KR100240828B1 - The recovery method of high purified magnesium chloride from the waste liquid of manufacturing of tetra butyl tin - Google Patents

The recovery method of high purified magnesium chloride from the waste liquid of manufacturing of tetra butyl tin Download PDF

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KR100240828B1
KR100240828B1 KR1019970078781A KR19970078781A KR100240828B1 KR 100240828 B1 KR100240828 B1 KR 100240828B1 KR 1019970078781 A KR1019970078781 A KR 1019970078781A KR 19970078781 A KR19970078781 A KR 19970078781A KR 100240828 B1 KR100240828 B1 KR 100240828B1
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magnesium chloride
waste liquid
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KR19990058638A (en
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정백영
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윤호근
정백영
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F5/00—Compounds of magnesium
    • C01F5/26—Magnesium halides
    • C01F5/30—Chlorides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/40—Valorisation of by-products of wastewater, sewage or sludge processing

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Abstract

본 발명은 염화마그네슘을 함유하는 4부틸주석 제조공정에서 부생되는 공정폐액을 중화, 산화, 여과, 숙성, 여과, 농축, 환원 공정을 순차적으로 적용하여 폐액으로 부터 불필요한 성분을 여과, 제거시켜 주므로서 고순도의 액상 염화마그네슘을 회수하는 방법에 관한 것이다.The present invention is to neutralize, oxidize, filter, ripen, filter, concentrate, and reduce the by-products of the process waste liquid produced in the manufacturing process of 4-butyltin containing magnesium chloride, thereby filtering and removing unnecessary components from the waste liquid. The present invention relates to a method for recovering high purity liquid magnesium chloride.

상기 폐액은 용도가 없어 폐기처리하고 있는바 폐기처리 비용이 계속 증대되어 4부틸주석 제조공정의 조업자체를 위협하고 있는 실정에서 본 발명은 상기 공정폐액으로 부터 고순도의 염화마그네슘을 회수하므로서 자원의 활용도를 높여주고 공정부생 폐기물의 발생량을 획기적으로 줄여주는 이점을 제공한다.In the situation where the waste liquid is disposed of because there is no use, the disposal cost continues to increase, threatening the operator of the 4-butyltin manufacturing process, and the present invention recovers high-purity magnesium chloride from the process waste liquid. It offers the benefits of increasing the cost and significantly reducing the amount of process by-product waste.

Description

4부틸주석 제조공정 폐액으로부터 고순도 염화마그네슘을 회수하는 방법How to recover high-purity magnesium chloride from wastewater

본 발명은 염화부틸, 테트라하이드로퓨란, 금속마그네슘 및 사염화주석을 반응매체로 하여 사부틸주석을 제조하는 공정에서 부생되는 폐액으로 부터 고순도의 염화마그네슘을 회수하는 방법에 관한 것이다. 염화마그네슘은 두부제조시 단백질 응고제, 도로결빙 방지제, 내화물, 건축용 등으로 널리 이용되고 있다.The present invention relates to a method for recovering high-purity magnesium chloride from waste liquid by-produced in the process of producing sabutyl tin using butyl chloride, tetrahydrofuran, metal magnesium and tin tetrachloride as a reaction medium. Magnesium chloride is widely used as a protein coagulant, road freezing inhibitor, refractory material, and building materials.

일반적으로 사부틸주석(Tetra Butyl Tin : 이하 TBT라 한다)은 염화부틸(Butyl chloride)을 테트라하이드로퓨란(Tetra Hydro Furan : 이하 THF라 한다) 중에서 금속마그네슘과 그리나드반응(Grignard reaction)시켜 부틸염화마그네슘(Butyl Magnesium Chloride)을 얻고 이를 사염화주석(Tetrachloro Tin)과 반응시켜서 제조한다.In general, tetrabutyl tin (hereinafter referred to as TBT) is a butyl chloride solution obtained by butyl chloride using metal magnesium and Grignard reaction in tetrahydrofuran (hereinafter referred to as THF). Magnesium (Butyl Magnesium Chloride) is obtained and prepared by reacting it with Tetrachloro Tin.

극성용매인 THF는 반응공정 중에서 양이온과 음이온의 분리작용을 하는 성능이 뛰어나므로 이 반응의 반응용매로서 매우 적합한 것으로 알려져 있다.THF, a polar solvent, is known to be very suitable as a reaction solvent for this reaction because of its excellent ability to separate cations and anions in the reaction process.

