JP2021143097A - Method for producing portland cement clinker - Google Patents
Method for producing portland cement clinker Download PDFInfo
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- JP2021143097A JP2021143097A JP2020043162A JP2020043162A JP2021143097A JP 2021143097 A JP2021143097 A JP 2021143097A JP 2020043162 A JP2020043162 A JP 2020043162A JP 2020043162 A JP2020043162 A JP 2020043162A JP 2021143097 A JP2021143097 A JP 2021143097A
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 239000011398 Portland cement Substances 0.000 title claims description 21
- 239000004568 cement Substances 0.000 claims abstract description 36
- 210000003278 egg shell Anatomy 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 25
- 239000002699 waste material Substances 0.000 claims abstract description 20
- 102000002322 Egg Proteins Human genes 0.000 claims description 12
- 108010000912 Egg Proteins Proteins 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 9
- 239000010440 gypsum Substances 0.000 claims description 8
- 229910052602 gypsum Inorganic materials 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 4
- 235000019738 Limestone Nutrition 0.000 abstract description 12
- 239000006028 limestone Substances 0.000 abstract description 12
- 241000272525 Anas platyrhynchos Species 0.000 abstract description 4
- 241000287828 Gallus gallus Species 0.000 abstract description 4
- 241000272201 Columbiformes Species 0.000 abstract description 2
- 241000286209 Phasianidae Species 0.000 abstract description 2
- 241000272534 Struthio camelus Species 0.000 abstract description 2
- 241000272168 Laridae Species 0.000 abstract 1
- 239000002893 slag Substances 0.000 description 7
- 239000000292 calcium oxide Substances 0.000 description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 239000010881 fly ash Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical group [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 235000013601 eggs Nutrition 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000002956 ash Substances 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 239000010883 coal ash Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000009614 chemical analysis method Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000010801 sewage sludge Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010920 waste tyre Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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Abstract
Description
本発明は、ポルトランドセメントクリンカーの製造方法に係る。詳しくは、当該ポルトランドセメントクリンカーの製造に係る原料に係る。 The present invention relates to a method for producing Portland cement clinker. Specifically, it relates to a raw material related to the production of the Portland cement clinker.
日本は卵の消費量が世界でも多く、卵の国内生産量は、年間２５０万トン以上にのぼる。卵殻の重量は卵の重量の１０〜２０％程度であり、年間２５万〜５０万トン程度が発生している。卵殻のリサイクルについては様々検討されており、焼成により酸化カルシウムとして利用される技術も開発されている。（例えば、特許文献１）
一方で、セメント産業は、各種の廃棄物、副産物を原料および熱エネルギー源として使用することで、資源循環型社会の構築に大きく貢献している。セメントの主成分はＣａＯ、ＳｉＯ２、Ａｌ２Ｏ３、Ｆｅ２Ｏ３であり、これらの成分を比較的多く含有する物は、特に大量に使用が可能である。廃棄物は、一般にＡｌ２Ｏ３を含む物が多く、代表的な物として石炭灰や建設発生土等が挙げられる。クリンカー鉱物のうちＣ３ＡやＣ４ＡＦを多くしたクリンカーは、Ａｌ２Ｏ３の使用量が多くなるため、このような廃棄物を多く使用可能であるとされる。（例えば、特許文献２）
さらにセメントクリンカーの主成分はＣａＯであり、例えば普通ポルトランドセメントクリンカーにおいては全体の６５％程度を占める。上述した通り、廃棄物・副産物は一般にＡｌ２Ｏ３を含む物が多いが、ＣａＯを多く含む物はこれまでにほとんど無く、セメント原料のＣａＯ源は、ほとんどが天然原料である石灰石を使用している。
Japan consumes the most eggs in the world, and the domestic production of eggs reaches more than 2.5 million tons per year. The weight of the eggshell is about 10 to 20% of the weight of the egg, and about 250,000 to 500,000 tons are generated annually. Various studies have been conducted on the recycling of eggshells, and a technique for using it as calcium oxide by firing has also been developed. (For example, Patent Document 1)
On the other hand, the cement industry has greatly contributed to the construction of a resource-recycling society by using various wastes and by-products as raw materials and heat energy sources. The main components of cement are CaO, SiO 2 , Al 2 O 3 , and Fe 2 O 3 , and those containing a relatively large amount of these components can be used in a particularly large amount. Most of the waste generally contains Al 2 O 3 , and typical examples include coal ash and soil generated from construction. Of the clinker minerals, clinker with a large amount of C 3 A and C 4 AF uses a large amount of Al 2 O 3 , so it is said that a large amount of such waste can be used. (For example, Patent Document 2)
Further, the main component of cement clinker is CaO, which accounts for about 65% of the total in ordinary Portland cement clinker, for example. As mentioned above, most of the wastes and by-products generally contain Al 2 O 3 , but there have been few products containing a large amount of CaO, and most of the CaO sources for cement raw materials are limestone, which is a natural raw material. ing.
