JPS58110423A - Treatment of slag containing sodium carbonate - Google Patents
Treatment of slag containing sodium carbonateInfo
- Publication number
- JPS58110423A JPS58110423A JP56202566A JP20256681A JPS58110423A JP S58110423 A JPS58110423 A JP S58110423A JP 56202566 A JP56202566 A JP 56202566A JP 20256681 A JP20256681 A JP 20256681A JP S58110423 A JPS58110423 A JP S58110423A
- Authority
- JP
- Japan
- Prior art keywords
- sodium carbonate
- extract
- value
- hydroxide
- mother liquor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、f#銑に炭酸ナトリウムtm加して脱硫また
は腕端と脱燐の両方を行なう際に生ずる鵬滓から未反応
の炭酸ナトリウム分を回収する方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for recovering unreacted sodium carbonate from the slag produced when f# pig iron is desulfurized or dephosphorized by adding sodium carbonate tm to f# pig iron.
一般に銑鉄中にはC0IL?〜4.8%、S目a3〜1
05% s M n g (l m〜(185%、S:
αo2〜αos4.およびP: (110−Q18N
という楊藏の各成分が含まれている、これらの成分のう
ち、SFi鋼の熱間加工性、衝撃性などを低下させ、ま
え、Pは靭性などを劣化させる。しえかりて、SとPは
高級鋼になるほどそれだけ可及的に少ない量にまで除去
16砧61%81
行なわれて龜九、巌酸ナト
リウムの方が嫌作向および脱硫効率の点ですぐれいるに
もかかわらず、主として経済的理由およびきた。しかし
、員環からソーダ分を効率的にしかV番AK除去回収で
きれば、上述の一点はとるにたらなくなL炭酸すFリウ
ムにょるS銑の脱硫を有利に採用することかで自る。Is there generally C0IL in pig iron? ~4.8%, S order a3~1
05% s M n g (l m~(185%, S:
αo2~αos4. and P: (110-Q18N
Among these components, P deteriorates the hot workability, impact resistance, etc. of SFi steel, and P deteriorates the toughness. In fact, the higher the quality of the steel, the more S and P are removed to the lowest possible amount. However, this was mainly due to economic reasons. However, if the soda content can only be efficiently removed and recovered from the V AK, the above-mentioned point becomes trivial and can be overcome by advantageously employing the desulfurization of S pigeon using L carbonate and F lium.
一方、rom去、すなわち脱燐は、転炉への生自灰投入
またはダブルスラグ法などにょp行なわれているが、j
れによ)生ずる転炉吹錬の廃滓(転炉#1)はPを含む
丸め、鳥炉へ装入することが必要であった。これに対し
て、浴銑に多量の炭酸ナトリウムを繊加して、転P装入
に先立りて鋳銑のm硫と脱燐を同時に何なうことが特開
昭52−12741号公権に提兼されている。かがる方
法では、脱燐恢に浴銑は転炉に装入されるため。On the other hand, ROM removal, that is, dephosphorization, is carried out by charging raw ash into a converter or by the double slag method.
The resulting converter blowing slag (converter #1) had to be rounded containing P and charged into the bird furnace. On the other hand, Japanese Patent Application Laid-Open Publication No. 12741/1983 discloses that a large amount of sodium carbonate is added to the bath pig iron to simultaneously sulfurize and dephosphorize the cast iron before charging it with P. It is also shared with. In the casting method, the hot iron is charged into a converter for dephosphorization.
そのと自得られる転炉滓はPを言まなくなり、転炉滓の
^デへの装入が可舵となp、有利である。Then, the converter slag obtained by itself does not require P, and the charging of the converter slag into the ニD can be steered, which is advantageous.
しかし、この方法は脱硫のみt何なう場合と比べて4〜
6倍菫の炭酸す) IJウムを必要とし、未反以上から
明らかなように、炭酸ナトリウムにょる浴銑のa&tま
たは脱硫・脱燐のいずれの場合にも、それにより生ずる
胸滓からのソーダ分(すなわち、主に未反応の炭酸ナト
リウム)の効率的かつ容易な回収方法を確立することが
この方法の工業化を図る上での大きな1IIIli!で
ある。However, this method only desulfurizes compared to the case where
6 times violet carbonic acid) is required, and as is clear from the above results, in both cases of A & T of bath iron using sodium carbonate or desulfurization/dephosphorization, soda from the resulting slag is Establishing an efficient and easy method for recovering the sodium carbonate (mainly unreacted sodium carbonate) is a major step toward industrializing this method! It is.