상기 공정에서 TBT 회수후 하기 표 1에 기재되어 있는 바와 같은 폐액이 대량으로 부생되는데 이 폐액중에는 THF는 물론 상당량의 염화마그네슘이 함유되어 있다.After the recovery of TBT in the process, a large amount of by-products, as shown in Table 1, is produced, which contains not only THF but also a significant amount of magnesium chloride.

TBT 공정폐액의 조성Composition of TBT Fair Waste 항목Item 성분ingredient 성상 및 외관Appearance and appearance 황색, 나쁜냄새가 남Yellow, bad smell 비중(20℃)Specific gravity (20 ℃) 1.29∼1.301.29-1.30 pHpH 0.5∼2.00.5 to 2.0 MgCl2함량(wt%)MgCl 2 content (wt%) 20.0∼27.020.0 to 27.0 T.H.F 함량(wt%)T.H.F content (wt%) 0.75∼2.200.75 to 2.20 철분(ppm)Iron (ppm) 35.0∼75.035.0-75.0

상기의 공정폐수는 현행 환경관리법상 특정 폐기물로 분류되며 이와같은 공정폐수를 폐수처리업체에 의뢰하여 폐기시키거나 자체 폐수처리설비를 구비하여 폐기시키는데에는 상당한 비용이 발생되고 환경규제가 점차 강화됨에 따라 그 비용도 계속 증대되어 TBT의 생산원가를 크게 높이는 결과를 가져올 뿐 아니라 폐기물 처리에 따른 환경 파괴문제가 매우 심각한 실정에 있으며, 경우에 따라서는 폐액의 처리가 원만하게 되지 않아 공장가동을 중단하는 사태가 발생하기도 하고 있다.The above process wastewater is classified as a specific waste under the current environmental management law, and this process wastewater is disposed of by requesting a wastewater treatment company or equipped with its own wastewater treatment facility. As the cost continues to increase, the production cost of TBT is greatly increased, and the environmental destruction problem caused by waste disposal is very serious. Is also happening.

본 발명의 목적은 TBT 공정폐액으로부터 각종 공업용 원료로 이용될 수 있는 고순도의 염화마그네슘을 회수하여 자원의 활용도를 높이는데만 그치는 것이 아니라 공정부생 폐기물의 발생량을 획기적으로 줄여 공정폐기물의 처리를 용이하게 하여 주는데 있다.The purpose of the present invention is not only to increase the utilization of resources by recovering high-purity magnesium chloride that can be used as various industrial raw materials from TBT process wastes, but also to greatly reduce the amount of process by-product wastes, thereby facilitating the treatment of process wastes. It is to give.

본 발명은 현재의 폐액처리 비용의 10% 정도의 경비로 고순도 염화마그네슘을 얻을 수 있고 또한 폐액의 재활용으로 폐수처리비용을 절감시킬 수 있는 이점을 갖는다.The present invention can obtain high purity magnesium chloride at a cost of about 10% of the current waste liquid treatment cost, and also has the advantage of reducing the waste water treatment cost by recycling the waste liquid.

본 발명은 4부틸주석 체조공정에서 부생되며 염화마그네슘을 다량함유하고 있는 공정부생폐액에 중화, 산화, 여과, 숙성, 여과, 농축, 환원공정을 순차적으로 적용하여 상기폐액중의 염화마그네슘을 제외한 불순물을 분리 제거하여 상기폐액으로부터 고순도의 염화마그네슘을 회수하므로서, 폐수처리 비용도 대폭 절감시키면서 폐기되는 염화마그네슘을 재활용할수있게 하는데 그 목적이 있다.The present invention is a by-product in the 4-butyltin gymnastic process, and by applying the neutralization, oxidation, filtration, ripening, filtration, concentration, reduction process sequentially to the process by-product waste containing a large amount of magnesium chloride impurities other than magnesium chloride in the waste solution By separating and removing the high-purity magnesium chloride from the waste liquid, the purpose is to allow the recycled magnesium chloride to be recycled while significantly reducing the waste water treatment cost.

일반적인 TBT 제조공정을 반응식으로 설명하면 다음과 같다.The general TBT manufacturing process will be described as follows.

Figure kpo00000
Figure kpo00000

상기의 TBT와 염화마그네슘의 혼합물을 물로 수세후 TBT를 분리 회수하면 다량의 염화마그네슘을 함유하고 있는 표 1에 기재된 공정폐액이 부생(副生)되게 된다.When the mixture of TBT and magnesium chloride is washed with water and the TBT is separated and recovered, the process waste liquid shown in Table 1 containing a large amount of magnesium chloride is by-product.

