JPH0316913A - Production of high-purity sodium carbonate - Google Patents
Production of high-purity sodium carbonateInfo
- Publication number
- JPH0316913A JPH0316913A JP14913989A JP14913989A JPH0316913A JP H0316913 A JPH0316913 A JP H0316913A JP 14913989 A JP14913989 A JP 14913989A JP 14913989 A JP14913989 A JP 14913989A JP H0316913 A JPH0316913 A JP H0316913A
- Authority
- JP
- Japan
- Prior art keywords
- sodium carbonate
- soda
- sodium
- carbonate
- solution
- 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
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 title claims abstract description 85
- 229910000029 sodium carbonate Inorganic materials 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 71
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 48
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims abstract description 37
- 235000017557 sodium bicarbonate Nutrition 0.000 claims abstract description 36
- 229940001593 sodium carbonate Drugs 0.000 claims abstract description 21
- 239000012452 mother liquor Substances 0.000 claims abstract description 11
- 229910000031 sodium sesquicarbonate Inorganic materials 0.000 claims abstract description 11
- 235000018341 sodium sesquicarbonate Nutrition 0.000 claims abstract description 11
- WCTAGTRAWPDFQO-UHFFFAOYSA-K trisodium;hydrogen carbonate;carbonate Chemical compound [Na+].[Na+].[Na+].OC([O-])=O.[O-]C([O-])=O WCTAGTRAWPDFQO-UHFFFAOYSA-K 0.000 claims abstract description 11
- MQRJBSHKWOFOGF-UHFFFAOYSA-L disodium;carbonate;hydrate Chemical compound O.[Na+].[Na+].[O-]C([O-])=O MQRJBSHKWOFOGF-UHFFFAOYSA-L 0.000 claims abstract description 6
- 229940076133 sodium carbonate monohydrate Drugs 0.000 claims abstract description 6
- 229940071207 sesquicarbonate Drugs 0.000 claims abstract description 4
- 235000017550 sodium carbonate Nutrition 0.000 claims description 22
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 20
- 239000011575 calcium Substances 0.000 claims description 18
- 229910052791 calcium Inorganic materials 0.000 claims description 15
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 15
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 14
- 239000012535 impurity Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 16
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 8
- 239000001569 carbon dioxide Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 229910001424 calcium ion Inorganic materials 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000356 contaminant Substances 0.000 abstract 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 abstract 1
- 238000009434 installation Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 25
- 239000000243 solution Substances 0.000 description 16
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 239000006228 supernatant Substances 0.000 description 8
- 235000019270 ammonium chloride Nutrition 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 239000000920 calcium hydroxide Substances 0.000 description 4
- 235000011116 calcium hydroxide Nutrition 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- -1 soda ash monohydrate Chemical class 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は高純度炭酸ソーダの製造法、特にカルシウム濃
度の低い高純度炭酸ソーダを経済的に製造する方法に関
する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for producing high-purity soda carbonate, and particularly to a method for economically producing high-purity soda carbonate with a low calcium concentration.
（従来技術）
炭酸ソーダは工業的に重要な無機薬品として通常は塩化
アンモニウムと重炭酸ナトリウム（以下重曹という）を
交互に析出せしめる所譚塩安ソーダ法、あるいは重曹の
みを析出せしめ、塩化アンモ′ニウムは蒸留してアンモ
ニアは回収し、これを循環使用する所讃アンモニアソー
ダ法等により製造されている。(Prior art) Soda carbonate is an industrially important inorganic chemical, and is usually produced using the ammonium chloride method, in which ammonium chloride and sodium bicarbonate (hereinafter referred to as baking soda) are precipitated alternately, or by the ammonium chloride method, in which only baking soda is precipitated. It is produced by the Tosan ammonia soda method, etc., in which the nium is distilled, the ammonia is recovered, and this is recycled.
