WO2013038908A1 - Lime slurry and clinker production method using same - Google Patents

Lime slurry and clinker production method using same Download PDF

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Publication number
WO2013038908A1
WO2013038908A1 PCT/JP2012/071881 JP2012071881W WO2013038908A1 WO 2013038908 A1 WO2013038908 A1 WO 2013038908A1 JP 2012071881 W JP2012071881 W JP 2012071881W WO 2013038908 A1 WO2013038908 A1 WO 2013038908A1
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Prior art keywords
lime
mass
gypsum
reducing agent
alumina
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PCT/JP2012/071881
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French (fr)
Japanese (ja)
Inventor
朝明 西岡
永治郎 向
雅夫 松本
那須　一郎
岩波　和英
白井　健太郎
一平 中島
亮悦 吉野
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電気化学工業株式会社
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Application filed by 電気化学工業株式会社 filed Critical 電気化学工業株式会社
Priority to JP2013533601A priority Critical patent/JP5941918B2/en
Priority to CN201280044419.6A priority patent/CN103796968B/en
Publication of WO2013038908A1 publication Critical patent/WO2013038908A1/en

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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
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C04B28/10—Lime cements or magnesium oxide cements
    • 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
    • C04B7/32—Aluminous cements
    • C04B7/323—Calcium aluminosulfate cements, e.g. cements hydrating into ettringite

Definitions

  • the present invention relates to a slurry containing lime.
  • the present invention also relates to a method for producing a clinker using the slurry as a raw material.
  • CSA Calcium sulfoaluminate
  • the dust generated from the calcium carbide manufacturing furnace is mainly made of slaked lime, so if it is used as a raw material for slurry, it can be used as a lime raw material instead of limestone, and it is possible to reduce the amount of CO 2 generated.
  • the use of the dust is large, but the dust has thixotropy, so it causes the failure of the slurry agitator at the slurry production stage, or the failure of the transport equipment such as a pump at the transportation stage. Was blocked.
  • the present invention has been created in view of the above circumstances. That is, the present invention provides a lime slurry capable of producing a clinker with a small load on the global environment, capable of suppressing the occurrence of an orifice-like coating in the kiln during firing of the clinker, and capable of suppressing clogging of piping during pumping. Providing is one of the issues. Another object of the present invention is to provide a method for producing a clinker using the lime slurry according to the present invention as a raw material.
  • the present inventor has made extensive studies to solve the above-mentioned problems.
  • slaked lime as a raw material, it is possible to add a water reducing agent as a raw material for slurry while suppressing the generation of CO 2 and coating during firing. It was found that gelation was prevented by this and that blockage of piping during slurry transportation could be reduced.
  • This invention is completed based on the said knowledge, and is specified by the following.
  • the present invention contains slaked lime, gypsum, alumina, water and a water reducing agent having an average particle size of 4 ⁇ m or more, the hydrotalcite content is less than 0.5 mass%, and the flow value is 200 mm. It is the lime slurry which is the above.
  • the water reducing agent is at least one selected from the group consisting of lignin, melamine, polycarboxylic acid, and naphthalene.
  • the polycarboxylic acid-based water reducing agent occupies 0.20% by mass or more based on the total mass of slaked lime, gypsum and alumina
  • Naphthalene-based water reducing agent occupies 0.28% by mass or more based on the total mass of slaked lime, gypsum and alumina
  • the lignin-based water reducing agent occupies 1.00% by mass or more based on the total mass of slaked lime, gypsum and alumina
  • the melamine water reducing agent occupies 1.00% by mass or more based on the total mass of slaked lime, gypsum and alumina.
  • the lime slurry contains slaked lime by-produced when acetylene is generated from calcium carbide.
  • the present invention includes slaked lime, gypsum, alumina, water, a polycarboxylic acid-based water reducing agent having an average particle size of 4 ⁇ m or more, and a hydrotalcite content of 0.5% by mass or more.
  • a lime slurry having a flow value of 200 mm or more.
  • the lime slurry contains dust having a thixotropy including slaked lime and hydrotalcite, which is captured in a wet dust collecting process of a calcium carbide electric furnace.
  • the polycarboxylic acid-based water reducing agent accounts for 1.00% by mass or more based on the total mass of slaked lime, gypsum and alumina.
  • the content of water in the lime slurry is 8 to 25% by mass, and the molar ratio of gypsum to alumina (CaSO 4 / Al 2 O 3 ) is 2 to 10, and the molar ratio of slaked lime to alumina (Ca (OH) 2 / Al 2 O 3 ) is 2 to 30.
  • the lime slurry is a clinker production raw material.
  • the present invention is a method for producing a clinker including a step of firing the lime slurry described above after piping transportation.
  • the clinker is calcium sulfoaluminate (CSA).
  • the generation of CO 2 is suppressed, and the clinker can be produced with a small amount of energy, so the burden on the global environment can be reduced.
  • the lime slurry according to the present invention is used as a raw material, it is possible to suppress the occurrence of an orifice-like coating in the kiln during clinker firing.
  • the viscosity of the lime slurry according to the present invention is ensured to an appropriate value by suppressing gelation, so that piping blockage during pumping can be suppressed, and the load on the basin rake can be reduced. . Therefore, the industrial utility value of the present invention is extremely large.
  • the lime slurry according to the present invention contains water, slaked lime, gypsum, alumina, and a water reducing agent.
  • the lime slurry can be used as a clinker production raw material.
  • a clinker is a pulverized product containing one or more minerals that is fired until a part of its components melts (semi-molten state), and is baked into a lump, and the type is particularly limited.
  • Illustrative examples include calcium sulfoaluminate (CSA) and clinker such as cement.
  • Calcium sulfoaluminate typically has CaO, CaSO 4 , and Al 2 O 3 as chemical compositions, and CaO, CaSO 4 , 3CaO ⁇ 3Al 2 O 3 ⁇ CaSO 4 (Yelimeite, or It is a reaction product containing a chemical substance called Hauine and defined in CAS No. 12005-25-3.
  • any of ground water, tap water, rain water and the like can be used. These waters are not limited to hardness and the like, and any of them can be used. Water plays a role of imparting fluidity.
  • the water content in the lime slurry may be appropriately adjusted in consideration of this point. However, if the amount is too small, pumping becomes difficult. On the other hand, if the amount is too large, phase separation from other components occurs. Therefore, the preferable water content in the lime slurry is 8 to 25% by mass, more preferably 10 to 20% by mass.
  • the lime used in the present invention is slaked lime. Since calcining limestone requires energy for decarboxylation, it is disadvantageous in terms of energy. Further, when limestone is fired, it is also disadvantageous in that an orifice-shaped coating is generated so as to close the inside of the furnace due to a decarboxylation reaction. If slaked lime is used, such inconvenience is eliminated.
  • the slaked lime is not particularly limited.
  • finely powdered lime produced by a sedimentation method chemically, finely powdered slaked lime for adsorption of dioxins in an incinerator obtained by pulverizing finely powdered slaked lime, and a process for producing acetylene gas by a calcium carbide method And by-product slaked lime contained in the dust captured in the wet dust collection process of the calcium carbide electric furnace.
  • the dust captured in the wet dust collection process of the calcium carbide electric furnace contains hydrotalcite (typically 1 to 10% by mass, more typically 2 to 8% by mass), and thereby thixotropic properties. Therefore, it was difficult to transport the piping. Therefore, although it was not used and generally discarded, according to the present invention, it can be recycled as a raw material of lime slurry. That is, the present invention also contributes to waste reduction.
  • the slaked lime needs to have an average particle size of 4 ⁇ m or more and preferably 5 ⁇ m or more in order to sufficiently obtain the effect of improving the fluidity by the water reducing agent.
  • the average particle diameter of slaked lime is less than 4 ⁇ m, the effect of improving the fluidity by the water reducing agent is small, so that the slurry is easily gelled, the viscosity increases, and the slurry is difficult to transport.
  • the average particle size of slaked lime exceeds 100 ⁇ m, material separation of slurry basin, poor firing in the kiln, etc. are likely to occur, and operation may be difficult.
  • the average particle size of slaked lime is preferably 80 ⁇ m or less, more preferably 60 ⁇ m or less, and even more preferably 50 ⁇ m or less.
  • the average particle diameter is 50% of the volume-based integrated fraction measured by “JIS R 1629 fine ceramic raw material particle diameter distribution measurement method by laser diffraction / scattering method”.
  • the content of slaked lime in the lime slurry may be appropriately adjusted according to the type of clinker to be produced.
  • any of dihydrate gypsum, hemihydrate gypsum, anhydrous gypsum, etc. can be used.
  • dihydrate gypsum natural dihydrate gypsum, flue gas desulfurization dihydrate gypsum generated from a thermal power plant Waste gypsum board generated as industrial waste
  • hemihydrate gypsum called calcined gypsum phosphoric acid byproduct anhydrous gypsum, natural anhydrous gypsum, and the like
  • the particle size is not limited, and any of lumps and pulverized materials can be used.
  • the content of gypsum in the lime slurry may be appropriately adjusted depending on the type of clinker to be produced. For example, when producing CSA, it is blended so that the molar ratio of CaSO 4 / Al 2 O 3 is 2 to 10. Can do.
