WO2017174012A1 - Molten-salt chlorinated-slag resource processing method - Google Patents

Molten-salt chlorinated-slag resource processing method Download PDF

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WO2017174012A1
WO2017174012A1 PCT/CN2017/079629 CN2017079629W WO2017174012A1 WO 2017174012 A1 WO2017174012 A1 WO 2017174012A1 CN 2017079629 W CN2017079629 W CN 2017079629W WO 2017174012 A1 WO2017174012 A1 WO 2017174012A1
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slag
molten salt
molten
chlorinated
salt
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PCT/CN2017/079629
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French (fr)
Chinese (zh)
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刘昌林
侯盛东
阳露波
张景垒
夏建辉
郑少华
成勇
査笑乐
黄子良
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攀钢集团攀枝花钢铁研究院有限公司
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Priority to UAA201809977A priority Critical patent/UA123164C2/en
Priority to RU2018136341A priority patent/RU2709915C1/en
Publication of WO2017174012A1 publication Critical patent/WO2017174012A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/02—Halides of titanium
    • C01G23/022—Titanium tetrachloride
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
    • C22B34/1204—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 preliminary treatment of ores or scrap to eliminate non- titanium constituents, e.g. iron, without attacking the titanium constituent
    • C22B34/1213—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 preliminary treatment of ores or scrap to eliminate non- titanium constituents, e.g. iron, without attacking the titanium constituent by wet processes, e.g. using leaching methods or flotation techniques
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B60/00—Obtaining metals of atomic number 87 or higher, i.e. radioactive metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • Embodiments of the present invention relate to the technical field of titanium tetrachloride production and the field of environmental protection technologies. More specifically, embodiments of the present invention relate to a method for recycling molten salt chlorinated slag, which is a chlorination of titanium slag to produce tetrachlorochloride.
  • a low-cost, resource-recycling process for molten salt chlorination slag produced during the process of titanium production provides a technical solution for the cleaning of the titanium tetrachloride process by the molten salt chlorination process.
  • Molten salt chlorination and boiling chlorination are the two major production methods of titanium tetrachloride.
  • the titanium tetrachloride produced by molten salt chlorination accounts for 40% of the annual global production of titanium tetrachloride.
  • Boiling chlorination has high quality requirements for titanium slag raw materials (Ca+Mg ⁇ 1.0%), and the pollution is small, while molten salt chlorination has low requirements on raw materials (also suitable for titanium slag raw materials with high calcium and magnesium), but the pollution is heavy and the production process is in progress.
  • There are no economical and effective treatment technologies for pollutants such as molten salt chlorinated slag discharged at home and abroad.
  • CN101343070A introduces crushing, leaching and filtering of molten salt chlorinated slag , filter cake landfill, filter cake treated with NaOH to prepare ionic membrane caustic soda raw material - NaCl solution, filter cake landfill method
  • Cao Dali et al CN103011203B introduced the molten salt chloride slag crushed, leached and filtered, filtered The cake is landfilled, and the filtrate is precipitated with alkali (NaOH, Ca(OH) 2 , EDTA, reducing agent powder) to remove iron, manganese and Cr ions.
  • the sediment is purified as smelting ferromanganese raw material, and the supernatant is precipitated with NaOH to remove Ca and Mg.
  • NaCl brine the solution containing calcium and magnesium slag through CO 2 treatment to obtain the flame retardant Mg(OH) 2 by using ammonia water
  • Panzhihua Iron and Steel Research Institute proposed to dissolve the molten salt chloride residue and recrystallize to obtain regenerative melting Method for producing rutile titanium dioxide by salt chlorination slag
  • Guizhou Magnesium Design and Research Institute has developed a method for grinding molten salt chlorinated slag, grinding with slag, calcining under air and steam, preparing hydrochloric acid and calcined material, and calcining the crushed alkali. .
  • the first three methods the material consumption is high, the processing cost is high, so far there has been no report of pilot and industrial application, the fourth has not been reported in the pilot and industrial application, and the sinter alkali prepared by the fifth method
  • the metal content is high and difficult to use, and has not been promoted and applied in the industry.
  • the invention overcomes the deficiencies of the prior art, and provides a method for recycling molten salt chlorinated slag, which is expected to solve the problem of large material consumption, high cost and difficult industrial application when the titanium slag molten salt chlorinated slag is treated.
  • an embodiment of the present invention adopts the following technical solutions:
  • a method for recycling molten salt chlorinated slag which is a leaching solution for treating molten salt chlorinated slag by using strong oxidizing, alkaline waste brine or chlor-alkali chemical tail gas absorption waste liquid produced by titanium slag molten salt chlorination tail gas purification
  • strong oxidizing, alkaline waste brine or chlor-alkali chemical tail gas absorption waste liquid produced by titanium slag molten salt chlorination tail gas purification In order to recover NaCl, crystalline magnesium chloride and iron-manganese slag, low-cost resource treatment of molten salt chlorinated slag is realized.
  • the exhaust gas absorption waste liquid is alkaline.
  • the method for recycling a molten salt chlorination slag specifically includes the following steps:
  • the leaching residue is washed with water until the salt content is less than 1.0%, that is, the final slag.
  • the final slag meets the general solid waste discharge standards.
  • the washing water produced by the washing is recycled back to the molten salt chlorinated slag or the waste molten salt to be immersed.
  • the main component of the iron-manganese slag is washed with water to be iron or manganese hydroxide or carbonate, the Cl content is ⁇ 0.5%, and the Mn is tetravalent, which is used as a metallurgical raw material.
  • the condensed water produced by the stepwise crystallization is reused as the wash water of the oxidized filter cake and the leaching residue.
  • the NaCl obtained by the resource treatment of the present invention is dried and used for smelting of molten salt, and the crystalline magnesium chloride is sold as a raw material for chemical raw materials or deep processing.