特許文献１に記載の発明のように卵殻のリサイクル方法も提案されているが、用途が限定されており、卵殻が廃棄物として埋立て処理されている量も少なくない。 Although a method for recycling eggshells has been proposed as in the invention described in Patent Document 1, its use is limited, and the amount of eggshells landfilled as waste is not small.
一方で、特許文献２に記載されるようなＡｌ２Ｏ３を多く含み得るセメントクリンカー組成であっても含有可能量には限界がある。そのため、廃棄物・副産物を従来型の組成のものよりは多く使用できるが、その使用量には限りがある。さらにまた、セメント原料におけるＣａＯ源は、現時点では事実上は天然原料である石灰石しかないが、その使用量を減らすことも求められる。 On the other hand, even if the cement clinker composition can contain a large amount of Al 2 O 3 as described in Patent Document 2, there is a limit to the amount that can be contained. Therefore, more waste and by-products can be used than those with conventional compositions, but the amount used is limited. Furthermore, the only source of CaO in cement raw materials is limestone, which is a natural raw material at present, but it is also required to reduce the amount used.
そこで本発明では、卵殻の有効利用方法を提供するとともに、廃棄物の使用量を増やし、かつ天然原料である石灰石使用量を削減可能なセメントクリンカーの製造方法を提供することを目的とする。 Therefore, an object of the present invention is to provide a method for effectively utilizing eggshells, and to provide a method for producing a cement clinker capable of increasing the amount of waste used and reducing the amount of limestone used as a natural raw material.
本発明者等は上記課題を解決するため鋭意検討を進め、卵殻の主成分はカルシウムであり、残余は有機物であって、カルシウム以外の成分（灰分）を殆ど含まないことに着目し、本発明を想到するに至った。 The present inventors have made diligent studies to solve the above problems, and have focused on the fact that the main component of the eggshell is calcium, the residue is an organic substance, and almost no component (ash) other than calcium is contained. I came up with the idea.
即ち、本発明は廃棄物を原料の一部として用いるポルトランドセメントクリンカーの製造方法であって、当該廃棄物の少なくとも一部として卵殻を用いるポルトランドセメントクリンカーの製造方法である。 That is, the present invention is a method for producing a Portland cement clinker that uses waste as a part of a raw material, and is a method for producing a Portland cement clinker that uses eggshell as at least a part of the waste.
本発明によれば、廃棄物として埋立処分されていた多量の卵殻をリサイクル原料として使用可能であり、かつセメント原料の廃棄物使用量を増加させることで、天然原料である石灰石の使用量を減らすことが可能である。 According to the present invention, a large amount of eggshells that have been landfilled as waste can be used as a recycling raw material, and the amount of limestone used as a natural raw material is reduced by increasing the amount of waste used as a cement raw material. It is possible.
本発明で使用される卵殻は、入手可能なものであれば、特に限定されず、種々の卵の卵殻を用いることができ、例えば、鶏、うずら、鴨、ダチョウ、カモメ、アヒル、鳩などが挙げられる。中でも、発生量が多く、入手の容易さから鶏の卵の卵殻を用いることが好ましい。また、単一種の卵殻を使用する必要もなく、異なる種類の卵の卵殻を使用してもよい。 The eggshell used in the present invention is not particularly limited as long as it is available, and various egg shells can be used, for example, chicken, quail, duck, ostrich, seagull, duck, pigeon and the like. Can be mentioned. Among them, it is preferable to use the eggshell of chicken eggs because of the large amount of generation and easy availability. Moreover, it is not necessary to use a single type of egg shell, and different types of egg shells may be used.