  • any of natural band shale, aluminum residual ash generated as aluminum dross, calcined alumina, alumina slurry generated as industrial waste, and the like can be used.
  • the particle size is not limited, and any of lumps and pulverized materials can be used.
  • the water reducing agent plays a role of preventing the lime slurry from gelling, lowers the viscosity, and improves the fluidity. This prevents the piping from being blocked when the lime slurry is transported by piping.
  • the amount of the water reducing agent added to the lime slurry is not particularly limited, but if the added amount is excessive, the effect is saturated and uneconomical, and conversely if the added amount is too small, a sufficient effect cannot be obtained. It is necessary to appropriately control the amount of water reducing agent relative to the total amount of slaked lime, alumina, gypsum and water reducing agent in the lime slurry. As will be described later, this appropriate amount varies depending on the type of water reducing agent, and also varies depending on whether or not the lime slurry exhibits thixotropy. Therefore, a sensible choice is required.
  • water reducing agents used in the present invention include lignin (typically lignin sulfonate), melamine (typically melamine sulfonate), and polycarboxylic acid (typically polycarboxylic acid).
  • lignin typically lignin sulfonate
  • melamine typically melamine sulfonate
  • polycarboxylic acid typically polycarboxylic acid
  • naphthalene type typically naphthalene sulfonic acid type
  • a polycarboxylic acid type and a naphthalene type are preferable, and a polycarboxylic acid type is the most preferable.
  • lignin-based water reducing agent “Darlex F-1, WRDA” (Grace Chemicals Co., Ltd.), “Pozoris No. 70 series” (BASF Pozzolith Co., Ltd.), melamine mainly composed of lignin sulfonate.
  • FT-700N series (Grace Chemicals Co., Ltd.) mainly composed of melamine sulfonic acid formaldehyde condensate salt as water reducing agent
  • "Darlex Super” of polycarboxylic acid polymer compound as polycarboxylic acid water reducing agent "100, 200, 300, 1000N” series (Grace Chemicals Co., Ltd.)
  • naphthalene-based water reducing agents include "FT-500V series” (Grace Chemicals Co., Ltd.) and the like mainly composed of alkyl naphthalene sulfonic acid formalin condensate.
  • “FT-80” (Grace Chemicals Co., Ltd.), which is a mixture of lignin and naphthalene, can also be used.
  • the amount of water reducing agent to be added varies greatly depending on the hydrotalcite content in the lime slurry.
  • the hydrotalcite content is less than 0.5% by mass, preferably less than 0.1% by mass, more preferably 0% by mass
  • the type of water reducing agent that can be used there is no particular limitation on the type of water reducing agent that can be used, and the flow value described later is What is necessary is just to adjust an addition amount suitably so that it may become 200 mm or more.
  • the effect is saturated even if added excessively.
  • the polycarboxylic acid-based water reducing agent has a lower limit of 0.20% by mass or more, preferably 0.25% by mass or more, and an upper limit of 10.00% with respect to the total mass of slaked lime, gypsum and alumina. It is at most mass%, preferably at most 5.00 mass%, more preferably at most 1.00 mass%.
  • the naphthalene-based water reducing agent has a lower limit of 0.28% by mass or more, preferably 0.50% by mass or more, and an upper limit of 10.00% by mass or less with respect to the total mass of slaked lime, gypsum and alumina. , Preferably it is 5.00 mass% or less, More preferably, it is 1 mass or less.
  • the lignin-based water reducing agent has a lower limit of 1.00% by mass or more, preferably 2.00% by mass or more, and an upper limit of 10.00% by mass with respect to the total mass of slaked lime, gypsum and alumina.
  • the melamine-based water reducing agent is 1.00% by mass or more, preferably 2.00% by mass or more, and the upper limit is 10.00% by mass or less, preferably based on the total mass of slaked lime, gypsum and alumina. Is 5.00 mass% or less, more preferably 3.00 mass% or less.
  • the types of water reducing agents that can be used are limited. Receive. Specifically, since there is no practically effective effect other than the polycarboxylic acid-based water reducing agent, it is necessary to use a polycarboxylic acid-based water reducing agent.
  • the addition amount of the water reducing agent in this case has a lower limit of 1.00% by mass or more, preferably 2.00% by mass or more, and an upper limit of 10.00% by mass or less with respect to the total mass of slaked lime, gypsum and alumina. , Preferably 5.00 mass or less, more preferably 3.00 mass% or less.
  • the lime slurry according to the present invention can be produced by kneading the above-described components with a ball mill or the like.
  • the flow value can be 200 mm or more, and in a preferred embodiment, it can be 250 mm or more. In a typical embodiment, Is 200 to 300 mm.
  • the flow value is an index of the fluidity of the slurry, and the higher the value, the better the fluidity.
  • the flow value can be increased by increasing the amount of water reducing agent added. Therefore, the amount of water reducing agent added may be increased until the flow value rises to a desired value.
  • the required addition amount varies depending on the average particle size of the slaked lime used as the raw material of the lime slurry, and the larger the average particle size of the slaked lime, the higher the fluidity improving effect.
  • the flow value is measured by a physical test method (flow test) of JIS R 5201 cement.
  • flow test a physical test method
  • the plastic body under test after impacting 15 times (one time / one second) after reversing the flow cone has the appearance shown in FIG. 1, and the powder is W1 in addition to W2 and W3. Showing spread.
  • the W1 value after impacting 15 times 15 seconds with respect to the W1 value at the time of reversing the flow cone shows a value larger than 1.5, more preferably a value larger than 2.0.
  • the obtained lime slurry can be transported by piping with a transport pump, for example, transported to a clinker firing furnace.
  • a transport pump for example, transported to a clinker firing furnace.
  • gelation is suppressed and the viscosity is hardly increased, so that piping transportation is possible.
  • the firing furnace is not limited, but a rotary kiln is common.
  • the conditions of the firing furnace may be appropriately adjusted depending on the type of clinker. For example, when firing CSA, firing is performed at a temperature of about 1100 to 1300 ° C.
  • the lime slurry according to the present invention does not require decarbonation energy in the firing stage, not only can the firing fuel rate be reduced, but also the amount of CO 2 generated can be reduced, which is effective for reducing the burden on the global environment. It is. Moreover, since the decarboxylation reaction does not occur, the occurrence of coating can be suppressed.
  • FIG. 2 schematically shows an example of a clinker manufacturing system using the lime slurry according to the present invention.
  • Water, slaked lime, gypsum, alumina, and a water reducing agent which are raw materials of the lime slurry, are supplied from a water feeder 1, a slaked lime feeder 2, a gypsum feeder 3, an alumina feeder 4, and a water reducing agent feeder 5 to a wet raw material mill 6 through piping. .
  • Each raw material is sufficiently kneaded in the wet raw material mill 6 to become a lime slurry, and is then temporarily stored in a buffer tank 8 with a stirrer through a pipe by a slurry transport pump 7, and then fired through the pipe by a slurry transport pump 9.
  • the clinker is manufactured by charging the furnace 10.
  • Raw material> The raw material of the lime slurry used for the invention example and the comparative example is shown below.
  • (1) Lime content Lime 1: Dust captured in the wet dust collection process of the calcium carbide electric furnace.
  • Lime 2 By-product slaked lime generated in the manufacturing process of acetylene gas by the carbide method.
  • Lime 3 The lime 2 is crushed.
  • Lime 4 Commercially available slaked lime ("Hishikar" Ryoko Lime Industry Co., Ltd.).
  • Lime 5 Limestone produced at Aomi factory of Electrochemical Industry Co., Ltd. Table 1 shows the composition and average particle size of these limes.
  • the exhaust gypsum is obtained by recovering SO 2 gas from the exhaust gas from the thermal power plant by using a flue gas desulfurization device and converting it into gypsum.
  • Alumina Aluminum residual ash in which Al 2 O 3 accounts for about 90% by mass was used in all inventive examples and comparative examples.
  • (4) Water General industrial water was used as the water in all the inventive examples and comparative examples.
  • each slurry is sent to a buffer tank with a stirring rake by a transport pump, and further transported by piping using a transport pump, and then charged into a rotary kiln (inner diameter 3 m, length 70 m) at a flow rate of 300 t / day, A CSA clinker firing test was performed. No. using limestone as a raw material of lime slurry. In No. 1, after about 3 days from the start of operation, the pressure in the kiln increased and the operation became impossible in about one week. When the inside of the rotary kiln was inspected, an orifice-like coating was generated inside the kiln. No.
  • Examples 2 to 8 are examples in which lime 1 (dust captured in a wet dust collecting process of a calcium carbide electric furnace) is used. Since lime 1 contains hydrotalcite significantly, the water reducing agent was only a polycarboxylic acid-based Super 1000, which had a practical fluidity improving effect. Therefore, the stirring rake stopped in about 1 hour. In addition, the transport pump was also blocked. Although not shown in the table, fluidity was hardly improved even when the amount of the water reducing agent was increased except for Super 1000.
  • No. 9 to 21 are examples using lime 2 (a by-product slaked lime generated in the process of producing acetylene gas by the carbide method). Since lime 2 does not contain hydrotalcite, it can be seen that various water reducing agents functioned effectively. No.

