JP2013142046A - Method of recovering raw material for slag phosphatic fertilizer - Google Patents
Method of recovering raw material for slag phosphatic fertilizer Download PDFInfo
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- JP2013142046A JP2013142046A JP2012001944A JP2012001944A JP2013142046A JP 2013142046 A JP2013142046 A JP 2013142046A JP 2012001944 A JP2012001944 A JP 2012001944A JP 2012001944 A JP2012001944 A JP 2012001944A JP 2013142046 A JP2013142046 A JP 2013142046A
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- 239000002893 slag Substances 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000002994 raw material Substances 0.000 title claims abstract description 28
- 239000003337 fertilizer Substances 0.000 title abstract description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 26
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 26
- 239000011574 phosphorus Substances 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000007787 solid Substances 0.000 claims abstract description 15
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 13
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 24
- 239000011707 mineral Substances 0.000 claims description 24
- 239000002686 phosphate fertilizer Substances 0.000 claims description 22
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 14
- 238000011084 recovery Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000010298 pulverizing process Methods 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 239000007789 gas Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 150000007522 mineralic acids Chemical class 0.000 description 4
- 238000009628 steelmaking Methods 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000009313 farming Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
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- Processing Of Solid Wastes (AREA)
- Fertilizers (AREA)
Abstract
Description
本発明は、鉱さい燐酸肥料用原料回収方法に関するものである。 The present invention relates to a raw material recovery method for mineral phosphate fertilizer.
溶銑脱燐処理において発生する塩基度１．４〜２．５程度の脱燐スラグには、ＣａＯ、ＳｉＯ２、ＭｇＯ、ＦｅＯ、ＭｎＯ、等の肥料成分が多く含まれており、これらの肥料成分は、従来から「鉱さいけい酸肥料」（ケイカル肥料）として、稲作用の他、畑作、牧草用として幅広く利用されている。 The dephosphorization slag having a basicity of about 1.4 to 2.5 generated in the hot metal dephosphorization treatment contains many fertilizer components such as CaO, SiO 2 , MgO, FeO, MnO, etc., and these fertilizer components Has been widely used as a “mineral acid fertilizer” (calcium fertilizer) for rice farming, field cropping and pasture use.
溶銑脱燐処理において発生する脱燐スラグには、その他、Ｐ２Ｏ５が含まれており、燐酸肥料としての活用への需要がある。近年、燐鉱石の枯渇問題や、諸外国における燐鉱石の囲い込みのため、燐資源が高騰しており、製鋼スラグ中に含有される燐が貴重な燐資源として見直されている観点からも、脱燐スラグ中に含有される燐の有効活用は急務である。 In addition, the dephosphorization slag generated in the hot metal dephosphorization treatment contains P 2 O 5 and there is a demand for utilization as a phosphoric acid fertilizer. In recent years, phosphorus resources have soared due to the problem of depletion of phosphate ore and the inclusion of phosphate ore in other countries. From the viewpoint that phosphorus contained in steelmaking slag has been reconsidered as a valuable phosphorus resource. Effective utilization of phosphorus contained in phosphorus slag is urgent.
ただし、肥料取締法に基づいて定められている肥料の工程規格では、「鉱さい燐酸肥料（製鋼鉱さいをいう）」との表記を行うための要件として、く溶性燐酸を３．０％以上含有することが定められているのに対し、通常、脱燐スラグ中のＰ２Ｏ５含有量は３．０％未満に留まるため、脱燐スラグ中に含有される燐を「鉱さい燐酸肥料」として活用するためには、燐の濃縮が必要になる。 However, in the fertilizer process standard established based on the Fertilizer Control Law, it contains 3.0% or more of soluble phosphoric acid as a requirement for the notation "mineral phosphoric acid fertilizer" (referring to steelmaking ore). However, since the P 2 O 5 content in dephosphorized slag is usually less than 3.0%, the phosphorus contained in dephosphorized slag is used as “mineral phosphate fertilizer” To do so, it is necessary to concentrate phosphorus.