かかる員環からのソーダ分の回収法としては、%−昭6
ja−148498号に、廃滓を熱水単独で処理して/
−ダ分を抽出し、抽出液rcco、を吹き込んでソーダ
分を重炭酸塩として回収する方法が開示されてiる。し
かし、この方法はソーダ分の抽出率が低く%また多量の
熱水を必要とする上に、回収された重責酸塩はそのtま
では再使用で龜r、方決の必要がある。しかも熱水単独
による処理ではケイ素及びイオウ分も抽出されるため。As a method for recovering the soda content from such member rings,
JA-148498, treatment of waste slag with hot water alone/
- A method is disclosed in which the soda content is extracted and the soda content is recovered as bicarbonate by blowing in an extract liquid rcco. However, this method has a low extraction rate of soda and requires a large amount of hot water, and the recovered heavy acid salt must be reused until the end of its life. Moreover, silicon and sulfur components are also extracted when hot water is used alone.
これらを抽出液から分離・除去する1揚も必要となる。A step to separate and remove these from the extract is also required.
さらにこの方法によると重炭酸ナトリウムは抽出液のa
#後に平均粒嫌が約IJOpiの微細結晶状で晶出する
丸め、濾過分離の効率および脱水性が總く、また抽出に
よ如得られ重炭酸すFリウム浴液にCO3を吸収させて
重責酸化するのはco雪吸収幼皐がよくないため、大量
のCOs DI (一般にはCO,含有廃ガス)が必要
となるなど、多くの一点をかかえている。Furthermore, according to this method, sodium bicarbonate is
#Afterwards, the average particle diameter is about IJOpi, which crystallizes in a fine crystal form, which has excellent filtration separation efficiency and dehydration properties, and also has a heavy duty by absorbing CO3 into the bicarbonate bath solution obtained by extraction. It has many problems, such as the fact that coco snow absorbers are not good at oxidizing, so a large amount of COs DI (generally CO, containing waste gas) is required.
これに対して1%闘昭86−8940−号には。On the other hand, 1% Tosho No. 86-8940-.
上記廃滓をCOヨを吹龜込みつつ熱水で処理して凪1G
−115の炭皺ナトリウム抽出液を4.これから−鰯・
P遍または蒸発t−によ如責鹸ナトリウムを回収する員
環処埴法が開示されている。この方法では、CO8吹き
込みにより抽出液のpHを上記範囲内にf塊することに
よって、ケイ酸分およびイオウの抽出液中への浴出を抑
えると共に、炭酸ナトリウムの重炭酸塩化を防止してお
り、シたがって前述の%開昭52−148498号の処
虐法の欠点はほぼ排除される。The above waste slag is treated with hot water while blowing with CO to create a calm 1G.
-115 anthrax sodium extract 4. From now on - Sardines
A member ring processing method is disclosed in which sodium saponite is recovered by evaporation or evaporation. In this method, by controlling the pH of the extract to within the above range by blowing CO8, the leaching of silicic acid and sulfur into the extract is suppressed, and the conversion of sodium carbonate to bicarbonate is prevented. Therefore, the shortcomings of the above-mentioned torture method of 1972-148498 are almost eliminated.
しかし、この方法を実用化するとなると、抽出液のpH
if境龜、影響因子が多くて、管理方法としては不適切
であることが判明した。However, if this method is to be put into practical use, the pH of the extract
It was found that it is inappropriate as a management method because there are many variables and influencing factors.
また、特開昭55−811409号の方法では、抽出液
からそのits縮などによシ炭峻ナトリウ゛ムを回収し
てお如1回収炭緻す) IJウムの結1分離性について
は’IIIFK考慮が払われておらす、これに関する記
述もない、しかし、本−切者らの知見によると、たとえ
ば、特開昭55−89409号の方法のように、810
.浴出が抑えられた抽出条件下で得た抽出液をそのまま
鎖線して炭酸ナトリウムを回収しようとしても、分m性
のよい結晶#i傅られず、*縮液の何らかの調整が必要
でbることが−められた。In addition, in the method of JP-A No. 55-811409, the sodium charcoal is recovered from the extract by its condensation, etc.). However, according to the knowledge of Hon-Kirishi et al., 810
.. Even if an attempt was made to recover sodium carbonate by directly applying a chain line to the extract obtained under extraction conditions where bathing was suppressed, crystals with good separation properties could not be obtained, and some adjustment of the liquid condensation was required. I realized that.
以上の知見に基き、さらに検討を進めた結果。Based on the above knowledge, this is the result of further consideration.