Abstract

Provided is a lime slurry able to produce clinker with a minimal burden on the global environment, suppress the generation of an orifice-shaped coating within a kiln during clinker firing, and suppress pipe blockage during pumping. A lime slurry containing slaked lime with an average particle size of at least 4 µm, gypsum, alumina, water and a water-reducing agent, the lime slurry having a hydrotalcite content of less than 0.5% by mass, and a flow value of at least 200 mm. Alternatively, a lime slurry containing slaked lime with an average particle size of at least 4 µm, gypsum, alumina, water and a polycarboxylic-acid-based water-reducing agent, the lime slurry having a hydrotalcite content of at least 0.5% by mass, and a flow value of at least 200 mm.

Description

石灰スラリー及びこれを用いたクリンカーの製造方法Lime slurry and method for producing clinker using the same
　本発明は石灰分を含有するスラリーに関する。また、本発明は当該スラリーを原料としてクリンカーを製造する方法に関する。 The present invention relates to a slurry containing lime. The present invention also relates to a method for producing a clinker using the slurry as a raw material.
　カルシウムサルフォアルミネート（３ＣａＯ・３Ａｌ2Ｏ3・ＣａＳＯ4、以下「ＣＳＡ」という。）は膨張性混和材料としてセメントに混和する事で膨張性能を有する為、コンクリートのひび割れ防止、ヒューム管等コンクリートのケミカルプレストレスを導入する材料として用いられている（国際公開第２００７／０２９３９９号；特許文献１）。 Calcium sulfoaluminate (3CaO · 3Al 2 O 3 · CaSO 4 , hereinafter referred to as “CSA”) is an expandable admixture material that has an expansion performance when mixed with cement. It is used as a material for introducing chemical pre-stress (International Publication No. 2007/029399; Patent Document 1).
　ＣＳＡの製造方法においては、原料調合精度が要求される為、石灰分（石灰石、生石灰、消石灰、アセチレン発生屑等）、石膏（化学石膏、天然石膏等）、アルミナ原料（ボーキサイト、アルミ残灰等）、及び水からなる湿式スラリーベーズンを、モル比でＣａＯ／Ａｌ2Ｏ3＝１～５又は２～６、ＣａＳＯ4／Ａｌ2Ｏ3＝２～４となるように調合し、スラリーベーズンをキルンにフィードしＣＳＡクリンカーを製造する湿式焼成方法が採用されてきた。これらのＣＳＡクリンカーの製造方法に関する特許文献としては、特公昭４２－２１８４０号公報（特許文献２）、特公昭４７－８４０号公報（特許文献３）、特公昭５１－２２０１３号公報（特許文献４）、特許第２６７２００８号公報（特許文献５）が挙げられる。 In the CSA manufacturing method, raw material preparation accuracy is required, so lime content (limestone, quicklime, slaked lime, acetylene generated waste, etc.), gypsum (chemical gypsum, natural gypsum, etc.), alumina raw material (bauxite, aluminum residual ash, etc.) And a wet slurry basin composed of water in a molar ratio of CaO / Al 2 O 3 = 1 to 5 or 2 to 6 and CaSO 4 / Al 2 O 3 = 2 to 4 A wet calcination method has been employed in which a CSA clinker is produced by feeding a metal to a kiln. Patent documents relating to the production method of these CSA clinker include Japanese Patent Publication No. 42-21840 (Patent Document 2), Japanese Patent Publication No. 47-840 (Patent Document 3), Japanese Patent Publication No. 51-222013 (Patent Document 4). ), Japanese Patent No. 2672008 (Patent Document 5).
国際公開第２００７／０２９３９９号International Publication No. 2007/029399 特公昭４２－２１８４０号公報Japanese Patent Publication No.42-21840 特公昭４７－８４０号公報Japanese Patent Publication No.47-840 特公昭５１－２２０１３号公報Japanese Examined Patent Publication No. 51-22013 特許第２６７２００８号公報Japanese Patent No. 2672008
　従来、ＣＳＡの原料となる石灰分として石灰石を使用することが一般的であったが、石灰石を原料として用いてＣＳＡクリンカーをロータリーキルンなどの焼成炉で焼成すると、脱炭酸エネルギーを必要とする為、焼成燃料率が悪く、また、ＣＯ2も多量に発生することから地球環境への負荷が大きいという問題がある。また、キルン内で次第に圧力障害が起こり、燃焼空気量が不足し、原料供給量を抑制せざるを得ず、又、不完全燃焼を呈する為、ＣＯガスが発生した段階で、爆発を回避する為、キルンの運転を停止しなければならなくなる事象が生じていた。これは、オリフィス状のコーティングがキルン内壁に徐々に成長し、キルン内の断面積を狭めていたことが原因であった。焼成炉内でコーティングが成長する箇所はランダムではなく、特定箇所において成長することが経験的に分かっている。 Conventionally, it was common to use limestone as the lime content that is the raw material of CSA, but when calcining CSA clinker in a kiln such as a rotary kiln using limestone as a raw material, decarbonation energy is required. There is a problem that the fired fuel ratio is bad and a large amount of CO 2 is generated, so that the burden on the global environment is large. In addition, pressure failure gradually occurs in the kiln, the amount of combustion air is insufficient, the raw material supply amount must be suppressed, and incomplete combustion occurs, so that explosion is avoided when CO gas is generated Therefore, there was an event that the kiln operation had to be stopped. This was due to the fact that the orifice-shaped coating gradually grew on the inner wall of the kiln and narrowed the cross-sectional area in the kiln. It has been empirically known that the location where the coating grows in the firing furnace is not random but grows at a specific location.
　一方、消石灰は石灰石と比較して、原材料として用いた場合、焼成段階で脱炭酸エネルギーを不要とする為、焼成燃料率が低減出来るのみならず、ＣＯ2発生量が低減出来、地球環境への負荷低減に有効である。また、脱炭酸反応が起きないことからコーティングの発生も抑制することができる。しかし、消石灰を含有する湿式スラリーベーズンを混練すると湿式スラリーベーズンがゲル化を起し、粘度が上昇する為、ポンプ閉塞、及びスラリー攪拌機の負荷過多を起し、配管輸送する事が出来ないという問題があった。
　特に、カルシウムカーバイド製造用電炉から発生したダストは、消石灰を主体とする為、スラリーの原料として使用すれば、石灰石代替の石灰原料として使用可能であり、ＣＯ2発生量を低減する事が可能となり、その使用の効用は大きいが、該ダストはチクソトロピー性を有する為、スラリー製造段階でスラリー攪拌機の故障を発生させ、又は、輸送段階でポンプ等の輸送機の故障を発生させるため、その大量使用が阻まれていた。 On the other hand, when slaked lime is used as a raw material compared to limestone, decarbonation energy is not required in the firing stage, so not only the firing fuel rate can be reduced, but also the amount of CO 2 generated can be reduced, leading to the global environment. It is effective for reducing the load. Moreover, since the decarboxylation reaction does not occur, the occurrence of coating can be suppressed. However, when a wet slurry basin containing slaked lime is kneaded, the wet slurry basin will gelate and the viscosity will increase, causing pump blockage and excessive load on the slurry stirrer, making it impossible to transport the piping. There was a problem.
In particular, the dust generated from the calcium carbide manufacturing furnace is mainly made of slaked lime, so if it is used as a raw material for slurry, it can be used as a lime raw material instead of limestone, and it is possible to reduce the amount of CO 2 generated. The use of the dust is large, but the dust has thixotropy, so it causes the failure of the slurry agitator at the slurry production stage, or the failure of the transport equipment such as a pump at the transportation stage. Was blocked.
　また、生石灰をスラリー原料として使用する方法も考えられるが、コストや安全面の観点から使用が難しい。 Also, although a method using quick lime as a slurry raw material is conceivable, it is difficult to use from the viewpoint of cost and safety.
　本発明は上記事情に鑑みて創作されたものである。すなわち、本発明は、少ない地球環境への負荷でクリンカーを製造でき、クリンカー焼成時にキルン内でのオリフィス状コーティングの発生を抑制可能で、且つ、ポンプ輸送時の配管閉塞を抑制可能な石灰スラリーを提供することを課題の一つとする。また、本発明は、本発明に係る石灰スラリーを原料としてクリンカーを製造する方法を提供することを別の課題の一つとする。 The present invention has been created in view of the above circumstances. That is, the present invention provides a lime slurry capable of producing a clinker with a small load on the global environment, capable of suppressing the occurrence of an orifice-like coating in the kiln during firing of the clinker, and capable of suppressing clogging of piping during pumping. Providing is one of the issues. Another object of the present invention is to provide a method for producing a clinker using the lime slurry according to the present invention as a raw material.
　本発明者は上記課題を解決するために鋭意検討を重ねたところ、消石灰を原料として使用することにより焼成時のＣＯ2及びコーティングの発生を抑制しつつ、スラリーの原料として減水剤を添加することによってゲル化が防止され、スラリー輸送時の配管の閉塞も低減できることが分かった。本発明は当該知見を基礎として完成したものであり、以下によって特定される。 The present inventor has made extensive studies to solve the above-mentioned problems. By using slaked lime as a raw material, it is possible to add a water reducing agent as a raw material for slurry while suppressing the generation of CO 2 and coating during firing. It was found that gelation was prevented by this and that blockage of piping during slurry transportation could be reduced. This invention is completed based on the said knowledge, and is specified by the following.