脱燐スラグ中のＰ２Ｏ５を濃縮して回収する技術に関し、例えば、特許文献１には、製鋼スラグを炭酸溶解水で洗浄してカルシウムを除去した後、鉱酸（塩酸や硫酸等の無機酸）を用いて、カルシウム除去済みのスラグから燐を抽出し、抽出液を中和することにより、脱燐スラグ中のＰ２Ｏ５を高純度の燐酸として回収する技術が開示されている。 Regarding the technology for concentrating and recovering P 2 O 5 in dephosphorized slag, for example, Patent Document 1 discloses that steelmaking slag is washed with carbonic acid-dissolved water to remove calcium, and then a mineral acid (such as hydrochloric acid or sulfuric acid). A technique for recovering P 2 O 5 in dephosphorized slag as high-purity phosphoric acid by extracting phosphorus from slag from which calcium has been removed using an inorganic acid) and neutralizing the extract is disclosed. .
しかし、鉱酸（塩酸や硫酸等の無機酸）を用いて、カルシウム除去済みのスラグから燐を抽出するという手法は、塩酸や硫酸等が高価で、かつ、取扱いも困難であるため、試薬コストや、設備コストが嵩み、「鉱さい燐酸肥料」の規定を満たす程度に濃縮すればよい「鉱さい燐酸肥料」の製造過程への適用には、実用性を欠くという問題があった。 However, the method of extracting phosphorus from slag from which calcium has been removed using a mineral acid (inorganic acid such as hydrochloric acid or sulfuric acid) is expensive because hydrochloric acid and sulfuric acid are expensive and difficult to handle. In addition, there is a problem that the equipment cost is high, and the application to the production process of “mineral phosphate fertilizer” which only needs to be concentrated to meet the requirements of “mineral phosphate fertilizer” lacks practicality.
本発明の目的は前記の問題を解決し、低コストかつ簡易な手法で、脱燐スラグ中のＰ２Ｏ５含有量を、「く溶性燐酸を３．０％以上含有する」レベルに濃縮して、鉱さい燐酸肥料用原料を回収する技術を提供することである。 The object of the present invention is to solve the above-mentioned problems, and to concentrate the P 2 O 5 content in the dephosphorized slag to a level of “containing at least 3.0% soluble phosphoric acid” by a low-cost and simple method. Thus, it is to provide a technique for recovering raw materials for slag phosphate fertilizer.
上記課題を解決するためになされた本発明の鉱さい燐酸肥料用原料回収方法は、溶銑の脱燐処理に伴い発生する脱燐スラグから、く溶性燐酸を３．０％以上含有する鉱さい燐酸肥料用原料を回収する方法であって、脱燐スラグを、炭酸ガスを溶解させた水中に投入して撹拌しながら炭酸化処理して、脱燐スラグ中の２ＣａＯ・ＳｉＯ２相を溶出するとともに、固体残渣を回収した後、該固体残渣を再度炭酸化処理する操作を複数回繰り返し、少なくとも、２回目以降の処理水から燐を回収することを特徴とするものである。 The raw material recovery method for mineral phosphite fertilizer of the present invention made to solve the above problems is for mineral phosphite fertilizer containing 3.0% or more of soluble phosphoric acid from dephosphorization slag generated by dephosphorization treatment of hot metal. A method of recovering a raw material, wherein dephosphorization slag is put into water in which carbon dioxide gas is dissolved and carbonized while stirring to elute the 2CaO.SiO 2 phase in the dephosphorization slag, and solid After the residue is collected, the operation of carbonating the solid residue again is repeated a plurality of times, and at least phosphorus is collected from the treated water after the second time.
請求項２記載の発明は、請求項１記載の鉱さい燐酸肥料用原料回収方法において、燐を固溶しているβ-２ＣａＯ・ＳｉＯ２相が溶出し始めた処理水から燐を回収することを特徴とするものである。 The invention according to claim 2 is the method for recovering raw materials for mineral phosphate fertilizer according to claim 1, wherein the phosphorus is recovered from the treated water from which the β-2CaO · SiO 2 phase in which the phosphorus is dissolved is started to elute. It is a feature.