これらの方法により製造された炭酸ソーダは、通常Ｃａ
Ｏが７０〜１５０ｐｐ’ｍ程度含まれており高純度の品
質確保の上では障害となっている。Soda carbonate produced by these methods usually contains Ca
It contains about 70 to 150 pp'm of O, which is an obstacle to ensuring high purity quality.
そのため原料の精製、更には工程内における循環母液に
石灰乳、消石灰等を添加し溶存するＣａ， Ｍｇ等の不
純物を共沈除去する方法（特公昭４６−１００５８）、
更には塩安分離母液の温度を５〜４０゜Ｃの範囲内にお
いて浮遊するＭｇＣＯ．・（ＮＩ＋４）２ＣＯ３・４１
ｈＯあるいはＣａＣ０３・Ｎａ２ＣＯ．， Ｈ ５８２
０の複塩を除去分離する方法（特公昭６１−８０１７）
。更には塩安分離母液の部分的炭酸化により生或する重
曹に、不純物を吸着共沈させたのち上澄液を再度炭酸化
する分割炭酸化法による精製法（特願昭６３−８０９１
）などがある。For this purpose, there is a method for purifying the raw materials, and further adding milk of lime, slaked lime, etc. to the circulating mother liquor in the process to remove dissolved impurities such as Ca and Mg by coprecipitation (Japanese Patent Publication No. 10058/1983).
Furthermore, the temperature of the ammonium chloride separated mother liquor is kept within the range of 5 to 40°C to remove floating MgCO.・(NI+4)2CO3・41
hO or CaC03/Na2CO. , H 582
Method for removing and separating the double salt of
. Furthermore, a purification method using a partial carbonation method in which impurities are adsorbed and co-precipitated on sodium bicarbonate produced by partial carbonation of the ammonium chloride-separated mother liquor, and then the supernatant liquid is carbonated again (Japanese Patent Application No. 8091/1983)
)and so on.
（発明が解決しようとする問題点）
しかしながら、かかる方法においては添加された石灰乳
、消石灰の大部分は、不純物の除去に寄与しながら炭酸
カルシウムの沈澱を生威、これは沈降分離されるが、な
お溶存するカルシウム等は炭酸化工程でその大部分は析
出する重曹側へ移行する。(Problems to be Solved by the Invention) However, in this method, most of the added milk of lime and slaked lime contributes to the removal of impurities while producing precipitates of calcium carbonate, which are separated by sedimentation. However, most of the dissolved calcium and the like migrate to the baking soda side where it precipitates during the carbonation process.
また、冷却により析出するカルシウム等含有複塩はその
冷却手段等エネルギー的にまた操作上煩雑であり、分割
炭酸化は炭酸化装置の区分化など設備が複雑となり投資
額も大きくなる。Furthermore, the double salt containing calcium and the like that is precipitated by cooling requires energy and operational complexity such as cooling means, and split carbonation requires complicated equipment such as the division of carbonation equipment, resulting in a large investment amount.
なお、ＣａＯを低減した高純度炭酸ソーダを得るには、
電解苛性ソーダの炭酸化により数ｐｐｍ〜２０ｐｐｍの
炭酸ソーダ、更には苛性ソーダの製造原料である精製塩
水を用いてアンモニアソーダ法でＣａＯの極めて少ない
高純度炭酸ソーダを製造する方法も考えられるが、いず
れも設備費および原料代等が高く、ひいては得られる炭
酸ソーダの製造コスト高につながる。In addition, in order to obtain high purity soda carbonate with reduced CaO,
It is also possible to produce high-purity soda carbonate with an extremely low CaO content by carbonation of electrolyzed caustic soda to a concentration of several ppm to 20 ppm, or even by the ammonia soda method using purified brine, which is the raw material for producing caustic soda, but none of these methods work. Equipment costs, raw material costs, etc. are high, which in turn leads to high production costs of the obtained soda carbonate.