　本発明は第一の側面において、平均粒径が４μｍ以上の消石灰、石膏、アルミナ、水及び減水剤を含有し、ハイドロタルサイトの含有量が０．５質量％未満であり、フロー値が２００ｍｍ以上である石灰スラリーである。 In the first aspect, the present invention contains slaked lime, gypsum, alumina, water and a water reducing agent having an average particle size of 4 μm or more, the hydrotalcite content is less than 0.5 mass%, and the flow value is 200 mm. It is the lime slurry which is the above.
　本発明の第一の側面に係る石灰スラリーの一実施形態においては、減水剤がリグニン系、メラミン系、ポリカルボン酸系、及びナフタレン系よりなる群から選択される１種以上である。 In one embodiment of the lime slurry according to the first aspect of the present invention, the water reducing agent is at least one selected from the group consisting of lignin, melamine, polycarboxylic acid, and naphthalene.
　本発明の第一の側面に係る石灰スラリーの別の一実施形態においては、以下の何れか一つ以上の条件を満たす。
（ａ）ポリカルボン酸系の減水剤が、消石灰、石膏及びアルミナの合計質量に対して０．２０質量％以上を占める、
（ｂ）ナフタレン系の減水剤が、消石灰、石膏及びアルミナの合計質量に対して０．２８質量％以上を占める、
（ｃ）リグニン系の減水剤が、消石灰、石膏及びアルミナの合計質量に対して１．００質量％以上を占める、
（ｄ）メラミン系の減水剤が、消石灰、石膏及びアルミナの合計質量に対して１．００質量％以上を占める。 In another embodiment of the lime slurry according to the first aspect of the present invention, one or more of the following conditions is satisfied.
(A) the polycarboxylic acid-based water reducing agent occupies 0.20% by mass or more based on the total mass of slaked lime, gypsum and alumina,
(B) Naphthalene-based water reducing agent occupies 0.28% by mass or more based on the total mass of slaked lime, gypsum and alumina,
(C) the lignin-based water reducing agent occupies 1.00% by mass or more based on the total mass of slaked lime, gypsum and alumina,
(D) The melamine water reducing agent occupies 1.00% by mass or more based on the total mass of slaked lime, gypsum and alumina.
　本発明の第一の側面に係る石灰スラリーの更に別の一実施形態においては、カルシウムカーバイドからアセチレンを発生する際に副生する消石灰を含有する。 In yet another embodiment of the lime slurry according to the first aspect of the present invention, the lime slurry contains slaked lime by-produced when acetylene is generated from calcium carbide.
　本発明は第二の一側面において、平均粒径が４μｍ以上の消石灰、石膏、アルミナ、水、ポリカルボン酸系の減水剤を含有し、ハイドロタルサイトの含有量が０．５質量％以上であり、フロー値が２００ｍｍ以上である石灰スラリーである。 In the second aspect, the present invention includes slaked lime, gypsum, alumina, water, a polycarboxylic acid-based water reducing agent having an average particle size of 4 μm or more, and a hydrotalcite content of 0.5% by mass or more. Yes, a lime slurry having a flow value of 200 mm or more.
　本発明の第二の側面に係る石灰スラリーの一実施形態においては、カルシウムカーバイド電気炉の湿式集塵工程で捕獲され、消石灰及びハイドロタルサイトを含みチクソトロピー性を有するダストを含有する。 In one embodiment of the lime slurry according to the second aspect of the present invention, the lime slurry contains dust having a thixotropy including slaked lime and hydrotalcite, which is captured in a wet dust collecting process of a calcium carbide electric furnace.
　本発明の第二の側面に係る石灰スラリーの更に別の一実施形態においては、ポリカルボン酸系の減水剤が消石灰、石膏及びアルミナの合計質量に対して１．００質量％以上を占める。 In yet another embodiment of the lime slurry according to the second aspect of the present invention, the polycarboxylic acid-based water reducing agent accounts for 1.00% by mass or more based on the total mass of slaked lime, gypsum and alumina.
　本発明の第一又は第二の側面に係る石灰スラリーの更に別の一実施形態においては、石灰スラリー中の水の含有量は８～２５質量％であり、アルミナに対する石膏のモル比（ＣａＳＯ4／Ａｌ2Ｏ3）が２～１０であり、アルミナに対する消石灰のモル比（Ｃａ（ＯＨ）2／Ａｌ2Ｏ3）が２～３０である。 In still another embodiment of the lime slurry according to the first or second aspect of the present invention, the content of water in the lime slurry is 8 to 25% by mass, and the molar ratio of gypsum to alumina (CaSO 4 / Al 2 O 3 ) is 2 to 10, and the molar ratio of slaked lime to alumina (Ca (OH) 2 / Al 2 O 3 ) is 2 to 30.
　本発明の第一又は第二の側面に係る石灰スラリーの更に別の一実施形態においては、石灰スラリーはクリンカーの製造原料である。 In yet another embodiment of the lime slurry according to the first or second aspect of the present invention, the lime slurry is a clinker production raw material.
　本発明は更に別の側面において、上記記載の石灰スラリーを配管輸送後に焼成する工程を含むクリンカーの製造方法である。 In yet another aspect, the present invention is a method for producing a clinker including a step of firing the lime slurry described above after piping transportation.
　本発明に係るクリンカーの製造方法の一実施形態においては、クリンカーが、カルシウムサルフォアルミネートＣＳＡ（Ｃａｌｃｉｕｍｓｕｌｆｏａｌｕｍｉｎａｔｅ）である。 In one embodiment of the clinker production method according to the present invention, the clinker is calcium sulfoaluminate (CSA).
　本発明に係る石灰スラリーを原料としてクリンカーを製造することで、ＣＯ2発生が抑制され、少ないエネルギーでクリンカーを製造できるため、地球環境への負荷を小さくすることができる。また、本発明に係る石灰スラリーを原料とすれば、クリンカー焼成時にキルン内でのオリフィス状コーティングの発生を抑制可能である。更に、本発明に係る石灰スラリーは、ゲル化が抑制されることで粘度が適正値に確保されるため、ポンプ輸送時の配管閉塞が抑制可能であり、また、ベーズンレーキへの負荷も小さくて済む。よって、本発明の工業的利用価値は極めて大きい。 By producing the clinker using the lime slurry according to the present invention as a raw material, the generation of CO 2 is suppressed, and the clinker can be produced with a small amount of energy, so the burden on the global environment can be reduced. Further, when the lime slurry according to the present invention is used as a raw material, it is possible to suppress the occurrence of an orifice-like coating in the kiln during clinker firing. Furthermore, the viscosity of the lime slurry according to the present invention is ensured to an appropriate value by suppressing gelation, so that piping blockage during pumping can be suppressed, and the load on the basin rake can be reduced. . Therefore, the industrial utility value of the present invention is extremely large.
フロー値測定時のフローコーン反転及び打突後の試料の様子を示す模式図である。It is a schematic diagram which shows the mode of the sample after the flow cone inversion at the time of flow value measurement and impact. 本発明に係るＣＳＡ製造システムの一実施形態を示す模式図である。It is a mimetic diagram showing one embodiment of a CSA manufacturing system concerning the present invention.
　本発明に係る石灰スラリーは水、消石灰、石膏、アルミナ、及び減水剤を含有する。当該石灰スラリーはクリンカーの製造原料として利用できる。クリンカーとは、一種又は二種以上の鉱物を含有する粉砕物をその成分の一部が溶融する（半融状態）まで焼成し、全体を塊状に焼きしめたものであり、その種類に特に制限はないが、例示的には、カルシウムサルフォアルミネートＣＳＡ（Ｃａｌｃｉｕｍｓｕｌｆｏａｌｕｍｉｎａｔｅ）、及びセメント等のクリンカーが挙げられる。カルシウムサルフォアルミネートは、典型的には化学組成としてＣａＯ、ＣａＳＯ4、及びＡｌ2Ｏ3を有し、主要鉱物としてＣａＯ、ＣａＳＯ4、３ＣａＯ・３Ａｌ2Ｏ3・ＣａＳＯ4（Ｙｅｅｌｉｍｉｔｅ、或いは、Ｈａｕｙｎｅと称され、ＣＡＳ　Ｎｏ．１２００５－２５－３で定義される化学物質）を含有する反応生成物質である。 The lime slurry according to the present invention contains water, slaked lime, gypsum, alumina, and a water reducing agent. The lime slurry can be used as a clinker production raw material. A clinker is a pulverized product containing one or more minerals that is fired until a part of its components melts (semi-molten state), and is baked into a lump, and the type is particularly limited. Illustrative examples include calcium sulfoaluminate (CSA) and clinker such as cement. Calcium sulfoaluminate typically has CaO, CaSO 4 , and Al 2 O 3 as chemical compositions, and CaO, CaSO 4 , 3CaO · 3Al 2 O 3 · CaSO 4 (Yelimeite, or It is a reaction product containing a chemical substance called Hauine and defined in CAS No. 12005-25-3.