本発明の製造方法は上述の如く卵殻をセメント原料の一部として用いる以外は、従来公知のセメントクリンカーの製造方法を適用すればよい。即ち、例えば石灰石、粘土、珪石、酸化鉄原料等の鉱物性原材料や各種廃棄物・副産物等の組成を測定し、その各成分の割合から所定のボーグ式による鉱物組成の値となるように、あるいは所定の三率の値となるように卵殻の使用割合に応じて他の原料の混合割合を計算すればよい。 As the production method of the present invention, a conventionally known method for producing cement clinker may be applied, except that eggshell is used as a part of the cement raw material as described above. That is, for example, the composition of mineral raw materials such as limestone, clay, silica stone, and iron oxide raw materials and various wastes and by-products is measured, and the value of the mineral composition according to a predetermined Borg formula is obtained from the ratio of each component. Alternatively, the mixing ratio of other raw materials may be calculated according to the ratio of eggshell used so as to have a predetermined value of three ratios.
使用可能な廃棄物・副産物をより具体的に例示すると、高炉スラグ、鉄鋼スラグ、非鉄鉱滓、石炭灰、下水汚泥、浄水汚泥、製紙スラッジ、建設発生土、鋳物砂、ばいじん、焼却飛灰、溶融飛灰、木屑、廃白土、ボタ、廃タイヤ、貝殻、都市ごみやその焼却灰等が挙げられる（なお、これらの中には、セメント原料になるとともに熱エネルギー源となるものもある）。 More specific examples of usable wastes and by-products are blast furnace slag, steel slag, non-iron slag, coal ash, sewage sludge, purified water sludge, paper sludge, construction-generated soil, casting sand, soot and dust, incineration fly ash, and melting. Examples include fly ash, wood chips, waste white clay, slag, waste tires, shells, municipal waste and its incineration ash (note that some of these can be used as a raw material for cement and as a source of heat energy).
本発明で使用される卵殻の分析結果の一例を表１に、Ｘ線回折測定によって得られたパターン図を図１に示す。 An example of the analysis result of the eggshell used in the present invention is shown in Table 1, and the pattern diagram obtained by the X-ray diffraction measurement is shown in FIG.
表１に示すように主成分はカルシウムであり、強熱減量や図１に示すパターン図から、その形態は炭酸カルシウムであることから石灰石の代替として問題なく使用することが可能である。 As shown in Table 1, the main component is calcium, and from the ignition loss and the pattern diagram shown in FIG. 1, since the form is calcium carbonate, it can be used as a substitute for limestone without any problem.
原料はセメントキルンでの焼成に適した粒度まで粉砕される。卵殻は石灰石など他の原料と混合してから粉砕してもよいし、単独で粉砕してから他の原料と混合してもよい。一般的に卵殻はセメント原料として受け入れる石灰石よりもサイズが小さく、硬度も柔らかいため、石灰石の代替として卵殻を使用することは粉砕のエネルギーを低減させる点でも非常に有効である。 The raw material is ground to a particle size suitable for firing in a cement kiln. The eggshell may be mixed with other raw materials such as limestone and then crushed, or may be crushed alone and then mixed with other raw materials. Generally, eggshells are smaller in size and softer than limestone accepted as a raw material for cement, so using eggshells as an alternative to limestone is also very effective in reducing crushing energy.
上述のように配合比率を調整した原料を焼成してセメントクリンカーとする。焼成方法は特に制限されず、公知の方法を適宜選択して行なえばよく、例えばＮＳＰキルンやＳＰキルンに代表されるセメントキルン等の高温加熱が可能な装置を用いて概ね１４５０℃を超える高温で焼成するのが一般的である。 The raw material whose blending ratio is adjusted as described above is calcined to obtain cement clinker. The firing method is not particularly limited, and a known method may be appropriately selected. For example, a device capable of high-temperature heating such as an NSP kiln or a cement kiln typified by an SP kiln may be used at a high temperature of approximately 1450 ° C. or higher. It is common to bake.
得られたセメントクリンカー中に含まれる各成分の定量は、例えばＪＩＳ Ｒ ５２０２に規定される化学分析方法や、ＪＩＳ Ｒ ５２０４に規定される蛍光Ｘ線分析法に従い行なえばよい。 The quantification of each component contained in the obtained cement clinker may be carried out according to, for example, the chemical analysis method specified in JIS R5202 or the fluorescent X-ray analysis method specified in JIS R5204.