（問題点を解決するための手段）
本発明は上記諸点を解消するため、炭酸ソーダ溶液にＣ
Ｏ２ガスを吹込み炭酸化して重曹が晶出する際に、カル
シウムイオンが吸着することに着目しこれを利用するも
のである。(Means for Solving the Problems) In order to solve the above-mentioned problems, the present invention provides carbon dioxide in soda solution.
This method takes advantage of the fact that calcium ions are adsorbed when baking soda is crystallized by blowing in O2 gas for carbonation.
第１図は炭酸化ラボテストにおける重曹晶出量と重曹を
沈降させたのち、上澄液中ＣａＯ濃度との関係を示した
ものである。該図からも判るように重曹晶出量の増加に
伴い上澄液のカルシウム濃度は急激に減少し、この傾向
は炭酸化工程に供給する炭酸ソーダ溶液中のＣａＯ濃度
に比例する。FIG. 1 shows the relationship between the amount of sodium bicarbonate crystallized in the carbonation laboratory test and the CaO concentration in the supernatant after the sodium bicarbonate was precipitated. As can be seen from the figure, as the amount of sodium bicarbonate crystallized increases, the calcium concentration in the supernatant liquid decreases rapidly, and this tendency is proportional to the CaO concentration in the sodium carbonate solution supplied to the carbonation process.
通常、炭酸ソーダ溶液中のカルシウムは炭酸カルシウム
として沈澱除去してある程度の除去は可能であるが、カ
ルシウムは温度による溶解度差がマグネシウム等他の不
純物に比べて殆どないため数ｐｐｍ以下にすることは濾
過及び再結晶法等の手段では不可能である。Normally, calcium in a sodium carbonate solution can be removed to some extent by precipitation as calcium carbonate, but since calcium has little difference in solubility depending on temperature compared to other impurities such as magnesium, it is difficult to reduce the amount to less than a few ppm. This is not possible with methods such as filtration and recrystallization.
したがって、本発明ではこれら微量の含有カルシウムを
除去するために炭酸化による重曹の晶出初期段階の晶出
重曹あるいはセスキ炭酸ソーダ自身にカルシウムの吸着
を行わせるものである。Therefore, in the present invention, in order to remove these trace amounts of calcium contained, calcium is adsorbed on the crystallized sodium bicarbonate or sodium sesquicarbonate itself in the initial stage of crystallization of sodium bicarbonate through carbonation.
３ＮａｚＣＯａ＋ＣＯｚ＋５ＨｚＯ
’＝ ２（Ｎａｚｃｏａ ’ ＮａＨＣＯ３’ ２Ｈｚ
Ｏ）Ｎａ２ＣＯ３＋ＣＯ２＋ｔｌｚＯ →２ＮａＨＣＯ
３即ち、炭酸化工程において重曹あるいはセスキ炭酸ソ
ーダ晶出量の一部を晶出させこれにカルシウム等の不純
物を吸着共沈せしめて生威する重曹と共に系外に取出し
、不純物除去後の精製母液に苛性ソーダ溶液を添加し残
存する重曹を分解して完全な炭酸ソーダ溶液としてから
これを濃縮して炭酸ソーダＩ水塩を析出、仮焼して高純
度の炭酸ソーダを得ることができる。3NazCOa+COz+5HzO'=2(Nazcoa'NaHCO3'2Hz
O) Na2CO3+CO2+tlzO →2NaHCO
3. In other words, in the carbonation step, a part of the sodium bicarbonate or sodium sesquicarbonate is crystallized, impurities such as calcium are adsorbed and co-precipitated thereon, and taken out of the system together with the viable sodium bicarbonate, and purified mother liquor is obtained after removing impurities. A caustic soda solution is added to decompose the remaining baking soda to form a complete sodium carbonate solution, which is then concentrated to precipitate sodium carbonate I hydrate, which is then calcined to obtain highly pure sodium carbonate.