　本発明で用いる水としては、地下水、水道水、雨水等いずれも利用可能である。これらの水は硬度等に限定されず、いずれも利用可能である。水は流動性を付与する役割を果たす。石灰スラリー中の水の含有量はこの点を考慮して適宜調整すればよいが、少なすぎるとポンプ輸送が困難となる一方で、多すぎると他成分と相分離を起こしてしまう。そこで、石灰スラリー中の好ましい水の含有量は８～２５質量％であり、より好ましくは１０～２０質量％である。 As the water used in the present invention, any of ground water, tap water, rain water and the like can be used. These waters are not limited to hardness and the like, and any of them can be used. Water plays a role of imparting fluidity. The water content in the lime slurry may be appropriately adjusted in consideration of this point. However, if the amount is too small, pumping becomes difficult. On the other hand, if the amount is too large, phase separation from other components occurs. Therefore, the preferable water content in the lime slurry is 8 to 25% by mass, more preferably 10 to 20% by mass.
　本発明で用いる石灰分は消石灰とする。石灰石を焼成すると脱炭酸反応のためのエネルギーを要するため、エネルギー的に不利となる。また、石灰石を焼成すると脱炭酸反応が原因となって炉内を閉塞させるようにオリフィス状のコーティングが生成する点でも不利である。消石灰を使用すればこのような不都合は解消される。消石灰としては、特に制限はないが、例えば化学的に沈降法により製造される微粉消石灰、微粉消石灰を粉砕する事により得られる焼却炉のダイオキシン吸着用微粉消石灰、カルシウムカーバイド法によるアセチレンガスの製造工程で副生される消石灰、カルシウムカーバイド電気炉の湿式集塵工程で捕獲されるダスト中に含まれる副生消石灰等が挙げられる。 The lime used in the present invention is slaked lime. Since calcining limestone requires energy for decarboxylation, it is disadvantageous in terms of energy. Further, when limestone is fired, it is also disadvantageous in that an orifice-shaped coating is generated so as to close the inside of the furnace due to a decarboxylation reaction. If slaked lime is used, such inconvenience is eliminated. The slaked lime is not particularly limited. For example, finely powdered lime produced by a sedimentation method chemically, finely powdered slaked lime for adsorption of dioxins in an incinerator obtained by pulverizing finely powdered slaked lime, and a process for producing acetylene gas by a calcium carbide method And by-product slaked lime contained in the dust captured in the wet dust collection process of the calcium carbide electric furnace.
　特に、カルシウムカーバイド電気炉の湿式集塵工程で捕獲されるダストはハイドロタルサイトを含有し（典型的には１～１０質量％、より典型的には２～８質量％）、これによりチクソトロピー性を有することから配管輸送が困難であった。そのため、利用用途がなく一般に廃棄されていたが、本発明によって石灰スラリーの原料としてリサイクルできるようになる。すなわち、本発明は廃棄物の減量にも寄与することになる。 In particular, the dust captured in the wet dust collection process of the calcium carbide electric furnace contains hydrotalcite (typically 1 to 10% by mass, more typically 2 to 8% by mass), and thereby thixotropic properties. Therefore, it was difficult to transport the piping. Therefore, although it was not used and generally discarded, according to the present invention, it can be recycled as a raw material of lime slurry. That is, the present invention also contributes to waste reduction.
　消石灰は、減水剤による流動性の向上効果を十分に得るためには、平均粒径が４μｍ以上であることが必要であり、５μｍ以上であることが好ましい。消石灰の平均粒径が４μｍ未満の場合は、減水剤による流動性の向上効果が小さいためにスラリーのゲル化が起こりやすく、粘度が上昇し、スラリーの輸送が困難となる。一方で、消石灰の平均粒径が１００μｍを超えると、スラリーベーズンの材料分離、キルンでの焼成不良等が起こりやすく、運転が困難となる可能性がある。そのため、消石灰の平均粒径は８０μｍ以下とすることが好ましく、６０μｍ以下がより好ましく、５０μｍ以下が更により好ましい。これらの消石灰を用いる事により、従来、石灰石、石膏、アルミナ原料、及び水からなる湿式スラリーを湿式ミルにより粉砕する工程での動力原単位が大幅に低下する。 The slaked lime needs to have an average particle size of 4 μm or more and preferably 5 μm or more in order to sufficiently obtain the effect of improving the fluidity by the water reducing agent. When the average particle diameter of slaked lime is less than 4 μm, the effect of improving the fluidity by the water reducing agent is small, so that the slurry is easily gelled, the viscosity increases, and the slurry is difficult to transport. On the other hand, when the average particle size of slaked lime exceeds 100 μm, material separation of slurry basin, poor firing in the kiln, etc. are likely to occur, and operation may be difficult. Therefore, the average particle size of slaked lime is preferably 80 μm or less, more preferably 60 μm or less, and even more preferably 50 μm or less. By using these slaked lime, the basic unit of power in the process of pulverizing a wet slurry composed of limestone, gypsum, alumina raw material, and water with a wet mill is greatly reduced.
　本発明において、平均粒径は「ＪＩＳ　Ｒ　１６２９ファインセラミックス原料のレーザ回折・散乱法による粒子径分布測定方法」により測定した体積基準の積算分率における５０％径とする。 In the present invention, the average particle diameter is 50% of the volume-based integrated fraction measured by “JIS R 1629 fine ceramic raw material particle diameter distribution measurement method by laser diffraction / scattering method”.
　石灰スラリー中の消石灰の含有量は製造するクリンカーの種類によって適宜調整すればよいが、例えばＣＳＡを製造する場合はモル比でＣａ（ＯＨ）2／Ａｌ2Ｏ3＝２～３０、好ましくはＣａ（ＯＨ）2／Ａｌ2Ｏ3＝２～２５となるように配合することができる。 The content of slaked lime in the lime slurry may be appropriately adjusted according to the type of clinker to be produced. For example, when producing CSA, Ca (OH) 2 / Al 2 O 3 = 2 to 30, preferably Ca. (OH) 2 / Al 2 O 3 = 2 to 25.
　本発明で用いる石膏としては、二水石膏、半水石膏、無水石膏等いずれも利用可能であり、例えば二水石膏としては、天然二水石膏、火力発電所から発生する排煙脱硫二水石膏、産業廃棄物として発生する排石膏ボード、焼き石膏と称される半水石膏、燐酸副生無水石膏、天然無水石膏等が利用可能である。粒度は限定されず、塊、粉砕物等いずれも利用可能である。 As the gypsum used in the present invention, any of dihydrate gypsum, hemihydrate gypsum, anhydrous gypsum, etc. can be used. For example, as dihydrate gypsum, natural dihydrate gypsum, flue gas desulfurization dihydrate gypsum generated from a thermal power plant Waste gypsum board generated as industrial waste, hemihydrate gypsum called calcined gypsum, phosphoric acid byproduct anhydrous gypsum, natural anhydrous gypsum, and the like can be used. The particle size is not limited, and any of lumps and pulverized materials can be used.
　石灰スラリー中の石膏の含有量は製造するクリンカーの種類によって適宜調整すればよいが、例えばＣＳＡを製造する場合はモル比でＣａＳＯ4／Ａｌ2Ｏ3＝２～１０となるように配合することができる。 The content of gypsum in the lime slurry may be appropriately adjusted depending on the type of clinker to be produced. For example, when producing CSA, it is blended so that the molar ratio of CaSO 4 / Al 2 O 3 is 2 to 10. Can do.
　本発明で用いるアルミナとしては、天然バンド頁岩、アルミドロスとして発生するアルミ残灰、仮焼アルミナ、産業廃棄物として発生するアルミナスラリー等いずれも利用可能である。粒度は限定されず、塊、粉砕物等いずれも利用可能である。 As the alumina used in the present invention, any of natural band shale, aluminum residual ash generated as aluminum dross, calcined alumina, alumina slurry generated as industrial waste, and the like can be used. The particle size is not limited, and any of lumps and pulverized materials can be used.
　本発明において、減水剤は石灰スラリーのゲル化を防止する役割を果たし、粘度を低下させて流動性を高める。これにより、石灰スラリーを配管輸送する際に配管が閉塞することが防止される。石灰スラリー中に添加する減水剤の量は特に制限はないが、添加量が過剰だと効果が飽和して非経済であり、逆に添加量が過小だと十分な効果が得られないので、石灰スラリー中の消石灰、アルミナ、石膏及び減水剤の合計量に対する減水剤の量を適切に管理する必要がある。この適切な量は、後述するように、減水剤の種類に応じて変化し、また、石灰スラリーがチクソトロピー性を示すか否かによっても変化するため、賢明な選択が要求される。 In the present invention, the water reducing agent plays a role of preventing the lime slurry from gelling, lowers the viscosity, and improves the fluidity. This prevents the piping from being blocked when the lime slurry is transported by piping. The amount of the water reducing agent added to the lime slurry is not particularly limited, but if the added amount is excessive, the effect is saturated and uneconomical, and conversely if the added amount is too small, a sufficient effect cannot be obtained. It is necessary to appropriately control the amount of water reducing agent relative to the total amount of slaked lime, alumina, gypsum and water reducing agent in the lime slurry. As will be described later, this appropriate amount varies depending on the type of water reducing agent, and also varies depending on whether or not the lime slurry exhibits thixotropy. Therefore, a sensible choice is required.