本発明で製造するポルトランドセメントクリンカーとしては、普通ポルトランドセメント、早強ポルトランドセメント、超早強ポルトランドセメント、中庸熱ポルトランドセメント、低熱ポルトランドセメント、耐硫酸塩ポルトランドセメント等のポルトランドセメント用のセメントクリンカーが例示される。 Examples of the Portland cement clinker produced in the present invention include cement clinker for Portland cement such as ordinary Portland cement, early-strength Portland cement, ultra-early-strength Portland cement, moderate heat Portland cement, low heat Portland cement, and sulfate-resistant Portland cement. Will be done.
本発明で製造するセメントクリンカーの鉱物組成はポルトランド組成の範囲に入るのであれば特に制限されないが、一般的にはＣ３Ｓが５０〜７０質量％、Ｃ２Ｓが１０〜２０質量％、Ｃ３Ａが１０〜１５質量％、Ｃ４ＡＦが８〜１５質量％である。 The mineral composition of the cement clinker produced in the present invention is not particularly limited as long as it falls within the range of Portland composition, but generally, C 3 S is 50 to 70% by mass, C 2 S is 10 to 20% by mass, and so on. C 3 A is 10 to 15% by mass, and C 4 AF is 8 to 15% by mass.
本発明の製造方法で製造されたセメントクリンカーは、従来公知のセメントクリンカーと同様、石こうと共に粉砕または個別に粉砕した後、混合することにより、セメントとすることができる。当該セメントとしては、普通ポルトランドセメント、早強ポルトランドセメント、超早強ポルトランドセメントが挙げられる。またポルトランドセメントとする以外にも、各種混合セメントや、土壌固化材等の固化材の構成成分として使用することも可能である。 The cement clinker produced by the production method of the present invention can be made into cement by crushing or individually crushing with gypsum and then mixing in the same manner as the conventionally known cement clinker. Examples of the cement include ordinary Portland cement, early-strength Portland cement, and ultra-early-strength Portland cement. In addition to Portland cement, it can also be used as a constituent of various mixed cements and solidifying materials such as soil solidifying materials.
石こうを加えてセメントとする場合、使用する石こうについては、二水石こう、半水石こう、無水石こう等のセメント製造原料として公知の石こうが特に制限なく使用できる。石こうの添加量は、ポルトランドセメントの場合、そのなかのＳＯ３量が１．５〜５．０質量％となるように添加することが好ましく、１．８〜３質量％となるような添加量がより好ましい。上記セメントクリンカーおよび石こうの粉砕方法については、公知の技術が特に制限なく使用できる。 When gypsum is added to make cement, gypsum known as a raw material for cement production such as dihydrate gypsum, hemihydrate gypsum, and anhydrous gypsum can be used without particular limitation. In the case of Portland cement, the amount of gypsum added is preferably such that the amount of SO3 in it is 1.5 to 5.0% by mass, and the amount of gypsum added is 1.8 to 3% by mass. Is more preferable. As for the method for crushing the cement clinker and gypsum, known techniques can be used without particular limitation.
また、当該セメントには、高炉スラグ、シリカ質混合材、フライアッシュ、炭酸カルシウム、石灰石等の混合材や粉砕助剤を適宜添加して混合粉砕するか、粉砕後に混合材と混合してもよい。また塩素バイパスダスト等を混合してもよい。 Further, the cement may be mixed and crushed by appropriately adding a mixed material such as blast furnace slag, siliceous mixed material, fly ash, calcium carbonate and limestone and a crushing aid, or may be mixed with the mixed material after crushing. .. Further, chlorine bypass dust or the like may be mixed.
セメントの粉末度は、特に制限されないが、ブレーン比表面積で２８００〜４５００ｃｍ２／ｇに調整されることが好ましい。 The degree of powderiness of the cement is not particularly limited, but it is preferable that the specific surface area of the brain is adjusted to 2800 to 4500 cm 2 / g.
さらに必要に応じ、粉砕後に高炉スラグ、フライアッシュ等を混合し、高炉スラグセメント、フライアッシュセメント等にすることも可能である。 Further, if necessary, it is also possible to mix blast furnace slag, fly ash and the like after crushing to obtain blast furnace slag cement, fly ash cement and the like.
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