상기 표 1에 기재된 성상의 공정폐액 1000ℓ를 반응기에 넣고 60RPM으로 교반시켜주면서 45∼55℃ 정도로 가온시킨다. 상기 폐액은 염소를 함유하는 산성용액이므로 여기에 탄산나트륨 3.5kg, 가성소다 1.0kg을 넣고 2∼3시간 중화시킨 다음 과산화수소(H2O2) 0.5Kg과 과망간산칼륨(KMnO4) 2.0kg을 넣어 불순물로 함유되어 있는 철분을 산화시킨다.1000 L of the process waste solution of the above-mentioned table 1 is put in a reactor and heated to about 45-55 ° C. while stirring at 60 RPM. Since the waste liquid is an acid solution containing chlorine was put 3.5kg sodium carbonate, sodium hydroxide 1.0kg here 2-3 hours, and then neutralizing the hydrogen peroxide (H 2 O 2) 0.5Kg and potassium permanganate (KMnO 4) Put 2.0kg impurities Oxidize iron content.

상기와 같이 처리한 공정폐액을 200메쉬(mesh) 정도의 여과포로 여과, 산화철 등의 금속산화물의 스럿지(Sludge)를 제거하고 여액을 숙성조로 이송시킨다. 숙성조에서 40∼50RPM으로 교반시키면서 제오라이트 1.5kg과 활성탄 2.0kg을 투입하고 50∼60℃로 승온시켜서 약 2시간 정도 숙성시킨다. 숙성이 끝나면 수산 1kg과 구연산 1.5kg을 투입하여 약 1시간 교반하고 200메쉬 여과포로 잔류 스럿지를 여과한 후 여액을 농축조로 이송후 농축조에서 80∼85℃로 8∼10시간 농축하여 250메쉬가 장착된 휠터프레스로 여과스럿지를 여과, 제거하면 다음표에 기재된 액상 염화마그네슘을 얻는다. 이상 설명한 바와 같이 본 발명의 기술적 골간(骨幹)은 염화마그네슘을 함유하는 4부틸주석 제조공정 폐액을 중화, 산화, 여과, 숙성, 여과, 농축, 환원 공정을 순차적으로 적용하여 상기 폐액으로 부터 불필요한 성분을 스럿지로 여과 제거시켜 주므로서 고순도의 염화마그네슘을 회수하는 방법을 제공하는데 있다.The process waste solution treated as described above is filtered through a 200 mesh (mesh) filter cloth to remove sludge of metal oxides such as iron oxide, and the filtrate is transferred to a aging tank. While stirring at 40 to 50 RPM in a aging tank, 1.5 kg of zeolite and 2.0 kg of activated carbon are added thereto, and the temperature is raised to 50 to 60 ° C. and aged for about 2 hours. After maturation, 1kg of fish and 1.5kg of citric acid were added, stirred for about 1 hour, the remaining sludge was filtered through a 200 mesh filter cloth, and the filtrate was transferred to a concentration tank, and then concentrated in a concentration tank for 8 to 10 hours at a concentration of 250 mesh. Filtration and removal of the filter sludge with a filtered filter press yields liquid magnesium chloride as shown in the following table. As described above, in the technical bone stem of the present invention, the wastewater of the 4-butyltin manufacturing process containing magnesium chloride is neutralized, oxidized, filtered, aged, filtered, concentrated, and reduced in order to apply unnecessary components from the wastewater. It is to provide a method for recovering high purity magnesium chloride by filtering off the sludge.

항 목Item 성 분ingredient 성상 및 외관Appearance and appearance 무색, 무취의 투명한 액체Colorless, odorless transparent liquid 비중(20℃)Specific gravity (20 ℃) 1.30∼1.311.30-1.31 pHpH 6.5∼8.26.5-8.2 MgCl2(wt%)MgCl 2 (wt%) 30∼3130-31 철분(PPM)Iron (PPM) 3.5이하3.5 or less T.H.F(wt%)T.H.F (wt%) 0.1이하0.1 or less

이렇게 하여서 얻어진 액상의 염화마그네슘은 공업용 원료로 직접 사용될 수 있다.The liquid magnesium chloride thus obtained can be used directly as an industrial raw material.