抽出液の管層をpHではなく、いわゆるz値により行な
い、また蒸発鰻線源の2値を水酸化す) リウ五の添加
により一定範囲に調整すると、管理が容易な上に、析出
した炭酸ナトリウムの分離性もよいことを見出し1本発
明を完成させた。The extraction liquid tube layer is determined not by pH but by the so-called z value, and the binary value of the evaporated eel source is hydroxylated. The present invention was completed by discovering that the separation of sodium was also good.
こむに1本発明は、(1)炭酸ナトリウムで溶銑を脱硫
または脱硫・脱燐する際に生ずる高滓の処理において、
抽出液の2値がa6G−LOGとなるようにCO1含有
ガスを吹き込みながら前記高滓を熱水で抽出処理して炭
酸すFリウム含有抽出液を得る抽出工@、次いで媛縮液
の2値を(140〜α51に81111Iシながら該濃
縮液を結晶が析出するまで濃縮する一一工程、および蚊
濃縮液から析出した炭酸す)9ウムl水塩を分離・回収
する分離回収1楢からな)、前記濃縮液の2値の1iI
111iは、#鎖縮液に酸化カルシラ五または水酸化カ
ルシウムを添加して水酸化ナトリウムを生成させること
により行なうことを特徴とする上記高滓の処理方法;お
よび
(2) 上記方法において、濃縮液から結晶を分離し
た後に残る分離母液を少なくとも1部ill記濃縮工根
に再循環する再傭櫃工楊をさらに包含し、l#11綱液
のZliltの調整はiId分−母液に酸化カル/ラム
または水酸化カルシウムをムカロして水酸化ナトリウム
を生成させることにより行なうことを%鑓とする。上記
員環の処理方法である。1. The present invention provides (1) treatment of high slag generated when desulfurizing or desulfurizing/dephosphorizing hot metal with sodium carbonate,
Extracting the high slag with hot water while blowing CO1-containing gas so that the binary value of the extract becomes a6G-LOG to obtain a carbonated Fium-containing extract, followed by the binary value of the Hime condensate. (Step 11 of concentrating the concentrated solution until crystals precipitate while heating 140 to α51, and carbonic acid precipitated from the mosquito concentrated solution) Separation and recovery step 1 of separating and recovering the 9 um l hydrate. ), binary 1iI of the concentrate
111i is the above-mentioned method for treating high slag, characterized in that it is carried out by adding calsilyl oxide or calcium hydroxide to the chain condensation solution to generate sodium hydroxide; and (2) in the above method, the concentrated solution is The preparation of the Zlilt of l#11 liquid further includes a recycling tank for recycling at least a portion of the separated mother liquor remaining after separating the crystals from the concentrate into the concentration plant, and the preparation of the Zlilt of the l#11 liquid is performed by adding oxidized calcium/chloride to the mother liquor. The process of producing sodium hydroxide by mucaring rum or calcium hydroxide is called % yin. This is a method for treating the above-mentioned member ring.
本明細書に用いた「21鉦」とは、轟栗者には一知なよ
うに、Cot/’Nh のモル比t’ 、t gする
。Z値は、たとえば塙誠中和一定により次のようにして
容易に求められる。すなわち、試料の塩酸浴液による中
和において、フェノールフタレインの赤色から無色)の
変化(pH約8)に侵した塩酸の童をmattとし、そ
の後さらにメチルオレンジのオレンジ色から赤色への変
化に妥し九塩酸のm倉batとするとき、Z = b/
(a+b )である。As used in the present specification, "21 gongs" refers to the molar ratio of Cot/'Nh, t', tg, as is well known to those who play chestnuts. The Z value can be easily obtained, for example, using the Makoto Hanawa neutralization constant as follows. In other words, when the sample was neutralized with a hydrochloric acid bath solution, the hydrochloric acid solution that changed from phenolphthalein (from red to colorless) (pH about 8) was used as matt, and then the methyl orange color changed from orange to red. If mkurabat is nine hydrochloric acid, then Z = b/
(a+b).
以下に本発明の方法について添付図1を参照しながら詳
述するが、特に以下に詳しく述べる条件を除いて、抽出
および曖縮の各工程の一般的操作争件、f装置その他に
関しては、先に述べた特開昭66−894011号に詳
述されているので、その記載を参照され丸い。The method of the present invention will be described in detail below with reference to the attached FIG. It is described in detail in Japanese Patent Application Laid-Open No. 66-894011 mentioned in 1988, so please refer to that description.