請求項３記載の発明は、請求項１または２記載の鉱さい燐酸肥料用原料回収方法において、炭酸化処理後の固体残渣と、処理水から燐を回収した燐を合わせて燐酸肥料用原料とすることを特徴とするものである。 The invention according to claim 3 is the method for recovering raw materials for mineral phosphate fertilizer according to claim 1 or 2, wherein the solid residue after carbonation treatment and the phosphorus recovered from the treated water are combined to make a raw material for phosphate fertilizer. It is characterized by this.
請求項４記載の発明は、請求項１または２記載の鉱さい燐酸肥料用原料回収方法法において、炭酸化処理後の固体残渣は、製鉄原料として再利用することを特徴とするものである。 The invention according to claim 4 is characterized in that, in the raw material recovery method for mineral phosphate fertilizer according to claim 1 or 2, the solid residue after carbonation is reused as an iron-making raw material.
請求項５記載の発明は、請求項１〜４の何れかに記載の鉱さい燐酸肥料用原料回収方法において、脱燐スラグを２ｍｍアンダーに粉砕処理後に炭酸化処理を行うことを特徴とするものである。 The invention according to claim 5 is characterized in that, in the raw material recovery method for mineral phosphoric acid fertilizer according to any one of claims 1 to 4, carbonation treatment is performed after pulverizing the dephosphorized slag under 2 mm. is there.
請求項６記載の発明は、請求項１〜４の何れかに記載の鉱さい燐酸肥料用原料回収方法において、脱燐スラグを２ｍｍアンダーに粉砕処理しながら同時に炭酸化処理を行うことを特徴とするものである。 The invention according to claim 6 is characterized in that, in the raw material recovery method for mineral phosphate fertilizer according to any one of claims 1 to 4, carbonation treatment is simultaneously performed while pulverizing dephosphorization slag to under 2 mm. Is.
本発明は、スラグ中に存在する２ＣａＯ・ＳｉＯ２相には、Ｐ２Ｏ５を固溶しているβ相と固溶していないγ相が並存しており、炭酸化処理時には、Ｐ２Ｏ５を固溶していないγ相が優先的に分解するという、本願発明者により見出された新たな知見に基づいてなされたものである。 The present invention is 2CaO · SiO 2 phase present in the slag has coexist is γ-phase which is not dissolved with β-phase in solid solution with P 2 O 5, at the time of carbonation process, P 2 This is based on a new finding found by the present inventor that the γ phase not dissolved in O 5 is preferentially decomposed.
本発明によれば、脱燐スラグを、炭酸ガスを溶解させた水中に投入して撹拌しながら炭酸化処理して、脱燐スラグ中の２ＣａＯ・ＳｉＯ２相を溶出するとともに、固体残渣を回収した後、該固体残渣を再度炭酸化処理する操作を複数回繰り返し、少なくとも、２回目以降の処理水から燐を回収する、という簡易な手法で、高価で取り扱いの難しい鉱酸（塩酸や硫酸等の無機酸）を用いることなく、脱燐スラグ中のＰ２Ｏ５含有量を、「く溶性燐酸を３．０％以上含有する」レベルに濃縮して、鉱さい燐酸肥料用原料を回収することができる。 According to the present invention, dephosphorization slag is poured into water in which carbon dioxide gas is dissolved and carbonized while stirring to elute the 2CaO.SiO 2 phase in the dephosphorization slag and collect a solid residue. After that, the operation of carbonating the solid residue again is repeated a plurality of times, and at least a simple technique of recovering phosphorus from the treated water after the second time, an expensive and difficult mineral acid (such as hydrochloric acid or sulfuric acid). The concentration of P 2 O 5 in the dephosphorized slag is concentrated to the level of “containing at least 3.0% soluble phosphoric acid” without using the inorganic acid), and the raw material for the mineral phosphate fertilizer is recovered. Can do.
以下に本発明の好ましい実施形態を示す。 Preferred embodiments of the present invention are shown below.
図１には、本発明の概略説明図を示し、図２には、炭酸化処理を５回繰り返し行う実施形態における装置構成の全体説明図を示している。また、図３には、炭酸化処理に先立って行う、脱燐スラグの前処理工程のフロー図を示している。 FIG. 1 is a schematic explanatory diagram of the present invention, and FIG. 2 is an overall explanatory diagram of an apparatus configuration in an embodiment in which the carbonation treatment is repeated five times. FIG. 3 shows a flow chart of a dephosphorization slag pretreatment step performed prior to the carbonation treatment.