본 발명의 고순도 염화마그네슘 용액의 회수방법에서 사용되는 탄산나트륨과 가성소다는 공정폐액중의 유리염소분을 중화시켜주며 탈취시켜 주는 역활을 하므로 0.35∼0.50 중량%, 가성소다 0.1∼0.15 중량%를 사용하는 것이 좋다. 가성소다와 탄산나트를 혼용하는 것은 pH 조정이 용이하기 때문이다. 과망간산칼륨은 용액속에 남아있는 철성분을 산화시켜주므로 0.2∼0.5 중량%를 사용하는 것이 매우 바람직하다.Sodium carbonate and caustic soda used in the high purity magnesium chloride solution of the present invention neutralize the free chlorine in the process waste and act as a deodorizing agent so that 0.35 to 0.50 wt% and caustic soda 0.1 to 0.15 wt% are used. Good to do. Mixing caustic soda and sodium carbonate is easy to adjust the pH. Since potassium permanganate oxidizes the iron component remaining in the solution, it is highly preferable to use 0.2 to 0.5% by weight.

과산화수소는 강력한 산화제 역활을 하는 것과 동시에 탈색, 탈취에 효능이 있으므로 0.01∼0.07 중량%를 사용하는 것이 적당하다.Since hydrogen peroxide is a powerful oxidant and is effective in discoloration and deodorization, it is appropriate to use 0.01 to 0.07% by weight.

다공성의 활성탄은 공정물 속의 고유 냄새인 T.H.F의 냄새를 흡취 및 탈취하는데 큰 역할을 하게되며 스럿지 여과시 여과성을 높여주므로 0.2∼0.5중량%를 사용하는 것이 좋으며 제오라이트는 활성탄과 비슷한 역할을 하지만 T.H.F 제거에 가장 효과가 높다. 이는 유기물을 흡수 제거하여 냄새 및 색도 제거에 가장 적합하므로 0.35∼0.50 중량%를 사용하는 것이 적당하며 수산(Oxalic Acid)은 강력한 환원제로써 잉여의 과망간산칼륨 등 잔여 산화물을 환원시켜준다. 본 공정에서 환원제로 수산을 사용하는 것이 바람직하여 1.0∼1.5중량%를 사용하는 것이 좋다.Porous activated carbon plays a big role in absorbing and deodorizing the odor of THF, which is an intrinsic odor in the process, and it is recommended to use 0.2 to 0.5% by weight since it improves filtration during sludge filtration. Most effective for removal. Since it is most suitable for removing odor and color by absorbing and removing organic substances, it is appropriate to use 0.35 to 0.50 wt%, and oxalic acid is a powerful reducing agent to reduce residual oxides such as excess potassium permanganate. In this step, it is preferable to use hydroxyl as the reducing agent, and it is preferable to use 1.0 to 1.5% by weight.

구연산나트륨은 안정제로서의 효능이 탁월하고 열 안정제로써의 특성을 가졌으므로 공정중 0.20∼0.30중량%를 사용하는 것이 바람직하다.Since sodium citrate has excellent efficacy as a stabilizer and has a property as a heat stabilizer, it is preferable to use 0.20 to 0.30 wt% in the process.

본 발명의 염화마그네슘 회수 방법에 있어서 추가로 소석회를 병행해서 사용하는 방법도 있다. 이때 사용범위는 탄산나트륨과 같은 용도로 처리되지만 사용량에 있어서는 0.1 중량%를 넘어설 수 없다. 염화마그네슘의 품질규격상 칼슘의 성분이 0.5%를 초과할 수 없다.In the magnesium chloride recovery method of the present invention, there is also a method of using slaked lime in parallel. At this time, the use range is treated for the same purpose as sodium carbonate, but the amount can not exceed 0.1% by weight. Due to the quality specification of magnesium chloride, the content of calcium cannot exceed 0.5%.