第1図は1本発v4に係る方法を簡略化して示すフロー
シートである。溶銑を炭酸ナトリウムて脱硫または脱硫
・脱燐する際に生じた、アルカリを多量に含有する員環
は、抽出機lに送られ、ここで00w含有ガスを吹き込
みながら加熱された水(熱水)Kよる抽出処理を受ける
。Co、含有ガスの供給量は、COlを吸収し九抽出液
の2値がQ50〜100の範囲内、好ましくは066〜
α60となるようにm*する。FIG. 1 is a flow sheet showing a simplified method for one shot v4. The ring containing a large amount of alkali, which is generated when hot metal is desulfurized or desulfurized/dephosphorized using sodium carbonate, is sent to the extractor 1, where it is heated with water (hot water) while blowing in 00W-containing gas. Extracted by K. The supply amount of Co and containing gas is within the range of Q50 to 100, preferably 066 to 100, and the binary value of the extracted liquid after absorbing COl
m* so that α60.
この抽出工程の主目的は員環中のケイ酸分(810m)
の溶出を極力抑制して、アルカリ分のみを液相中に抽出
することである0本発明者らは。The main purpose of this extraction process is the silicic acid content (810m) in the member rings.
The purpose of the present inventors is to extract only the alkaline content into the liquid phase while suppressing the elution of the alkali as much as possible.
CO1吹込量を変えることによりて抽出液2値を変えて
高滓の抽出実験(温[80℃)を行ない、第2図に示す
結果を得た。この結果から明らかなように、抽出液の2
値がa6より小さくなると、810、の溶出は顕著とな
如、(f!の抽出液の処理が複雑となるので、SlOm
pei出置を低水単装抑えるために2値はα6以下とす
る。一方、2値が0521直をα6以下としたのは、α
6〜LOではあまりS i Otの溶出に差がなく、し
たがって、α6橿次いで、得られた抽出混合物をP通機
2で抽残と抽出液とに分離した後、抽出液I/i蒸発器
8に送られ、ここで炭酸ナトリウムl水塩の結晶が析出
するまで加熱濃縮される。この製線1楊において1喪な
ことは、濃11mのZflliを酸化カルシウムまたは
水酸化カルシウムの添加により、つまり、後述するよう
に水酸化ナトリウムのam増大によりα4θ〜061.
好ましくはQ4?〜α50に常に制御することである。A high dregs extraction experiment (at a temperature of 80°C) was conducted by changing the binary values of the extract by changing the CO1 injection amount, and the results shown in FIG. 2 were obtained. As is clear from this result, the extract
When the value is smaller than a6, the elution of 810 becomes remarkable, and the processing of the extract of (f!) becomes complicated, so SlOm
In order to suppress pei emplacement by a low water unit, the binary value is set to α6 or less. On the other hand, the reason why the binary value is 0521 direct is less than α6 is α
There is not much difference in the elution of S i Ot between α6 and LO, therefore, the obtained extraction mixture is separated into a raffinate and an extract in the P passer 2, and then the extract I/i evaporator 8, where it is heated and concentrated until crystals of sodium carbonate hydrate precipitate. The most unfortunate thing about this wire manufacturing process is that by adding calcium oxide or calcium hydroxide to Zflli with a concentration of 11 m, that is, by increasing the am of sodium hydroxide as described later, α4θ~061.
Preferably Q4? ~ α50.
このため本発明にありては蒸発48に入るに先立りであ
るiは必要によっては蒸発器8に入りてから濃縮液(す
なわち、濃縮を行なう抽出液をいう)の2値を所定の範
囲内に調贅するとともに、澁縮工程の期間中も該濃縮液
の2値を上記所定範囲内に調整する。Therefore, in the present invention, before entering the evaporator 48, i is set to a binary value of the concentrated liquid (that is, the extract to be concentrated) after entering the evaporator 8, if necessary, within a predetermined range. At the same time, the binary value of the concentrated liquid is adjusted within the above-mentioned predetermined range during the contraction process.
本発明省らの知見によると、z値がα61よシ^く、α
61以下の範囲内の溶液からはセス中炭誠ナトリウム(
N&@Co@ ” NaHCO@ ” i!HIO)が
析出し、これはノリ状の結晶で分離が非常に困−である
。また、zl[が(161−LOGの範囲内の溶液から
は重炭酸すFリクムが析出する0重炭酸ナトリウムを析
出させるのは前出の特開昭62−148498号におい
て採用された方法であるが、既に述ぺえように1重炭酸
ナトリウムはそのiまでは脱硫等に再使用できない上に
、結晶が微細であるため、結晶の分離効率および脱水性
がよくない。According to the findings of the Ministry of Invention and others, the z value is higher than α61, and α
From solutions within the range of 61 or less, sodium carbonate in cess (
N&@Co@ ” NaHCO@ ” i! HIO) is precipitated and is a glue-like crystal that is very difficult to separate. In addition, from a solution where zl [ is within the range of (161-LOG), bicarbonate (Flicum) is precipitated.0 Precipitating sodium bicarbonate is the method adopted in the above-mentioned JP-A-62-148498. However, as already mentioned, sodium bicarbonate cannot be reused for desulfurization or the like up to i, and the crystals are fine, so the crystal separation efficiency and dehydration properties are poor.