溶銑脱燐処理において発生した脱燐スラグは、図３に示すフローに従って、冷却・粉砕・地金分離・粉砕・篩い分けの各工程を経て、図１に示す炭酸化処理槽に投入される。炭酸化処理を効率よく行うために、脱燐スラグは、２ｍｍアンダーに粉砕処理後に炭酸化処理槽に投入することが好ましい。 The dephosphorization slag generated in the hot metal dephosphorization process is fed into the carbonation treatment tank shown in FIG. 1 through the steps shown in FIG. 3 through the steps of cooling, crushing, metal separation, crushing, and sieving. In order to efficiently perform the carbonation treatment, it is preferable that the dephosphorization slag is put into a carbonation treatment tank after being pulverized under 2 mm.
炭酸化処理槽には、２ｍｍアンダーに粉砕処理された脱燐スラグと水が投入され、下部からＣＯ２ガスを吹き込みながら槽内の撹拌が行われる。 The carbonation tank is filled with dephosphorized slag and water pulverized under 2 mm, and the tank is agitated while CO 2 gas is blown from below.
撹拌に伴い、槽内では下記の反応により、脱燐スラグが溶出する。
脱燐スラグ中のＰ２Ｏ５は、主に、２ＣａＯ・ＳｉＯ２相に固溶され、更に、２ＣａＯ・ＳｉＯ２相には、Ｐ２Ｏ５を固溶しているβ相と固溶していないγ相が並存している。炭酸化処理時には、Ｐ２Ｏ５を固溶していないγ-２ＣａＯ・ＳｉＯ２相が優先的に分解するため、燐を固溶しているβ-２ＣａＯ・ＳｉＯ２相を主体とする固体残渣を回収すると、スラグ中のＰ２Ｏ５濃度の増加が確認される。 P 2 O 5 of dephosphorization slag is mainly solid-dissolved 2CaO · SiO 2 phase, further, the 2CaO · SiO 2 phase, solid solution with β-phase in solid solution with P 2 O 5 Not γ phase coexists. During carbonation treatment, the γ-2CaO · SiO 2 phase not dissolved in P 2 O 5 is preferentially decomposed, so that a solid residue mainly composed of β-2CaO · SiO 2 phase in which phosphorus is dissolved. Is recovered, an increase in the concentration of P 2 O 5 in the slag is confirmed.
当該操作を複数回繰り返し、炭酸化処理の総時間が所定時間経過すると、炭酸化処理槽内では、燐を固溶しているβ-２ＣａＯ・ＳｉＯ２相の溶出が生じ始め、処理水中のＰ２Ｏ５濃度が増加し始める。 When this operation is repeated a plurality of times and the total time of carbonation treatment elapses for a predetermined time, elution of β-2CaO.SiO 2 phase in which phosphorus is dissolved in the carbonation treatment tank starts to occur, and P in the treated water The 2 O 5 concentration begins to increase.
燐資源の有効活用の観点からは、処理水中に溶出したＰ２Ｏ５は全て回収して再利用することが好ましい。ただし、本発明は、脱燐スラグ中に含有される燐を「鉱さい燐酸肥料」として活用するために、燐の濃縮を行うものであり、肥料取締法に基づいて定められている肥料の公定規格では、「鉱さい燐酸肥料（製鋼鉱さいをいう）」との表記を行うための要件として、く溶性燐酸を３．０％以上含有することが定められているため、Ｐ２Ｏ５濃度が所定値以上となった処理水のみ回収して再利用を行っている。図２に示す実施形態では、前段の炭酸化処理槽１〜３では、処理水中に溶出したＰ２Ｏ５の回収は行わず、前段の炭酸化処理槽４〜５において処理水中に溶出したＰ２Ｏ５の回収を行っている。 From the viewpoint of effective utilization of phosphorus resources, it is preferable to recover and reuse all P 2 O 5 eluted in the treated water. However, the present invention concentrates phosphorus in order to utilize phosphorus contained in dephosphorized slag as “mineral phosphate fertilizer”, and is an official standard for fertilizers established based on the Fertilizer Control Law Then, since it is stipulated that 3.0% or more of soluble phosphoric acid is contained as a requirement for performing the notation “mineral phosphate fertilizer (refers to steelmaking ore)”, the P 2 O 5 concentration is a predetermined value. Only the treated water is recovered and reused. In the embodiment shown in FIG. 2, P 2 O 5 eluted in the treated water is not collected in the preceding carbonation treatment tanks 1 to 3, and P eluted in the treated water in the preceding carbonation treatment tanks 4 to 5. 2 O 5 is being recovered.