본 발명의 방법으로 처리된 공정폐액의 조성Composition of process wastewater treated by the method of the present invention 항 목Item 처리전Before treatment 처리후After treatment 외관 및 성상Appearance and appearance 악취, 황색Odor, yellow 무색, 무취Colorless, odorless 비중(20℃)Specific gravity (20 ℃) 1.29∼1.301.29-1.30 1.30∼1.311.30-1.31 pHpH 0.5∼2.00.5 to 2.0 6.5∼8.26.5-8.2 MgCl2(%)MgCl 2 (%) 20.0∼27.020.0 to 27.0 30∼3130-31 T.H.F(%)T.H.F (%) 0.75∼2.200.75 to 2.20 0.1이하0.1 or less 철분(ppm)Iron (ppm) 35.0∼75.035.0-75.0 3.5이하3.5 or less

종래 콩류의 단백질을 응고시키는데 사용되는 염화마그네슘은 금속마그네슘을 염산에 용해하여 제조하는 방법과 고즙을 응축 정제하여 식용으로 사용가능한 고순도의 염화마그네슘을 얻는 방법이 있으나 전자는 경제적인 면에서 고가이고 후자는 식용으로 적합하여야 하는 기술적인 면에서 불순물의 제거가 한계에 도달한 실정이다. 상기 방법들에서 부생되는 폐수의 처리는 환경회손을 유발시킬 뿐 아니라 폐수로 처리하게 되면 소요경비의 부담으로 실효성있는 운영이 어려울 수 밖에 없다.Magnesium chloride, which is used to coagulate soy protein, is prepared by dissolving metal magnesium in hydrochloric acid, and condensing and purifying the juice to obtain high purity magnesium chloride for food use, but the former is expensive and the latter is economical. In the technical aspect that must be suitable for edible removal of impurities has reached the limit. The treatment of wastewater by-produced in the above methods not only causes environmental damage, but when treated with wastewater, effective operation is difficult due to the burden of necessary expenses.

본 발명은 공정에서 부생되는 공정폐액을 재활용하므로서 그간 고체염화마그네슘을 액화시켜 사용하는데 따르는 부대경비를 대폭 경감시킬 수 있다. 본 발명품은 액체제품이므로 별도로 용해 액화시킬 필요없이 액상 그대로 사용할 수 있어 사용자에게도 사용상 편리한 이점을 제공하게 된다.The present invention can greatly reduce the side costs associated with liquefying the solid magnesium chloride while using the process waste liquid by-produced in the process. Since the present invention is a liquid product, it can be used as it is without the need to separately dissolve and liquefy, thus providing a user-friendly advantage.

Claims (3)

염화마그네슘을 함유하는 4부틸주석 제조공정 폐액을 중화, 산화, 여과, 숙성, 여과, 농축, 환원 공정을 순차적으로 적용하여 염화마그네슘을 함유하는 4부틸주석 제조공정 폐액으로 부터 고순도의 염화마그네슘을 회수하는 방법.High-purity magnesium chloride is recovered from the 4-butyltin-tin wastewater containing magnesium chloride by sequentially applying neutralization, oxidation, filtration, aging, filtration, concentration, and reduction processes. How to. 제 1항에 있어서, 중화공정에서 중화제로서 탄산나트륨 및 가성소다를 사용하고 산화공정에서 산화제로서 과망간산칼륨 및 과산화수소를 사용하고, 숙성공정에서 제오라이트 및 활성탄을 투입 숙성시키고 농축공정에서 80∼85℃에서 8∼10시간 농축시키고, 환원 공정에서 수산을 환원제로 사용하여 고순도의 염화마그네슘을 회수하는 방법.The method of claim 1, wherein sodium carbonate and caustic soda are used as neutralizing agents in the neutralization process, potassium permanganate and hydrogen peroxide as oxidizing agents are used in the oxidation process, zeolite and activated carbon are added to the aging process, and aged at 80 to 85 ° C in the concentration process. A method of concentrating for 10 hours and recovering high purity magnesium chloride using hydroxyl as a reducing agent in a reduction step. 제 2항에 있어서, 4부틸주석 폐액을 기준으로 하여 0.35∼0.5 중량%의 탄산나트륨, 0.1∼0.15 중량%의 가성소다, 0.2∼0.5중량%의 과망간산칼륨, 0.01∼0.07중량%의 과산화수소, 0.2∼0.5 중량%의 제오라이트 또는 활성탄, 0.1∼0.15중량%의 수산을 첨가하여 고순도의 염화마그네슘을 회수하는 방법.The method according to claim 2, wherein 0.35 to 0.5% by weight sodium carbonate, 0.1 to 0.15% by weight caustic soda, 0.2 to 0.5% by weight potassium permanganate, 0.01 to 0.07% by weight hydrogen peroxide, 0.2 to 0 A method for recovering high purity magnesium chloride by adding 0.5 wt% zeolite or activated carbon and 0.1 to 0.15 wt% hydroxyl.
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