これに対して1本発明におけるように、濃縮時の2値が
α51以下の溶液から析出するのは炭酸ナトリウム1水
塩(Na、CO,・H,0)であシ、これは平均粒子径
が約160声の結晶であって1分離用態率位が急激に増
加する九め経済性に欠け、好ましくない。On the other hand, as in the present invention, it is sodium carbonate monohydrate (Na, CO, .H, 0) that precipitates from a solution with a binary value of α51 or less during concentration, and this has an average particle size of is a crystal of about 160 tones, and the rate of use per minute increases rapidly, which is undesirable because it lacks economy.
前出の特開昭56−89409号の方法でも、本発明の
方法の抽出工程におけると同様に、S10゜の溶出が抑
制される範囲内にCot吹込みIn制呻しつつ廃線の抽
出を行なうが、抽出液はそのまま1紬に付すため、析出
し九結晶は、必すしも分離性のよい炭酸ナトリウムl水
塩でtjなく、多くの場合、分離が非常に困龜なセスキ
炭酸塩の析出を生ずるものと考えられる。llk@工機
に工程て、例えば蒸発器による蒸発時、濃縮液温度はは
’ff170℃程度であるため、(jIJk極液からは
00重がでてゆくよりもむしろCO8を吸収する傾向が
あり、したがって、2値は容易に上昇する傾向にある。In the method of JP-A No. 56-89409 mentioned above, as in the extraction step of the method of the present invention, the waste wire is extracted while suppressing Cot injection within the range where the elution of S10° is suppressed. However, since the extract is directly applied to the pongee, the nine crystals that precipitate are not necessarily sodium carbonate hydrate, which is easily separated, but are often sesquicarbonate, which is extremely difficult to separate. It is thought that precipitation occurs. For example, during evaporation using an evaporator, the temperature of the concentrated liquid is about 170°C, so the extremely liquid tends to absorb CO8 rather than releasing 00 weight. , Therefore, the binary value tends to increase easily.
そして、このように2値が容易に上昇する結果、何ら手
段を祷じなI+’h限シ速やかにその値はα51を越え
てしまい、濃縮液からは主としてセスキ炭酸塩が析出し
てくるのである。As a result of the binary value rising easily in this way, the value quickly exceeds α51 in the I+'h limit without any measures being taken, and sesquicarbonate mainly precipitates from the concentrated liquid. be.
なお、水酸化す) IJウムの嫌に増大により濃縮液の
2値をα40〜α61に*IIすることは、a縮液に直
接水酸化ナトリウムを添加することによっても轟然SA
總できる。しかし、水酸化ナトリウムは比較的^愉であ
るので、水酸化ナトリウムの添加ii経済的には不利を
伴なう。In addition, increasing the binary value of the concentrated liquid to α40 to α61 due to an undesirable increase in IJ (hydroxide) can also be achieved by adding sodium hydroxide directly to the a-condensed liquid.
I can do it. However, since sodium hydroxide is relatively cheap, the addition of sodium hydroxide is economically disadvantageous.
本発明によれば、すでに述べたように、濃縮液の2億1
liIIIE(すなわち、水酸化ナトリウム濃度の増大
)/fi、抽出F[(抽残分離後の抽出液)に酸化カル
シウムまたは水酸化カルシウムを添加することにより行
なわれる。これらのカルシウム化合物は、抽出液中の炭
酸ナトリウムと次式のように反応して、水酸化ナトリウ
ムの生成を生ずる。According to the present invention, as already mentioned, 210 million yen of the concentrated liquid
liIIIE (i.e., increase in sodium hydroxide concentration)/fi, extraction F [is carried out by adding calcium oxide or calcium hydroxide to (the extract after raffinate separation). These calcium compounds react with sodium carbonate in the extract as shown in the following formula to produce sodium hydroxide.