５−
ＮａＨＣＯ３＋ＮａＯＨ −＋ ＮａｚＣＯ３ Ｈ
Ｈ２ｏここで炭酸化工程での重曹晶出量を調節すること
により所望するＣａＯ濃度の炭酸ソーダを容易に得るこ
とができるが、一般的には炭酸ソーダ溶液中の全Ｎａｚ
ＣＯ３の５〜５０重量％が適当、好ましくは２０〜３５
重量％である。５％以下では脱カルシウム効果が乏し＜
、５０％以上ではそれ相応の効果は得られない。また、
炭酸化の反応温度が３５℃以上の場合には、カルシウム
は重曹結晶に吸着されにくくなるので反応温度は３５℃
以下にする必要がある。5- NaHCO3+NaOH −+ NazCO3 H
H2o Here, by adjusting the amount of sodium bicarbonate crystallized in the carbonation step, it is possible to easily obtain sodium carbonate with a desired CaO concentration, but in general, the total Naz in the sodium carbonate solution
5-50% by weight of CO3 is suitable, preferably 20-35%
Weight%. Below 5%, the decalcification effect is poor.
, 50% or more, no corresponding effect can be obtained. Also,
If the carbonation reaction temperature is 35°C or higher, calcium will be difficult to adsorb to the baking soda crystals, so the reaction temperature should be 35°C.
It is necessary to do the following.
なお、炭酸化に供する炭酸ソーダ溶液の濃度は晶出させ
る重曹、セスキ炭酸ソーダによって異なるが重曹の場合
は大略２１％以下であることが望まし《、それ以上の濃
度のものを炭酸化するとセスキ炭酸ソーダが重曹と共に
晶出し重曹の純度低下を招く。またＮａ２ＣＯ３濃度が
低いと製造コストが対応して高くなるため１０〜２１％
の範囲が望ましい。The concentration of the sodium carbonate solution used for carbonation varies depending on the sodium bicarbonate and sesquicarbonate to be crystallized, but in the case of baking soda, it is preferably about 21% or less. Soda carbonate crystallizes together with baking soda, leading to a decrease in the purity of baking soda. In addition, if the Na2CO3 concentration is low, the manufacturing cost will be correspondingly high, so 10-21%
A range of is desirable.
一方、セスキ炭酸ソーダを晶出させる場合は、６
炭酸ソーダの溶解度が３３％で３５℃であることから、
飽和溶液はそれ以下の温度ではＮａ２ＧＯ．，・１０｝
１２０が晶出するため取扱いが煩雑であり、Ｎａ２ＧＯ
３濃度が低いとセスキ炭酸ソーダの晶出量が少なくなり
脱カルシウムの効果が劣るためその濃度は２１〜３３％
程度が望ましい。On the other hand, in the case of crystallizing sodium sesquicarbonate, since the solubility of sodium carbonate is 33% and the temperature is 35°C,
At lower temperatures, a saturated solution becomes Na2GO. ,・10}
Handling is complicated because 120 crystallizes, and Na2GO
3. If the concentration is low, the amount of sodium sesquicarbonate crystallized will decrease and the decalcification effect will be inferior, so the concentration will be 21 to 33%.
degree is desirable.
炭酸化の反応温度は、供給する炭酸ソーダ溶液の温度に
左右され、また炭酸化反応は発熱反応であるため、効率
的な炭酸化のためには冷却が必要であるが、反応温度を
あまり下げると重曹あるいはセスキ炭酸ソーダの晶出速
度が速くなり脱カルシウム効果が薄れ、エネルギー的に
も不利である。The carbonation reaction temperature depends on the temperature of the sodium carbonate solution supplied, and since the carbonation reaction is exothermic, cooling is necessary for efficient carbonation, but the reaction temperature cannot be lowered too much. This increases the crystallization rate of baking soda or sodium sesquicarbonate, weakens the decalcification effect, and is disadvantageous in terms of energy.
