certain environmental protection benefit, and the quality of cement clinker products such as the compressive strength of clinker is slightly increased.
As can be seen from tables 1 to 3, the depolymerization reaction solution of waste polyester and/or the waste material after fractionation of the depolymerization reaction solution of the present disclosure have various effects of grinding aid, yield increase, desulfurization and calcination improvement, and the effect can be remarkably improved after the addition of the adjustment additive and the alkalinity enhancer.
The preferred embodiments of the present disclosure have been described in detail above, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all fall within the protection scope of the present disclosure.
It should be noted that, in the foregoing embodiments, various features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various combinations that are possible in the present disclosure are not described again.
In addition, any combination of various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present disclosure, as long as it does not depart from the spirit of the present disclosure.
Claims (10)
1. The cement raw material additive is characterized by comprising depolymerization reaction liquid of waste polyester and/or waste material after fractionation of the depolymerization reaction liquid, an alkaline enhancer and an alcamines additive;
the depolymerization reaction liquid of the waste polyester is depolymerization reaction liquid of polyester terephthalate;
the depolymerization reaction liquid of the polyterephthalate is at least one of depolymerization reaction liquid of polyethylene terephthalate, depolymerization reaction liquid of polytrimethylene terephthalate and depolymerization reaction liquid of polybutylene terephthalate.
2. The cement raw meal additive as set forth in claim 1, wherein the depolymerization reaction liquid of the waste polyester is a depolymerization reaction liquid of polyethylene terephthalate and/or a depolymerization reaction liquid of polybutylene terephthalate.
3. The cement raw meal additive as set forth in claim 1, wherein the depolymerization reaction liquid of the polyester comprises 30 to 99% by weight of a polybasic acid salt, 0 to 65% by weight of a polyhydric alcohol, and 0 to 10% by weight of an inorganic base, or 30 to 70% by weight of a polybasic acid, 0 to 50% by weight of a polyhydric alcohol, and 5 to 70% by weight of an inorganic acid salt, based on the total weight of the depolymerization reaction liquid of the polyester;
the waste material after the fractionation of the depolymerization reaction solution contains 30-99 wt% of polybasic acid salt, 0-65 wt% of polyhydric alcohol and 0-10 wt% of inorganic base, or the waste material after the fractionation of the depolymerization reaction solution contains 30-70 wt% of polybasic acid, 0-50 wt% of polyhydric alcohol and 5-70 wt% of inorganic acid salt, based on the total weight of the waste material after the fractionation of the depolymerization reaction solution;
wherein the polybasic acid is terephthalic acid; the polybasic acid salt is at least one of sodium salt, potassium salt, lithium salt, calcium salt and magnesium salt of the polybasic acid; the polyalcohol is at least one of ethylene glycol, propylene glycol and butanediol; the inorganic base is at least one of sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, magnesium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, calcium carbonate, magnesium carbonate, sodium bicarbonate, potassium bicarbonate and trisodium phosphate; the inorganic acid salt is at least one of sodium salt, potassium salt, lithium salt, calcium salt and magnesium salt corresponding to hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, methanesulfonic acid, p-benzenesulfonic acid and sodium bisulfate.
4. The cement raw meal additive as set forth in claim 1, wherein the depolymerization reaction liquid of the waste polyester is a reaction liquid obtained by depolymerization of the waste polyester by a hydrolysis method or a reaction liquid obtained by depolymerization of the waste polyester by an alcohol-base combination method.
5. 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 enhancer is at least one selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, magnesium hydroxide, calcium oxide, magnesium oxide, sodium carbonate, potassium carbonate, sodium methoxide, sodium ethoxide, potassium methoxide and potassium ethoxide.
6. The cement raw meal additive as claimed in claim 1, wherein the proportion of the alcohol amine based additive is less than 99% by weight of the cement raw meal additive; the alkanolamine additive is at least one selected from triethanolamine, triisopropanolamine, tricyclohexylamine, diethanolisopropanolamine, diethanolisocyclolamine, diisopropanolamine, dicyclohexylamine, and dicyclohexylamine monoisopropanolamine.
7. 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.
8. Use of a cement raw meal additive in cement raw meal, characterized in that the use comprises:
mixing a cement raw material to be ground with a cement raw additive, and then grinding to obtain a cement raw product mixed with the cement raw additive;
or, the cement raw material is ground while being mixed with the cement raw material additive to obtain a cement raw material product mixed with the cement raw material additive;
or mixing the ground cement raw material with a cement raw additive to obtain a cement raw product mixed with the cement raw additive;
the cement raw material additive is the cement raw material additive as defined in any one of claims 1 to 7, or the cement raw material additive is the depolymerization reaction solution of the waste polyester as defined in any one of claims 1 to 7 and/or the waste after fractionation of the depolymerization reaction solution.
9. The use according to claim 8, wherein the cement raw material additive as set forth in any one of claims 1 to 7 is contained in an amount of 0.03 to 2% by weight based on the total weight of the cement raw material and the cement raw material additive; the depolymerization reaction solution of waste polyester and/or the waste material after the fractionation of the depolymerization reaction solution according to any one of claims 1 to 7 is 0.03 to 2% by weight based on the total weight of the cement raw material and the depolymerization reaction solution of waste polyester and/or the waste material after the fractionation of the depolymerization reaction solution; the raw materials of the cement raw material comprise 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.
10. A cement production process, characterized in that the process comprises:
calcining the cement raw material product obtained by the application of claim 8 or 9 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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