上記プロセスで回収したＰ２Ｏ５は、炭酸化処理後の固体残渣と共に、あるいは単独で肥料製造の原料とすることができる。炭酸化処理を複数回繰り返し行い、スラグ中のＰ２Ｏ５濃度が低下した固体残渣は、製鉄原料として再利用してもよい。 The P 2 O 5 recovered by the above process can be used alone or as a fertilizer production raw material together with the solid residue after carbonation treatment. The solid residue in which the carbonation treatment is repeated a plurality of times and the P 2 O 5 concentration in the slag is lowered may be reused as an iron-making raw material.
本願発明の実施例を示す。
本実施例に用いた溶銑脱燐スラグの組成を表１に示す。本スラグは、高炉溶銑を転炉形式の炉にスクラップとともに装入し、ＣａＯ源と酸素源を用い、攪拌を付与しつつ脱燐処理を行った際に生成したスラグを、脱燐処理終了後、溶銑を排出した後、炉内から排出されたスラグであり、これを冷却処理し、破砕後、磁選処理を行って大きな粒鉄分を除去した後のものである。
The Example of this invention is shown.
Table 1 shows the composition of the hot metal dephosphorization slag used in this example. This slag is prepared by charging blast furnace hot metal together with scrap into a converter-type furnace, using a CaO source and an oxygen source, and performing dephosphorization treatment while applying agitation. This is slag discharged from the furnace after discharging the hot metal, and after cooling, crushing, and performing magnetic separation to remove large iron particles.
（実施例１）
本スラグの一部を粉砕し、２ｍｍアンダーとし、反応容器に装入してインペラーにて攪拌を付与しつつ、ＣＯ２を２０％含む、室温に冷却された燃焼廃ガスを吹き込みながら炭酸化処理を行った。
Example 1
A part of this slag is pulverized, made under 2 mm, charged into a reaction vessel, stirred with an impeller, and carbonized while blowing combustion waste gas containing 20% CO 2 and cooled to room temperature. Went.
表１に示す組成のスラグのうち、５ｋｇを水中に懸濁させ、処理を行った。予め２０％ＣＯ２を含む排ガスを通じ、インペラー攪拌を付与した容器中の２５０Lの水中にスラグ試料を投入した。その後、６０分間の処理を行った。一旦、スラグ試料をろ過、分離し、新たに準備した炭酸ガスを通じ、インペラー攪拌を行っている水２５０Lに投入し、更に６０分間の処理を行った。はじめの処理で得られた水残渣中Ｐ２Ｏ５濃度は０％であったが、更に、再び処理を行った後に得られた残渣中Ｐ２Ｏ５濃度は４．６６％であった。 Of the slag having the composition shown in Table 1, 5 kg was suspended in water for treatment. A slag sample was put into 250 L of water in a container provided with impeller stirring through an exhaust gas containing 20% CO 2 in advance. Then, the process for 60 minutes was performed. Once the slag sample was filtered and separated, the newly prepared carbon dioxide gas was added to 250 L of water with impeller agitation, and further treated for 60 minutes. Mizuzan渣中P 2 O 5 concentration obtained at the beginning of treatment was 0%, but further were again residue P 2 O 5 concentration obtained after processing is 4.66%.