従って、経済的（冷却エネルギー）な反応温度は４０〜
２０℃の範囲、より好適には３５〜２５℃である。この
ようにして生威する重曹またはセスキ炭酸ソーダあるい
はこれらの混合物にはカルシウム等の不純物を効率よく
吸着共沈させることができる。結晶は分離し、母液には
ＮａＨＣＯ．が溶存しているため、Ｍａｉｌを添加して
分解を行いＮａ２ＣＯ．・ＨｚＯとなしこれを濃縮して
炭酸ソーダ１水塩を析出させるものである。ＮａＯＨの
添加量はＮａＨＣ０３当量分が必要であるが、これより
多いとＮａＯＨがＮａｚＣＯｉ Ｈ ｔｔＺｏ中に移行
し、少ないと未分解となりいずれも炭酸ソーダ製品の純
度低下を招く。これら当量添加の目標として通常はｐｎ
制伽、例えば３０℃におけるｐ旧２．５を目途に当量添
加を行えばよい。Therefore, the economical (cooling energy) reaction temperature is 40~
It is in the range of 20°C, more preferably 35-25°C. In this way, impurities such as calcium can be efficiently adsorbed and coprecipitated into the viable sodium bicarbonate, sodium sesquicarbonate, or a mixture thereof. The crystals separated and the mother liquor contained NaHCO. Since Na2CO. is dissolved, Mail is added to decompose it and Na2CO.・HzO and concentrate it to precipitate sodium carbonate monohydrate. The amount of NaOH added is required to be equivalent to NaHC03, but if it is more than this, NaOH will migrate into NazCOi H ttZo, and if it is less, it will remain undecomposed, both of which will lead to a decrease in the purity of the soda carbonate product. The goal for these equivalent additions is usually pn
For example, an equivalent amount may be added to aim for a p value of 2.5 at 30°C.
なお、添加するＮａＯＨ濃度はＮａＣＯ３・ＨｚＯ晶出
工程での濃縮負荷を考慮すると、高純度ほど望ましいが
実用上は３５〜４８％程度の使用が推奨される。Note that, considering the concentration load in the NaCO3.HzO crystallization step, the concentration of NaOH to be added is preferably as high as possible, but it is recommended to use a concentration of about 35 to 48% in practice.
なお、苛性ソーダ溶液の使用量は、アンモニアソーダ法
あるいは塩安ソーダ法により得られる粗重曹と苛性ソー
ダ溶液との反応で炭酸ソーダ１水塩を得る方法（特開昭
６１−２９１４１２）に比べ、本システムでは重曹晶出
３０％のとき炭酸化率はたかだか５５％で、重曹分離後
の精製母液中の重曹濃度は約８重量％であり、炭酸ソー
ダ１トンを得るのに使用する苛性ソーダ溶液の量は少な
くてすむ。また、セスキ炭酸ソーダを晶出する場合はさ
らに苛性ソーダ溶液の使用量を低減できるのでより経済
的である。Note that the amount of caustic soda solution used in this system is smaller than that in the method of obtaining sodium carbonate monohydrate by the reaction of crude sodium bicarbonate obtained by the ammonia soda method or the ammonium chloride method with a caustic soda solution (Japanese Patent Application Laid-Open No. 61-291412). So, when the sodium bicarbonate crystallizes at 30%, the carbonation rate is at most 55%, and the concentration of sodium bicarbonate in the purified mother liquor after separating the sodium bicarbonate is about 8% by weight, and the amount of caustic soda solution used to obtain 1 ton of sodium carbonate is Less is needed. Further, when sesquicarbonate soda is crystallized, the amount of caustic soda solution used can be further reduced, which is more economical.