　本発明で用いる減水剤としては、リグニン系（典型的にはリグニンスルホン酸塩系）、メラミン系（典型的にはメラミンスルホン酸塩系）、ポリカルボン酸系（典型的にはポリカルボン酸系高分子化合物系）、ナフタレン系（典型的にはナフタレンスルホン酸系）が用いられる。これらの中でも、流動性向上効果が大きいことから、ポリカルボン酸系及びナフタレン系が好ましく、ポリカルボン酸系が最も好ましい。例示的には、リグニン系減水剤として、リグニンスルホン酸塩を主体とした「ダーレックスＦ－１、ＷＲＤＡ」（グレースケミカルズ株式会社）、「ポゾリスＮｏ．７０シリーズ」（ＢＡＳＦポゾリス株式会社）、メラミン系減水剤として、メラミンスルホン酸ホルムアルデヒド縮合物の塩を主体とした「ＦＴ－７００Ｎシリーズ」（グレースケミカルズ株式会社）、ポリカルボン酸系減水剤として、ポリカルボン酸系高分子化合物の「ダーレックススーパー１００、２００、３００、１０００Ｎ」シリーズ（グレースケミカルズ株式会社）、ナフタレン系減水剤として、アルキルナフタレンスルホン酸ホルマリン縮合物を主体とした「ＦＴ－５００Ｖシリーズ」（グレースケミカルズ株式会社）等が挙げられる。また、リグニン系とナフタレン系の混合物である「ＦＴ－８０」（グレースケミカルズ株式会社）等も挙げられる。 Examples of water reducing agents used in the present invention include lignin (typically lignin sulfonate), melamine (typically melamine sulfonate), and polycarboxylic acid (typically polycarboxylic acid). High molecular compound type) and naphthalene type (typically naphthalene sulfonic acid type) are used. Among these, since a fluid improvement effect is large, a polycarboxylic acid type and a naphthalene type are preferable, and a polycarboxylic acid type is the most preferable. Illustratively, as a lignin-based water reducing agent, “Darlex F-1, WRDA” (Grace Chemicals Co., Ltd.), “Pozoris No. 70 series” (BASF Pozzolith Co., Ltd.), melamine mainly composed of lignin sulfonate. "FT-700N series" (Grace Chemicals Co., Ltd.) mainly composed of melamine sulfonic acid formaldehyde condensate salt as water reducing agent, and "Darlex Super" of polycarboxylic acid polymer compound as polycarboxylic acid water reducing agent "100, 200, 300, 1000N" series (Grace Chemicals Co., Ltd.), and naphthalene-based water reducing agents include "FT-500V series" (Grace Chemicals Co., Ltd.) and the like mainly composed of alkyl naphthalene sulfonic acid formalin condensate. Moreover, “FT-80” (Grace Chemicals Co., Ltd.), which is a mixture of lignin and naphthalene, can also be used.
　添加すべき減水剤の量は、石灰スラリー中のハイドロタルサイトの含有量で大きく異なる。ハイドロタルサイトの含有量が０．５質量％未満、好ましくは０．１質量％未満、より好ましくは０質量％においては、使用可能な減水剤の種類に特段制限はなく、後述するフロー値が２００ｍｍ以上となるように適宜添加量を調整すればよい。ただし、過剰に添加しても効果が飽和することに注意する必要がある。 The amount of water reducing agent to be added varies greatly depending on the hydrotalcite content in the lime slurry. When the hydrotalcite content is less than 0.5% by mass, preferably less than 0.1% by mass, more preferably 0% by mass, there is no particular limitation on the type of water reducing agent that can be used, and the flow value described later is What is necessary is just to adjust an addition amount suitably so that it may become 200 mm or more. However, it should be noted that the effect is saturated even if added excessively.
　この場合の減水剤の添加量は、例えば、以下の何れか一つ以上の条件を満たすことが望ましい。
（ａ）ポリカルボン酸系の減水剤は、消石灰、石膏及びアルミナの合計質量に対して下限値が０．２０質量％以上、好ましくは０．２５質量％以上であり、上限値が１０．００質量％以下、好ましくは５．００質量％以下、より好ましくは１．００質量％以下である。
（ｂ）ナフタレン系の減水剤は、消石灰、石膏及びアルミナの合計質量に対して下限値が０．２８質量％以上、好ましくは０．５０質量以上であり、上限値が１０．００質量％以下、好ましくは５．００質量％以下、より好ましくは１質量以下である。
（ｃ）リグニン系の減水剤は、消石灰、石膏及びアルミナの合計質量に対して下限値が１．００質量％以上、好ましくは２．００質量％以上であり、上限値が１０．００質量％以下、好ましくは５．００質量％以下であり、より好ましくは３．００質量％以下である。
（ｄ）メラミン系の減水剤は、消石灰、石膏及びアルミナの合計質量に対して１．００質量％以上、好ましくは２．００質量％以上であり、上限値が１０．００質量％以下、好ましくは５．００質量％以下であり、より好ましくは３．００質量％以下である。 In this case, it is desirable that the amount of the water reducing agent added satisfies, for example, one or more of the following conditions.
(A) The polycarboxylic acid-based water reducing agent has a lower limit of 0.20% by mass or more, preferably 0.25% by mass or more, and an upper limit of 10.00% with respect to the total mass of slaked lime, gypsum and alumina. It is at most mass%, preferably at most 5.00 mass%, more preferably at most 1.00 mass%.
(B) The naphthalene-based water reducing agent has a lower limit of 0.28% by mass or more, preferably 0.50% by mass or more, and an upper limit of 10.00% by mass or less with respect to the total mass of slaked lime, gypsum and alumina. , Preferably it is 5.00 mass% or less, More preferably, it is 1 mass or less.
(C) The lignin-based water reducing agent has a lower limit of 1.00% by mass or more, preferably 2.00% by mass or more, and an upper limit of 10.00% by mass with respect to the total mass of slaked lime, gypsum and alumina. Hereinafter, it is preferably 5.00% by mass or less, and more preferably 3.00% by mass or less.
(D) The melamine-based water reducing agent is 1.00% by mass or more, preferably 2.00% by mass or more, and the upper limit is 10.00% by mass or less, preferably based on the total mass of slaked lime, gypsum and alumina. Is 5.00 mass% or less, more preferably 3.00 mass% or less.
　石灰スラリー中のハイドロタルサイトの含有量が０．５質量％以上、典型的には１～８質量％、より典型的には２～５質量％においては、使用可能な減水剤の種類は制約を受ける。具体的には、ポリカルボン酸系の減水剤以外は実用上有効な効果が認められないのでポリカルボン酸系の減水剤を使用する必要がある。この場合の減水剤の添加量は、消石灰、石膏及びアルミナの合計質量に対して下限値が１．００質量％以上、好ましくは２．００質量以上であり、上限値は１０．００質量％以下、好ましくは５．００質量以下、より好ましくは３．００質量％以下である。 When the content of hydrotalcite in the lime slurry is 0.5% by mass or more, typically 1 to 8% by mass, more typically 2 to 5% by mass, the types of water reducing agents that can be used are limited. Receive. Specifically, since there is no practically effective effect other than the polycarboxylic acid-based water reducing agent, it is necessary to use a polycarboxylic acid-based water reducing agent. The addition amount of the water reducing agent in this case has a lower limit of 1.00% by mass or more, preferably 2.00% by mass or more, and an upper limit of 10.00% by mass or less with respect to the total mass of slaked lime, gypsum and alumina. , Preferably 5.00 mass or less, more preferably 3.00 mass% or less.
　本発明に係る石灰スラリーは上述した成分をボールミル等で混練することで製造可能である。このようにして得られた本発明に係る石灰スラリーの一実施形態において、フロー値を２００ｍｍ以上とすることができ、好ましい一実施形態において、２５０ｍｍ以上とすることができ、典型的な実施形態においては２００～３００ｍｍである。フロー値はスラリーの流動性の指標であり、その値が高いほど流動性が優れていることを表す。フロー値は減水剤の添加量を増加させることで上昇させることができる。従って、フロー値が所望の値に上昇するまで減水剤の添加量を増やせばよい。ただし、石灰スラリーの原料となる消石灰の平均粒径によって必要な添加量が変化し、消石灰の平均粒径が大きいほど流動性の向上効果は高い。 The lime slurry according to the present invention can be produced by kneading the above-described components with a ball mill or the like. In one embodiment of the lime slurry according to the present invention thus obtained, the flow value can be 200 mm or more, and in a preferred embodiment, it can be 250 mm or more. In a typical embodiment, Is 200 to 300 mm. The flow value is an index of the fluidity of the slurry, and the higher the value, the better the fluidity. The flow value can be increased by increasing the amount of water reducing agent added. Therefore, the amount of water reducing agent added may be increased until the flow value rises to a desired value. However, the required addition amount varies depending on the average particle size of the slaked lime used as the raw material of the lime slurry, and the larger the average particle size of the slaked lime, the higher the fluidity improving effect.