  • the invention does not add alkali, adopts the alkaline waste brine produced by the purification of the tail gas of the molten salt chlorination furnace or the chlor-alkali chemical tail gas absorption waste liquid to oxidize and precipitate the Fe, Mn, Ca plasma in the mixed brine prepared by the molten salt chlorinated slag.
  • Strong oxidizing substances NaClO, NaClO 3
  • alkaline waste brine or chlor-alkali chemical tail gas absorption waste liquid oxidize ferrous iron into ferric iron, divalent manganese is oxidized to tetravalent, and completely precipitates at a lower pH.
  • MgCl 2 is retained in the solution to obtain a mixed solution of magnesium chloride and NaCl, and the mixed solution is subjected to fractional crystallization to obtain NaCl and crystalline magnesium chloride, and the NaCl is recycled for molten salt chlorination, crystalline magnesium chloride for export or as anhydrous magnesium chloride. raw material.
  • the leaching residue is washed and desalted and then landfilled, and the iron-manganese slag is desalted and purified as a metallurgical raw material.
  • the invention adopts waste treatment and waste, has simple process and low treatment cost.
  • the invention Compared with the prior art, the invention has the beneficial effects that the present invention utilizes the waste liquid chlorinated tail gas purification or the waste liquid generated in the chlor-alkali chemical exhaust gas purification process to treat the molten salt chlorinated slag leaching solution, thereby eliminating waste treatment, thereby not only solving the problem.
  • the problem of contamination of molten salt chlorinated slag, recycling of NaCl, MgCl 2 and iron-manganese raw materials in molten salt slag has good economic benefits, and has the bottleneck significance of eliminating the application of TiCl 4 in the smelting of titanium slag molten salt. It is widely used in the domestic and international molten salt chlorination-magnesium thermal electrolytic sponge titanium enterprises and molten salt chlorinated sponge titanium enterprises, and has broad prospects for promotion.
  • FIG. 1 is a block diagram showing the flow of a method for recycling molten salt chlorinated slag according to the present invention.
  • the molten salt chlorination slag resource treatment method of the present invention is as shown in Fig. 1.
  • the molten salt chlorinated slag is leached and filtered to obtain a leaching solution and a leaching residue, and the leaching solution is purified by molten salt chlorination tail gas or chlor-alkali chemical exhaust gas purification.
  • the waste liquid generated in the process is treated to obtain qualified brine and oxidized filter cake, and the qualified brine is crystallized stepwise to obtain sodium chloride and crystalline magnesium chloride, and the oxidized filter cake is washed to obtain iron-manganese slag.
  • the molten salt slag is leached and the residue obtained by filtration is washed to obtain a final slag.
  • the final slag is a general solid waste and is transported to the yard for landfill.
  • composition of the molten salt chlorinated slag crushing material to be resourced in this embodiment is shown in Table 1.
  • the molten salt chlorinated slag is leached to obtain a slurry, which is then filtered to obtain a leaching solution and a leaching residue.
  • the results of water quality analysis of the leachate are shown in Table 2.
  • the leaching residue is washed with water until the salt content is less than 1.0%, and the liquid-solid ratio at the time of washing is about 3.0:1. After the washing is completed, the final slag is obtained, and the final slag is landfilled.
  • the final slag composition analysis results are shown in Table 3.
  • the strong oxidizing and alkaline waste brine containing NaCl, NaClO, Na 2 CO 3 produced by purifying the leachate and molten salt chlorination tail gas are mixed according to a volume ratio of 1:0.76, and after fully reacting, no bubbles are generated and precipitated. Clarification, the slurry was about 45% of the volume of the brine, filtered to give an oxidized cake and a clear, clear, qualified brine.
  • the water quality analysis results of the waste brine are shown in Table 4.
  • the water quality analysis of qualified brine is shown in Table 5.
  • the oxidation cake was washed with water twice the volume of the slurry to a Cl content of ⁇ 0.5% to obtain iron-manganese slag, the dry components of which are shown in Table 6, and the iron-manganese slag was used as a metallurgical raw material.
  • the iron-manganese slag was calcined at 600 ° C for 2 h, and the burned loss was about 44%.
  • the calcined material had a TFE of 48.2% and a Mn of 7.64%.
  • the qualified brine was crystallized in portions to prepare NaCl and MgCl 2 ⁇ 6H 2 O.
  • the purity of the crude NaCl salt obtained by stepwise crystallization of qualified brine is about 96.8%, the purity of the refined salt is about 98.4%, and the yield is about 97.8%.
  • the yield of crystalline magnesium chloride is about 64.8%, and the MgCl 2 content is about 46.1%, which is in line with the white industrial magnesium chloride quality standard.
  • the washing water produced by the washing is recycled to the molten salt slag or the waste molten salt, and the condensed water produced by the stepwise crystallization is reused as the washing water for the oxidizing cake and the leaching residue.
  • the specific method for the resource treatment of the molten salt chlorinated slag of the present embodiment is basically the same as that of the first embodiment, but the leaching solution is oxidized by the chlor-alkali plant waste liquid shown in Table 10, and the waste liquid dosing ratio is 0.87 times the volume of the leachate.
  • composition of the molten salt chlorinated slag crushing material to be resourced in this embodiment is shown in Table 7.
  • the leachate was oxidized with the chlor-alkali plant waste liquid, and the water quality analysis results of the waste liquid are shown in Table 10. Mix well, wait until no bubbles are generated and precipitate to clarify. The slurry is about 40% of the volume of the brine. Filtered to obtain clear and transparent qualified brine, the water quality analysis is shown in Table 11.
  • the iron-manganese slag was calcined at 600 ° C for 2 h, and the burned loss was about 28%.
  • the calcined material had a TFE of 54.6% and a Mn of 10.77%.
  • the qualified brine is crystallized step by step, and the purity of the crude salt of NaCl is about 95.42%, the purity of the refined salt is about 98.0%, and the yield is about 97.5%.
  • the yield of crystalline magnesium chloride is about 95.8%, and the content of MgCl 2 is about 45.5%, which is in line with the quality standard of ordinary industrial magnesium chloride.