（実施例２）
表１の組成のスラグを、２５０/５の水/スラグ比で３０分間の処理を５回行った。その結果、最終スラグのＰ２Ｏ５濃度は、５．６９％であった。また、抽出液の残渣中のＰ２Ｏ５濃度は３回目以降で、元のスラグＰ２Ｏ５濃度（２．４１％）より高くなった。この場合、これら３、４、５回目の液残渣と、処理後スラグを利用して肥料製造の原料とした。
(Example 2)
The slag having the composition shown in Table 1 was treated 5 times at a water / slag ratio of 250/5 for 30 minutes. As a result, the final slag had a P 2 O 5 concentration of 5.69%. Further, the P 2 O 5 concentration in the residue of the extract was higher than the original slag P 2 O 5 concentration (2.41%) after the third time. In this case, it was set as the raw material of fertilizer manufacture using these 3rd, 4th, 5th liquid residue and post-process slag.
上記のように、本発明によれば、脱燐スラグを、炭酸ガスを溶解させた水中に投入して撹拌しながら炭酸化処理を行って、燐を固溶していないγ-２ＣａＯ・ＳｉＯ２相を処理水中に溶出させ、燐を固溶しているβ-２ＣａＯ・ＳｉＯ２相を主体とする固体残渣を回収する、という簡易な手法で、高価で取り扱いの難しい鉱酸（塩酸や硫酸等の無機酸）を用いることなく、脱燐スラグ中のＰ２Ｏ５含有量を、「く溶性燐酸を３．０％以上含有する」レベルに濃縮して、鉱さい燐酸肥料用原料を回収することができる。 As described above, according to the present invention, dephosphorization slag is poured into water in which carbon dioxide gas is dissolved, and carbonation is performed while stirring, so that γ-2CaO · SiO 2 in which phosphorus is not solid-dissolved. The mineral acid (hydrochloric acid, sulfuric acid, etc.) that is expensive and difficult to handle is simply obtained by eluting the phase into the treated water and recovering the solid residue mainly composed of β-2CaO · SiO 2 phase in which phosphorus is dissolved. The concentration of P 2 O 5 in the dephosphorized slag is concentrated to the level of “containing at least 3.0% soluble phosphoric acid” without using the inorganic acid), and the raw material for the mineral phosphate fertilizer is recovered. Can do.
Claims (6)
脱燐スラグを、炭酸ガスを溶解させた水中に投入して撹拌しながら炭酸化処理して、脱燐スラグ中の２ＣａＯ・ＳｉＯ２相を溶出するとともに、固体残渣を回収した後、該固体残渣を再度炭酸化処理する操作を複数回繰り返し、少なくとも、２回目以降の処理水から燐を回収することを特徴とする鉱さい燐酸肥料用原料回収方法。 A method of recovering a raw material for mineral slag phosphate fertilizer containing 3.0% or more of soluble phosphoric acid from dephosphorization slag generated by dephosphorization of hot metal,
The dephosphorized slag is put into water in which carbon dioxide gas is dissolved and carbonized while stirring to elute the 2CaO.SiO 2 phase in the dephosphorized slag and collect the solid residue. A method for recovering a raw material for slag phosphate fertilizer, characterized in that the operation of carbonating again is repeated a plurality of times, and phosphorus is recovered from at least the second and subsequent treated water.
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| CN103708918A (en) * | 2013-12-09 | 2014-04-09 | 山东金科天元生物肥料有限公司 | Active medium trace element mineral fertilizer and preparation method thereof |
| JP2015140294A (en) * | 2014-01-30 | 2015-08-03 | Ｊｆｅスチール株式会社 | Phosphoric acid fertilizer raw material, phosphoric acid fertilizer and manufacturing method therefor |
| WO2015114703A1 (en) | 2014-01-28 | 2015-08-06 | 日新製鋼株式会社 | Phosphorus and calcium collection method, and mixture produced by said collection method |
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| WO2019107116A1 (en) * | 2017-11-30 | 2019-06-06 | 日新製鋼株式会社 | Method for eluting calcium from steel-making slag, method for collecting calcium from steel-making slag, and device for eluting calcium from steel-making slag |
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2012
- 2012-01-10 JP JP2012001944A patent/JP2013142046A/en active Pending
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| US9783418B2 (en) | 2014-01-28 | 2017-10-10 | Nisshin Steel Co., Ltd. | Phosphorus and calcium collection method, and mixture produced by said collection method |
| WO2015114703A1 (en) | 2014-01-28 | 2015-08-06 | 日新製鋼株式会社 | Phosphorus and calcium collection method, and mixture produced by said collection method |
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