　本発明において、フロー値の測定方法は、ＪＩＳ　Ｒ　５２０１セメントの物理試験方法（フロー試験）による。尚、粉体状を示す時は、フローコーン反転後、１５回（１回／１秒）打突後の被試験塑性体は図１の様相を呈し、粉体はＷ２、Ｗ３に加えＷ１の広がりを示す。粉体状では、フローコーン反転時のＷ１値に対する１５秒１５回打突後のＷ１値は１．５より大きな値を示し、より好ましくは２．０より大きな値を示す。 In the present invention, the flow value is measured by a physical test method (flow test) of JIS R 5201 cement. In addition, when showing a powder form, the plastic body under test after impacting 15 times (one time / one second) after reversing the flow cone has the appearance shown in FIG. 1, and the powder is W1 in addition to W2 and W3. Showing spread. In the powder form, the W1 value after impacting 15 times 15 seconds with respect to the W1 value at the time of reversing the flow cone shows a value larger than 1.5, more preferably a value larger than 2.0.
　得られた石灰スラリーは輸送ポンプにより配管輸送することができ、例えば、クリンカー焼成炉へ輸送することができる。本発明に係る石灰スラリーはゲル化が抑制されており、粘度の上昇も生じにくいので、配管輸送が可能となる。焼成炉としては、限定的ではないが、ロータリーキルンが一般的である。焼成炉の条件はクリンカーの種類によって適宜調節すればよいが、例えばＣＳＡを焼成する場合には１１００～１３００℃程度の温度で焼成する。先述したように、本発明に係る石灰スラリーは焼成段階で脱炭酸エネルギーを不要とする為、焼成燃料率が低減出来るのみならず、ＣＯ2発生量が低減出来、地球環境への負荷低減に有効である。また、脱炭酸反応が起きないことからコーティングの発生も抑制することができる。 The obtained lime slurry can be transported by piping with a transport pump, for example, transported to a clinker firing furnace. In the lime slurry according to the present invention, gelation is suppressed and the viscosity is hardly increased, so that piping transportation is possible. The firing furnace is not limited, but a rotary kiln is common. The conditions of the firing furnace may be appropriately adjusted depending on the type of clinker. For example, when firing CSA, firing is performed at a temperature of about 1100 to 1300 ° C. As described above, since the lime slurry according to the present invention does not require decarbonation energy in the firing stage, not only can the firing fuel rate be reduced, but also the amount of CO 2 generated can be reduced, which is effective for reducing the burden on the global environment. It is. Moreover, since the decarboxylation reaction does not occur, the occurrence of coating can be suppressed.
　図２に、本発明に係る石灰スラリーを利用したクリンカー製造システムの一例を模式的に示す。石灰スラリーの原料である水、消石灰、石膏、アルミナ及び減水剤はそれぞれ水フィーダー１、消石灰フィーダー２、石膏フィーダー３、アルミナフィーダー４、及び減水剤フィーダー５から湿式原料ミル６へ配管を通じて供給される。各原料は湿式原料ミル６内で十分に混練されて石灰スラリーとなった後、スラリー輸送ポンプ７により、配管を通じていったん攪拌機付きのバッファータンク８に貯蔵され、その後、スラリー輸送ポンプ９によって配管を通じて焼成炉１０へ投入され、クリンカーが製造される。 FIG. 2 schematically shows an example of a clinker manufacturing system using the lime slurry according to the present invention. Water, slaked lime, gypsum, alumina, and a water reducing agent, which are raw materials of the lime slurry, are supplied from a water feeder 1, a slaked lime feeder 2, a gypsum feeder 3, an alumina feeder 4, and a water reducing agent feeder 5 to a wet raw material mill 6 through piping. . Each raw material is sufficiently kneaded in the wet raw material mill 6 to become a lime slurry, and is then temporarily stored in a buffer tank 8 with a stirrer through a pipe by a slurry transport pump 7, and then fired through the pipe by a slurry transport pump 9. The clinker is manufactured by charging the furnace 10.
　以下、本発明の実施例について説明するが、これらは例示目的であって本発明が限定されることを意図するものではない。 Examples of the present invention will be described below, but these are for illustrative purposes and are not intended to limit the present invention.
＜１．原料＞
　以下に、発明例及び比較例に使用した石灰スラリーの原料を示す。
（１）石灰分
　石灰１：カルシウムカーバイド電気炉の湿式集塵工程で捕獲されたダストである。
　石灰２：カーバイド法によるアセチレンガスの製造工程で発生する副産消石灰である。
　石灰３：石灰２を粉砕したものである。
　石灰４：市販品の消石灰である（「ヒシカール」菱光石灰工業株式会社）。
　石灰５：電気化学工業株式会社の青海工場で生産された石灰石である。
　表１にこれら石灰分の組成及び平均粒径を示す。
Figure JPOXMLDOC01-appb-T000001
 （２）石膏
　すべての発明例及び比較例において下記の表２に記載の組成を有する排脱石膏を使用した。当該排脱石膏は火力発電所からの排煙から排煙脱硫装置によってＳＯ2ガスを回収し、石膏化したものである。
Figure JPOXMLDOC01-appb-T000002
 （３）アルミナ
　すべての発明例及び比較例においてＡｌ2Ｏ3が約９０質量％を占めるアルミ残灰を使用した。
（４）水
　すべての発明例及び比較例において水は一般的な工業用水を使用した。
（５）減水剤
・「ＦＴ－５００Ｖ」（グレースケミカルズ株式会社）：アルキルナフタレンスルホン酸ホルマリン縮合物（以降、「β－ＮＳ」と呼ぶ。）
・「ダーレックススーパー１０００Ｎ」（グレースケミカルズ株式会社）：ポリカルボン酸系高分子化合物（以降、「スーパー１０００」と呼ぶ。） 
・「ＦＴ－８０」（グレースケミカルズ株式会社）：リグニンスルホン酸塩とアルキルナフタレンスルホン酸ホルマリン縮合物の１：１（質量比）の混合物（グレースケミカルズ株式会社）（以降、「ＦＴ－８０」と呼ぶ。）
・「ＦＴ－７００Ｎ」（グレースケミカルズ株式会社）：メラミンスルホン酸ホルムアルデヒド縮合物の塩（以降、「ＦＴ－７００Ｎ」と呼ぶ。）
・「ダーレックスＷＲＤＡ」（グレースケミカルズ株式会社）：リグニンスルホン酸塩系（以降、「ＷＲＤＡ」と呼ぶ。） <1. Raw material>
The raw material of the lime slurry used for the invention example and the comparative example is shown below.
(1) Lime content Lime 1: Dust captured in the wet dust collection process of the calcium carbide electric furnace.
Lime 2: By-product slaked lime generated in the manufacturing process of acetylene gas by the carbide method.
Lime 3: The lime 2 is crushed.
Lime 4: Commercially available slaked lime ("Hishikar" Ryoko Lime Industry Co., Ltd.).
Lime 5: Limestone produced at Aomi factory of Electrochemical Industry Co., Ltd.
Table 1 shows the composition and average particle size of these limes.
Figure JPOXMLDOC01-appb-T000001
 (2) Gypsum Exhaust gypsum having the composition described in Table 2 below was used in all invention examples and comparative examples. The exhaust gypsum is obtained by recovering SO 2 gas from the exhaust gas from the thermal power plant by using a flue gas desulfurization device and converting it into gypsum.
Figure JPOXMLDOC01-appb-T000002
 (3) Alumina Aluminum residual ash in which Al 2 O 3 accounts for about 90% by mass was used in all inventive examples and comparative examples.
(4) Water General industrial water was used as the water in all the inventive examples and comparative examples.
(5) Water reducing agent “FT-500V” (Grace Chemicals Co., Ltd.): Alkylnaphthalenesulfonic acid formalin condensate (hereinafter referred to as “β-NS”)
"Darlex Super 1000N" (Grace Chemicals Co., Ltd.): Polycarboxylic acid polymer compound (hereinafter referred to as "Super 1000")
"FT-80" (Grace Chemicals Co., Ltd.): 1: 1 (mass ratio) mixture of lignin sulfonate and alkylnaphthalene sulfonic acid formalin condensate (Grace Chemicals Co., Ltd.) (hereinafter referred to as "FT-80") Call it.)