(1) NamC0a十〇a(OH)1−+CaC0
,B↓+gNaO)1(2) Na@COs+C
aO+H*0 −+ Caco、 ↓+!!NaO
Hすなわち、水酸化カルシウムiたは酸化カルシウムの
添加はNaOHの生成を引起し、001分を沈澱として
固相に移行させるので、結果として抽出液の2値を低下
させる。上記の反応式から明らかなように、1モルのカ
ルシウム化合−の添加は#A場的には(上記の反応が1
0(l進行したとして)、2モルの水酸化ナトリウムの
添加に相当する。友とえは上記(1)式の反応率が70
%である(すなわち、1モルのCa(OH)tからL4
モルのNaQHが生成)と仮定しても、水酸化カルシウ
ムの1モル″!iシの価格は水酸化ナトリウムの1モル
の価格の約5496にすぎないので、同じZlmt−得
るのに。(1) NamC0a10a(OH)1-+CaC0
,B↓+gNaO)1(2) Na@COs+C
aO+H*0 −+ Caco, ↓+! ! NaO
In other words, the addition of calcium hydroxide or calcium oxide causes the formation of NaOH and causes 001 min to be transferred to the solid phase as a precipitate, resulting in a decrease in the binary value of the extract. As is clear from the above reaction formula, addition of 1 mol of calcium compound is #A field (the above reaction is 1 mole).
0 (assuming 1 progressed), corresponding to the addition of 2 mol of sodium hydroxide. Tomatoe has a reaction rate of 70 in the above formula (1).
% (i.e. from 1 mol Ca(OH)t to L4
Even assuming that 1 mole of NaQH is produced), the price of 1 mole of calcium hydroxide is only about 5496 of the price of 1 mole of sodium hydroxide, so to obtain the same Zlmt-.
水酸化す) IJウムの直接添加の礪せの約88〜89
%の費用ですむことになる。About 88-89% of the decay of direct addition of IJium (hydroxide)
% of the cost.
なお、カルシウム化合物の添加で生成し九〇theO@
の沈澱物は予め濾過等の適宜手段で除去してもよい。Furthermore, 90theO@ is produced by adding calcium compounds.
The precipitate may be removed in advance by appropriate means such as filtration.
蒸発器8で結晶が析出するまでさらに噴輔された濃縮液
は次いで結晶分離慎4に送られ、ここで析出した炭酸ナ
トリウム1水塩の結晶が分離・回収され、回収された結
晶は乾燥処理後浴銑の脱硫または脱硫・脱燐にそのまま
再使用することができる。The concentrated liquid that is further spouted in the evaporator 8 until crystals are precipitated is then sent to the crystal separation station 4, where the precipitated crystals of sodium carbonate monohydrate are separated and collected, and the collected crystals are subjected to drying treatment. It can be reused as is for desulfurization or desulfurization/dephosphorization of after-bath pig iron.
分離母液は高濃度(飽和?#度)の炭酸ナトリウムを含
有しているので1通常は第1図に破線で示すように蒸発
器8に戻される。このような場合。Since the separated mother liquor contains a high concentration (saturated level) of sodium carbonate, it is normally returned to the evaporator 8 as shown by the broken line in FIG. In such cases.
濃縮液のzWlの調整は、抽出f液つまり濃縮液に直接
に酸化カルシウムまたは水酸化カルシウムを添加する代
りに、やは)第1図に破線で示すように蒸発−に少なく
とも1部再循壌される分離母液に上記カルシウム化合物
を添加することによっても実施できる0分離母液にカル
シウム化合物を添加する場合には、抽出F液より分離母
液の方が炭酸ナトリウム含有量が高い丸めに、水酸化ナ
トリウムを生ずる上記反応式の反応効率が大龜くなると
いう利点がめる。また、水酸化ナトリウムの生成により
アルカリ溶解匿が上昇するために1分離母猷中Kfi#
してiる微細結晶の溶解が期費され、これは回収される
結晶性状の安定化につながると同時に蒸発工程の軸条を
安定化させる。Adjustment of the zWl of the concentrate can be achieved by adding at least a portion of the evaporation to the evaporation process, as shown by the dashed line in Figure 1, instead of adding calcium oxide or hydroxide directly to the extract or concentrate. When adding a calcium compound to the separated mother liquor, sodium hydroxide may be added to the separated mother liquor, which has a higher sodium carbonate content than the extracted F solution. This has the advantage that the reaction efficiency of the above reaction formula that produces . In addition, since the alkali dissolution increases due to the generation of sodium hydroxide, Kfi #
The dissolution of the microcrystals during the process is delayed, which leads to stabilization of the recovered crystalline state and at the same time stabilizes the axis of the evaporation process.