なお、本発明は炭酸化工程に供給する炭酸ソーダの濃度
を変更することにより重曹とセスキ炭酸ソーダを任意に
得ることができ、生威した重曹及びセスキ炭酸ソーダは
高純度を要求されない一般向製品として扱うため全く無
駄は生じない。In addition, in the present invention, baking soda and sodium sesquicarbonate can be obtained arbitrarily by changing the concentration of soda carbonate supplied to the carbonation process, and the raw baking soda and sodium sesquicarbonate can be used as products for general use that do not require high purity. Since it is treated as such, there is no waste at all.
以上の如く本発明は、苛性ソーダまたは精製塩水から高
純度炭酸ソーダを得る方法に比べ、経済面、設備面とも
に非常に有効な方法と云える。As described above, the present invention can be said to be a very effective method both economically and in terms of equipment, compared to methods for obtaining high purity soda carbonate from caustic soda or purified brine.
以下、本発明を実施例によって説明するがこれらによっ
て本発明が限定されるものではない。EXAMPLES The present invention will be explained below with reference to examples, but the present invention is not limited by these examples.
実施例１
塩安ソーダ法で製造した軽灰を用い、２０重量％Ｎａｚ
ＣＯ３溶液２ １ （Ｃａ０ １４．６ｐｐｍ）をつく
りこれに炭酸ガスを吹き込み３５℃、４時間で全Ｎａｚ
ＣＯ．，の約２９％の重曹を晶出させた。重曹を沈降分
離９
後の上澄液のＣａＯは１．５ｐｐｍであった。この上澄
液に、４８％ＮａＯＨ（４７１ｋｇ／ｔ ・ソーダ灰）
を添加したのち、減圧下（−５５０■／Ｈｇ、温度６８
℃）で濃縮して炭酸ソーダ、１水塩を析出、水洗分離後
、仮焼して無水炭酸ソーダを製造した。得られたＮａｇ
ＣＯｉ中のＣａＯ濃度は１０ｐｐｍであった。一方、炭
酸ソーダ分離母液はソーダ灰１水塩濃縮工程に循環使用
した。Example 1 Using light ash produced by ammonium chloride soda method, 20% by weight Naz
A CO3 solution 2 1 (Ca0 14.6 ppm) was prepared, carbon dioxide gas was blown into it, and total Naz was reduced in 4 hours at 35°C.
C.O. , about 29% of baking soda was crystallized. The CaO content of the supernatant after the baking soda was separated by sedimentation 9 was 1.5 ppm. Add 48% NaOH (471 kg/t・soda ash) to this supernatant liquid.
was added, then under reduced pressure (-550■/Hg, temperature 68
℃) to precipitate sodium carbonate and monohydrate, which were washed and separated with water and then calcined to produce anhydrous soda carbonate. Obtained Nag
The CaO concentration in COi was 10 ppm. On the other hand, the separated mother liquor of sodium carbonate was recycled and used in the soda ash monohydrate concentration process.
実施例２
実施例１と同一濃度のＮａ．ＣＯ．溶液で、但し、Ｃａ
Ｏ １３．４ｐｐｍのものをもちいてこれに炭酸ガスを
吹き込み２８℃、５時間で全ＮａｚＣＯ３の約１２％の
重曹を析出させ、重曹を沈降分離後の上澄液のＣａＯは
４． ０ｐｐｍであった。この上澄液に４８％ＮａＯＨ
（３７５ｋｇ／ｔ・ソーダ灰）を添加し以下実施例１と
同様に無水炭酸ソーダを製造した。Ｎａ．Ｃ０３中のＣ
ａＯ濃度は２０ｐｐｍであった。Example 2 The same concentration of Na. C.O. In solution, however, Ca
Using one containing 13.4 ppm of O, carbon dioxide gas was blown into it at 28°C for 5 hours to precipitate about 12% of the total NazCO3, and the CaO of the supernatant liquid after the baking soda was sedimented and separated was 4. It was 0 ppm. Add 48% NaOH to this supernatant.