“FT-700N” (Grace Chemicals Co., Ltd.): Salt of melamine sulfonic acid formaldehyde condensate (hereinafter referred to as “FT-700N”)
"Darlex WRDA" (Grace Chemicals Co., Ltd.): Lignin sulfonate (hereinafter referred to as "WRDA")
＜２．石灰スラリーの特性試験＞
　上記の各原料を表３に記載の各配合比で原料毎にフィーダーから供給して湿式原料ボールミル内で混練し、発明例及び比較例の石灰スラリーを得た。各スラリーについて、フロー値及び湿式原料ボールミルの動力原単位を測定したので、結果を表３に示す。 <2. Characteristics test of lime slurry>
Each raw material was supplied from the feeder for each raw material at each mixing ratio shown in Table 3 and kneaded in a wet raw material ball mill to obtain lime slurries of invention examples and comparative examples. Since the flow value and the power unit of the wet raw material ball mill were measured for each slurry, the results are shown in Table 3.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　次に、各スラリーを輸送ポンプで撹拌レーキ付きのバッファータンクに送り、そこから更に輸送ポンプを用いて配管輸送して、ロータリーキルン（内径３ｍ、長さ７０ｍ）へ３００ｔ／日の流量で投入し、ＣＳＡクリンカーの焼成試験を行った。
　石灰スラリーの原料として石灰石を用いたＮｏ．１では、運転開始から３日程度経過した後にキルン内圧力が上昇し、１週間程度で運転不可能になったため、ロータリーキルン内を点検したところ、オリフィス状コーティングがキルン内部に発生していた。
　Ｎｏ．２～８では、石灰１（カルシウムカーバイド電気炉の湿式集塵工程で捕獲されたダスト）を使用した例である。石灰１はハイドロタルサイトを有意に含有するため、減水剤はポリカルボン酸系のスーパー１０００しか実用的な流動性向上効果がなかった。そのため、１時間程度で撹拌レーキが停止してしまった。また、輸送ポンプも閉塞してしまった。なお、表には示していないが、スーパー１０００以外は減水剤の添加量を増やしても流動性の向上はほとんど見られなかった。
　Ｎｏ．９～２１は、石灰２（カーバイド法によるアセチレンガスの製造工程で発生する副産消石灰）を使用した例である。石灰２はハイドロタルサイトを含有しないため、各種の減水剤が有効に機能したことが分かる。
　Ｎｏ．２２～２３は石灰３（石灰２の粉砕物）を使用した例である。石灰３は平均粒径が小さすぎたため、減水剤を添加しても実用的な流動性向上効果を得ることはできなかった。そのため、１時間程度で撹拌レーキが停止してしまった。また、輸送ポンプも閉塞してしまった。
　Ｎｏ．２４～２５は石灰４（市販品の消石灰）を使用した例である。石灰４は平均粒径が小さすぎたため、減水剤を添加しても実用的な流動性向上効果を得ることはできなかった。そのため、１時間程度で撹拌レーキが停止してしまった。また、輸送ポンプも閉塞してしまった。 Next, each slurry is sent to a buffer tank with a stirring rake by a transport pump, and further transported by piping using a transport pump, and then charged into a rotary kiln (inner diameter 3 m, length 70 m) at a flow rate of 300 t / day, A CSA clinker firing test was performed.
No. using limestone as a raw material of lime slurry. In No. 1, after about 3 days from the start of operation, the pressure in the kiln increased and the operation became impossible in about one week. When the inside of the rotary kiln was inspected, an orifice-like coating was generated inside the kiln.
No. Examples 2 to 8 are examples in which lime 1 (dust captured in a wet dust collecting process of a calcium carbide electric furnace) is used. Since lime 1 contains hydrotalcite significantly, the water reducing agent was only a polycarboxylic acid-based Super 1000, which had a practical fluidity improving effect. Therefore, the stirring rake stopped in about 1 hour. In addition, the transport pump was also blocked. Although not shown in the table, fluidity was hardly improved even when the amount of the water reducing agent was increased except for Super 1000.
No. 9 to 21 are examples using lime 2 (a by-product slaked lime generated in the process of producing acetylene gas by the carbide method). Since lime 2 does not contain hydrotalcite, it can be seen that various water reducing agents functioned effectively.
No. 22 to 23 are examples using lime 3 (pulverized product of lime 2). Since the average particle diameter of lime 3 was too small, even if a water reducing agent was added, a practical fluidity improving effect could not be obtained. Therefore, the stirring rake stopped in about 1 hour. In addition, the transport pump was also blocked.
No. 24 to 25 are examples using lime 4 (commercially available slaked lime). Since the average particle diameter of lime 4 was too small, even if a water reducing agent was added, a practical fluidity improvement effect could not be obtained. Therefore, the stirring rake stopped in about 1 hour. In addition, the transport pump was also blocked.
１　　水フィーダー
２　　消石灰フィーダー
３　　石膏フィーダー
４　　アルミナフィーダー
５　　減水剤フィーダー
６　　湿式原料ミル
７　　スラリー輸送ポンプ
８　　バッファータンク
９　　スラリー輸送ポンプ
１０　焼成炉 DESCRIPTION OF SYMBOLS 1 Water feeder 2 Slaked lime feeder 3 Gypsum feeder 4 Alumina feeder 5 Water reducing agent feeder 6 Wet raw material mill 7 Slurry transport pump 8 Buffer tank 9 Slurry transport pump 10 Firing furnace

Claims (11)

  1. 　平均粒径が４μｍ以上の消石灰、石膏、アルミナ、水及び減水剤を含有し、ハイドロタルサイトの含有量が０．５質量％未満であり、フロー値が２００ｍｍ以上である石灰スラリー。 A lime slurry containing slaked lime, gypsum, alumina, water and a water reducing agent having an average particle size of 4 μm or more, a hydrotalcite content of less than 0.5 mass%, and a flow value of 200 mm or more.
  2. 　減水剤がリグニン系、メラミン系、ポリカルボン酸系、及びナフタレン系よりなる群から選択される１種以上である請求項１に記載の石灰スラリー。 The lime slurry according to claim 1, wherein the water reducing agent is at least one selected from the group consisting of lignin, melamine, polycarboxylic acid, and naphthalene.
  3. 　以下の何れか一つ以上の条件を満たす請求項２に記載の石灰スラリー：
    （ａ）ポリカルボン酸系の減水剤が、消石灰、石膏及びアルミナの合計質量に対して０．２０質量％以上を占める、
    （ｂ）ナフタレン系の減水剤が、消石灰、石膏及びアルミナの合計質量に対して０．２８質量％以上を占める、
    （ｃ）リグニン系の減水剤が、消石灰、石膏及びアルミナの合計質量に対して１．００質量％以上を占める、
    （ｄ）メラミン系の減水剤が、消石灰、石膏及びアルミナの合計質量に対して１．００質量％以上を占める。     The lime slurry according to claim 2, satisfying any one or more of the following conditions:
    (A) the polycarboxylic acid-based water reducing agent occupies 0.20% by mass or more based on the total mass of slaked lime, gypsum and alumina,
    (B) Naphthalene-based water reducing agent occupies 0.28% by mass or more based on the total mass of slaked lime, gypsum and alumina,
    (C) the lignin-based water reducing agent occupies 1.00% by mass or more based on the total mass of slaked lime, gypsum and alumina,
    (D) The melamine water reducing agent occupies 1.00% by mass or more based on the total mass of slaked lime, gypsum and alumina.
  4. 　カルシウムカーバイドからアセチレンを発生する際に副生する消石灰を含有する請求項１～３の何れか一項に記載の石灰スラリー。 The lime slurry according to any one of claims 1 to 3, comprising slaked lime by-produced when acetylene is generated from calcium carbide.
  5. 　平均粒径が４μｍ以上の消石灰、石膏、アルミナ、水、ポリカルボン酸系の減水剤を含有し、ハイドロタルサイトの含有量が０．５質量％以上であり、フロー値が２００ｍｍ以上である石灰スラリー。 Containing slaked lime, gypsum, alumina, water, polycarboxylic acid-based water reducing agent with an average particle size of 4 μm or more, lime having a hydrotalcite content of 0.5 mass% or more and a flow value of 200 mm or more slurry.
  6. 　カルシウムカーバイド電気炉の湿式集塵工程で捕獲され、消石灰及びハイドロタルサイトを含みチクソトロピー性を有するダストを含有する請求項５に記載の石灰スラリー。 The lime slurry according to claim 5, which contains dust having a thixotropic property including slaked lime and hydrotalcite, which is captured in a wet dust collecting process of a calcium carbide electric furnace.
  7. 　ポリカルボン酸系の減水剤が消石灰、石膏及びアルミナの合計質量に対して１．００質量％以上を占める請求項５又は６に記載の石灰スラリー。 The lime slurry according to claim 5 or 6, wherein the polycarboxylic acid-based water reducing agent occupies 1.00% by mass or more based on the total mass of slaked lime, gypsum and alumina.
  8. 　石灰スラリー中の水の含有量は８～２５質量％であり、アルミナに対する石膏のモル比（ＣａＳＯ4／Ａｌ2Ｏ3）が２～１０であり、アルミナに対する消石灰のモル比（Ｃａ（ＯＨ）2／Ａｌ2Ｏ3）が２～３０である請求項１～７の何れか一項に記載の石灰スラリー。 The water content in the lime slurry is 8 to 25% by mass, the molar ratio of gypsum to alumina (CaSO 4 / Al 2 O 3 ) is 2 to 10, and the molar ratio of slaked lime to alumina (Ca (OH)) The lime slurry according to any one of claims 1 to 7, wherein 2 / Al 2 O 3 ) is 2 to 30.
  9. 　クリンカーの製造原料である請求項１～８の何れか一項に記載の石灰スラリー。 The lime slurry according to any one of claims 1 to 8, which is a raw material for producing clinker.
  10. 　請求項１～９の何れか一項に記載の石灰スラリーを配管輸送後に焼成する工程を含むクリンカーの製造方法。 A method for producing a clinker, comprising a step of firing the lime slurry according to any one of claims 1 to 9 after piping transportation.
  11. 　クリンカーが、カルシウムサルフォアルミネートＣＳＡ（Ｃａｌｃｉｕｍｓｕｌｆｏａｌｕｍｉｎａｔｅ）である請求項１０に記載のクリンカーの製造方法。 The method for producing a clinker according to claim 10, wherein the clinker is calcium sulfoaluminate (CSA).
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