なお1分離母液の再循環については、母液の全1を蒸発
ムに再循環すると、5totその他の不純物が系内に次
第に蓄積され、回収された結晶の純度低下などの悪影響
が出てくる。したがって、これを避ける丸め1分離母液
の一部は、第1図には示していないが、P通mgよシ上
1側の抽出液に戻すのが好ましい、それによシネ#1物
は固相側に移行し、濾過@2を経て残渣の一部として系
外に除去される。Regarding recycling of the separated mother liquor, if all of the mother liquor is recycled to the evaporator, 5tot and other impurities will gradually accumulate in the system, resulting in adverse effects such as a decrease in the purity of the recovered crystals. Therefore, to avoid this, it is preferable to return a part of the separated mother liquor to the extract on the upper side of the plate, although it is not shown in Figure 1. It moves to the side and is removed from the system as part of the residue through filtration@2.
tた。後出の実施例で示すように、温度が高いほどカル
シウム化合物から水酸化ナトリウムへの転化率が高くな
るので、カルシウム添加時のm度は比較的高m(例、8
0℃以上)とするのが好ましい。It was. As shown in the examples below, the higher the temperature, the higher the conversion rate from calcium compounds to sodium hydroxide.
(0°C or higher) is preferable.
上述したように、本発明の方法では抽出液および護−液
の管理にいずれもZ値を官坤パラメータとして利用する
が、Z[による−#坤はpH官城に比べて影響因子が少
なく、適切なコントロールが可能という利点がめる。As mentioned above, in the method of the present invention, the Z value is used as a control parameter for both extraction liquid and protection liquid management, but the Z value has fewer influencing factors than the pH control, and The advantage is that appropriate control is possible.
次に実施列によυ本発明をさらに説明する。Next, the present invention will be further explained with reference to examples.
実施例
本例はカルシウム化合(1!+ 15770によるzl
−変化の例を示すものである。来操業上得た抽出液から
残本を戸別して4+、150 f/ l(D NatC
Omを含有する抽出F液(2値−α55)500CC1
−1/、ビーカーに入れ、恒温情によす温fを一定に保
持しながら、水酸化カルシウム粉末または酸化カルシウ
ム粉末を添加し、2時間攪拌した。その後、溶練の2値
を測定し、得られた2値からカルシウム化合切の転化率
(%)を計算した。結果を下記の繭1表に示す。Example This example is a calcium compound (1!+ zl by 15770
-Illustrates examples of changes. From the extract obtained during the previous operation, the remaining volume was collected from each household to 4+, 150 f/l (D NatC
Extract F solution containing Om (binary - α55) 500CC1
-1/, was placed in a beaker, and calcium hydroxide powder or calcium oxide powder was added thereto while keeping the temperature f constant under constant temperature conditions, and the mixture was stirred for 2 hours. Thereafter, the two values of melting were measured, and the conversion rate (%) of calcium compound removal was calculated from the two values obtained. The results are shown in Table 1 below.
同様の実験を2809/lのNamCO5lr金含有る
分離母液(2値α6G)についても行なった。結果を第
2表に示す。A similar experiment was carried out on a separated mother liquor (binary α6G) containing 2809/l NamCO5lr gold. The results are shown in Table 2.
wns 抽出P液(Na、CO1濃[150f/l)
へのCa添加
第2表 分離母液(NltCOmlllf28Or、/
l)へのCa奈加
上記の結果から、温度が高くなるほどカルシウム化合物
の転化率(反応率)が大きくなること。Wns Extract P solution (Na, CO1 concentration [150f/l)
Table 2 Addition of Ca to Separated mother liquor (NltCOmlllf28Or, /
From the above results, the conversion rate (reaction rate) of calcium compounds increases as the temperature increases.
および炭酸ナトリウム濃度の高い分離母液の方が転化率
が大きいことがわかる。なお酸化カルシウムを添加した
場合には、これが一旦水と反応してCa(OH)寓を生
成するが、その生成熱のために温に上昇が起る。そのた
め、#I化カル7ウムの場合の方が反応温度が高くなっ
ている。It can be seen that the conversion rate is higher for the separated mother liquor with a higher concentration of sodium carbonate. Note that when calcium oxide is added, it once reacts with water to produce Ca(OH), but the temperature rises due to the heat of its formation. Therefore, the reaction temperature is higher in the case of #I calcium.
このように、カルシウム化合物の添加によっていずれの
場合もZl[を低下させることができることが分かる。Thus, it can be seen that Zl[ can be reduced in any case by adding a calcium compound.
したがりて、実際の操業にありても上記カル7りム化合
物の添加が2属調節の有効な手設であることが分かる。Therefore, it can be seen that the addition of the above-mentioned cal-7-lim compound is an effective means of controlling genus 2 even in actual operation.