(375 kg/t soda ash) was added to produce anhydrous soda carbonate in the same manner as in Example 1. Na. C in C03
The aO concentration was 20 ppm.
実施例３
実施例１と同一濃度のＮａ２ＣＯ３溶液で、但し、Ｃａ
０ １７．５ｐｐｍのものをもちいてこれに炭酸ガス１
〇一
を吹き込み２８℃、２時間で全ＮａｚＣＯ，，の約１５
％の重曹を析出させ、重曹を沈降分１１ｆ＆の上澄後の
ＣａＯはｓ．２ｐｐｍであった。実施例ｌ同様に無水炭
酸ソーダを製造した。Ｎａ２ＧＯ＝中のＣａＯ濃度は３
８ｐｐｍであった。Example 3 A Na2CO3 solution with the same concentration as in Example 1, except that Ca
0 Use 17.5 ppm and add 1 carbon dioxide gas to it.
About 15 of the total NazCO was blown in at 28℃ for 2 hours.
% of sodium bicarbonate is precipitated, and the CaO after the precipitated portion of 11f & supernatant is s. It was 2 ppm. Anhydrous soda carbonate was produced in the same manner as in Example 1. The concentration of CaO in Na2GO is 3
It was 8 ppm.
比較例
実施例１と同一濃度（ＣａＯ １４．６ｐｐｍ）の炭酸
ソーダ溶液に炭酸ガスを吹き込み、炭酸化を完結して重
曹を析出、仮焼して得たＮａｚＣＯｉ中のＣａＯは５０
ｐｐｍであった。Comparative Example Carbon dioxide gas was blown into a sodium carbonate solution with the same concentration (CaO 14.6 ppm) as in Example 1 to complete carbonation and baking soda was precipitated.The CaO in NazCOi obtained by calcining was 50%.
It was ppm.
（発明の効果）
本発明によって製造された炭酸ソーダは、不純物特にカ
ルシウムの低減ができるため、カルシウムの存在を嫌う
例えば過炭酸ソーダの製造原料として極めて有用である
。(Effects of the Invention) Since the soda carbonate produced according to the present invention can reduce impurities, particularly calcium, it is extremely useful as a raw material for producing soda percarbonate, for example, which dislikes the presence of calcium.
Claims (1)
炭酸ソーダあるいはセスキ炭酸ソーダとして晶出させ、
これにカルシウム等の不純物を吸着共沈せしめて系外に
取出し、不純物除去後の精製母液に苛性ソーダ溶液を加
えたのち、濃縮して炭酸ソーダ１水塩を析出、母液と分
離し、該母液は炭酸ソーダ溶液として循環使用し、炭酸
ソーダ１水塩を仮焼することを特徴とする高純度炭酸ソ
ーダの製造法。 ２）重炭酸ソーダまたはセスキ炭酸ソーダの一部晶出量
が炭酸ソーダ溶液中の全Ｎａ＿２ＣＯ＿３の５〜５０重
量％である請求項１記載の高純度炭酸ソーダの製造法。 ３）炭酸化の反応温度が０〜３５℃の間で行う請求項１
記載の高純度炭酸ソーダの製造法。[Claims] 1) Carbonating a soda carbonate solution and crystallizing a portion of the soda carbonate as sodium bicarbonate or soda sesquicarbonate;
Impurities such as calcium are adsorbed and co-precipitated on this and taken out of the system, and a caustic soda solution is added to the purified mother liquor after removing the impurities, and then it is concentrated to precipitate sodium carbonate monohydrate, which is separated from the mother liquor. A method for producing high-purity soda carbonate, which is characterized by recycling sodium carbonate solution and calcining sodium carbonate monohydrate. 2) The method for producing high-purity soda carbonate according to claim 1, wherein the amount of partially crystallized sodium bicarbonate or sodium sesquicarbonate is 5 to 50% by weight of the total Na_2CO_3 in the sodium carbonate solution. 3) Claim 1 in which the carbonation reaction temperature is between 0 and 35°C.