1lk1図Fi、本発明の方法の概略を示すフローシー
ト;および
第8図は、抽出液の2値と8i0.Ill出量との関係
を示すグラフである。
l:抽出@St蒸発器
ZgPAWA 4:結晶分離機
−出願人代理人 弁理士 広瀬章−1lk1 Figure Fi, a flow sheet showing an outline of the method of the present invention; and Figure 8 shows the binary values of the extract and 8i0. It is a graph showing the relationship with Ill output amount. l: Extraction @ St evaporator ZgPAWA 4: Crystal separator - Applicant's agent Patent attorney Akira Hirose -
Claims (2)
燐する際に生ずゐ員環の処理において、抽出液のz値が
α60〜LOOとなるようKCO,含有ガスを吹き込み
ながら前記廃欅を熱水で抽出処理して炭酸ナトリクム含
有抽出液を得る抽出1橘、′次いで111m液の2mを
α40〜α51に1整しながらlW讃縮液を結晶が析出
するまで濃縮する濃縮工程および、該濃縮液から析出し
た炭酸ナトリウムl水塩を分離・略収する分離回収工程
からなシ。 前戯磯縮液の2値の調整は、鋏濃縮液に酸化カルシウム
または水酸化カルシウムを添加して水酸化ナトリウムを
生成させることによシ行なうことを%値とする。炭酸ナ
トリウム含有員環の処理方法。(1) In the treatment of membered rings generated when desulfurizing hot metal or desulfurizing and dephosphorizing hot metal with sodium carbonate, the waste keyhole is heated while blowing KCO and gas containing it so that the z value of the extract becomes α60 to LOO. Extracting with hot water to obtain a sodium carbonate-containing extract, a concentration step of concentrating the lW condensate until crystals precipitate, while adjusting 2m of the 111m liquid to α40 to α51; There is no separation and recovery step for separating and approximately collecting the sodium carbonate hydrate precipitated from the concentrated solution. The binary adjustment of the foreplay condensate is carried out by adding calcium oxide or calcium hydroxide to the scissor concentrate to generate sodium hydroxide, which is expressed as a percentage value. A method for treating a membered ring containing sodium carbonate.
燐する除に生ずる鳥滓O処11に−おりて、抽出液のZ
iU)i60〜LOGとなりようKCO,含有ガスを吹
き込みながら前記員環を熱水で抽出処纏して炭酸ナトリ
ウム含有抽出液を僧る悄出工根、次いで濃縮液のZnk
を140〜αb1に1贅しながら該濃縮液を結晶が部分
的に析出する壕で磯−する1llllli1工相、該濃
縮液から析出した炭慮ナトリウムー1水塩を分離・回収
する分離回収工程、および得られる分#Il母液の少な
くともl鄭を前配幽−工鴨に再儂壌する丹循穣工撫から
なり、削記製線液の2値の調整は1Ill記分−母液に
酸化カルシウムまたは水酸化カルシウムを添加して水酸
化ナトリウムを生成させることによプ行なうことを%像
とする、炭酸ナトリウム含有員環の処理方法。(2) Sulfurize the pig iron using sodium carbonate.
iU) i60~LOG KCO, extraction treatment of the member ring with hot water while blowing the contained gas to obtain a sodium carbonate-containing extract, and then Znk as a concentrated solution
1llllli1 process phase in which the concentrated liquid is washed in a trench where crystals are partially precipitated while increasing the concentration to 140 to αb1, a separation and recovery step in which sodium carbonate monohydrate precipitated from the concentrated liquid is separated and recovered; And the obtained part #Il mother liquor consists of adding at least 1 part of the mother liquor to the mother liquor and re-incubating it. Or, a method for treating a sodium carbonate-containing member ring, which is carried out by adding calcium hydroxide to produce sodium hydroxide.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP56202566A JPS58110423A (en) | 1981-12-17 | 1981-12-17 | Treatment of slag containing sodium carbonate |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP56202566A JPS58110423A (en) | 1981-12-17 | 1981-12-17 | Treatment of slag containing sodium carbonate |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS58110423A true JPS58110423A (en) | 1983-07-01 |
JPS615656B2 JPS615656B2 (en) | 1986-02-20 |
Family
ID=16459612
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP56202566A Granted JPS58110423A (en) | 1981-12-17 | 1981-12-17 | Treatment of slag containing sodium carbonate |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS58110423A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2589671A1 (en) * | 2011-11-04 | 2013-05-08 | Frank Werfel | Method and apparatus for integrating and using environmentally harmful carbon dioxide |
-
1981
- 1981-12-17 JP JP56202566A patent/JPS58110423A/en active Granted
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2589671A1 (en) * | 2011-11-04 | 2013-05-08 | Frank Werfel | Method and apparatus for integrating and using environmentally harmful carbon dioxide |
Also Published As
Publication number | Publication date |
---|---|
JPS615656B2 (en) | 1986-02-20 |
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