The method for producing high purity soda carbonate as described.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14913989A JPH0621033B2 (en) | 1989-06-12 | 1989-06-12 | Manufacturing method of high-purity sodium carbonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14913989A JPH0621033B2 (en) | 1989-06-12 | 1989-06-12 | Manufacturing method of high-purity sodium carbonate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0316913A true JPH0316913A (en) | 1991-01-24 |
| JPH0621033B2 JPH0621033B2 (en) | 1994-03-23 |
Family
ID=15468610
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14913989A Expired - Lifetime JPH0621033B2 (en) | 1989-06-12 | 1989-06-12 | Manufacturing method of high-purity sodium carbonate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0621033B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08282029A (en) * | 1995-04-20 | 1996-10-29 | Nec Data Terminal Ltd | Paper cutting mechanism for printer |
| WO2001030698A1 (en) * | 1999-10-25 | 2001-05-03 | Airborne Industrial Minerals Inc. | Method for formulating food grade sodium bicarbonate |
| JP2007074838A (en) * | 2005-09-08 | 2007-03-22 | Oriental Motor Co Ltd | Structure and method for terminal processing for end of winding of stator in rotary electric machine |
| WO2007144973A1 (en) * | 2006-06-16 | 2007-12-21 | Tsurumi Soda Co., Ltd. | Method for purification of alkali metal carbonate solutions, purification apparatus and alkali metal carbonate solutions |
| JP2010269975A (en) * | 2009-05-22 | 2010-12-02 | Hitachi Zosen Corp | Sodium extraction apparatus |
| CN102476816A (en) * | 2010-11-24 | 2012-05-30 | 江苏省勤奋药业有限公司 | Production process of pharmaceutical-grade anhydrous sodium carbonate |
| CN115404110A (en) * | 2021-05-26 | 2022-11-29 | 中国石油化工股份有限公司 | Wellhead carbon dioxide recovery device |
| EP4276070A1 (en) * | 2022-05-04 | 2023-11-15 | Renforth, Phil | Method of producing a solid metal carbonate hydrate |
-
1989
- 1989-06-12 JP JP14913989A patent/JPH0621033B2/en not_active Expired - Lifetime
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08282029A (en) * | 1995-04-20 | 1996-10-29 | Nec Data Terminal Ltd | Paper cutting mechanism for printer |
| WO2001030698A1 (en) * | 1999-10-25 | 2001-05-03 | Airborne Industrial Minerals Inc. | Method for formulating food grade sodium bicarbonate |
| JP2007074838A (en) * | 2005-09-08 | 2007-03-22 | Oriental Motor Co Ltd | Structure and method for terminal processing for end of winding of stator in rotary electric machine |
| WO2007144973A1 (en) * | 2006-06-16 | 2007-12-21 | Tsurumi Soda Co., Ltd. | Method for purification of alkali metal carbonate solutions, purification apparatus and alkali metal carbonate solutions |
| JP2007331993A (en) * | 2006-06-16 | 2007-12-27 | Tsurumi Soda Co Ltd | Method for purifying alkali metal carbonate solution, purification apparatus, and alkali metal carbonate solution |
| JP2010269975A (en) * | 2009-05-22 | 2010-12-02 | Hitachi Zosen Corp | Sodium extraction apparatus |
| CN102476816A (en) * | 2010-11-24 | 2012-05-30 | 江苏省勤奋药业有限公司 | Production process of pharmaceutical-grade anhydrous sodium carbonate |
| CN115404110A (en) * | 2021-05-26 | 2022-11-29 | 中国石油化工股份有限公司 | Wellhead carbon dioxide recovery device |
| EP4276070A1 (en) * | 2022-05-04 | 2023-11-15 | Renforth, Phil | Method of producing a solid metal carbonate hydrate |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0621033B2 (en) | 1994-03-23 |
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