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Abstract

Provided is a salt chlorinated-slag resource processing method; in said method, the strong oxidizing or alkaline waste brine or chlor-alkali chemical tail-gas absorption waste liquid produced by purifying molten-salt chlorinated tail gas is used to process molten-salt chlorinated-slag leachate, thus recovering NaCl, crystallized magnesium chloride, and ferromanganese slag and performing low-cost resource processing of molten-salt chlorinated slag. The method uses waste to process waste, not only solving the problem of pollution by molten-salt chlorinated slag, but also recycling NaCl, MgCL2, and ferromanganese raw materials from molten-salt slag; it has good economic benefit and is of significant interest in eliminating the bottleneck in the development of techniques for preparing TiCl4 by titanium slag molten-salt chlorination; it is widely applicable in China and abroad among companies producing molten-salt chlorination and magnesium electrolytic titanium sponges and companies producing molten-salt chlorination titanium sponges, and has broad prospects for widespread use.

Description

熔盐氯化渣资源化处理方法Molten salt chlorination residue resource treatment method 技术领域Technical field
本发明的实施方式涉及四氯化钛生产技术领域及环保技术领域，更具体地，本发明的实施方式涉及一种熔盐氯化渣资源化处理方法，是钛渣熔盐氯化生产四氯化钛过程中产生的熔盐氯化渣低成本、资源化处理的一种工艺，为熔盐氯化法生产四氯化钛工艺的清洁化提供了一种技术方案。Embodiments of the present invention relate to the technical field of titanium tetrachloride production and the field of environmental protection technologies. More specifically, embodiments of the present invention relate to a method for recycling molten salt chlorinated slag, which is a chlorination of titanium slag to produce tetrachlorochloride. A low-cost, resource-recycling process for molten salt chlorination slag produced during the process of titanium production provides a technical solution for the cleaning of the titanium tetrachloride process by the molten salt chlorination process.
背景技术Background technique
熔盐氯化、沸腾氯化是四氯化钛的两大生产方法，熔盐氯化所生产的四氯化钛占全球四氯化钛年产量的40％。沸腾氯化对钛渣原料质量要求高(Ca+Mg＜1.0％)，污染小，而熔盐氯化对原料要求低(也适合钙镁高的钛渣原料)，但污染重，生产过程中所排放的熔盐氯化渣等污染物国内外尚无经济有效的处理技术，均以石灰拌和后荒原堆置(国外)或专业渣场填埋(国内)的方式处理，环境危害大，资源浪费严重，已成为熔盐氯化法应用发展的限制瓶颈。Molten salt chlorination and boiling chlorination are the two major production methods of titanium tetrachloride. The titanium tetrachloride produced by molten salt chlorination accounts for 40% of the annual global production of titanium tetrachloride. Boiling chlorination has high quality requirements for titanium slag raw materials (Ca+Mg<1.0%), and the pollution is small, while molten salt chlorination has low requirements on raw materials (also suitable for titanium slag raw materials with high calcium and magnesium), but the pollution is heavy and the production process is in progress. There are no economical and effective treatment technologies for pollutants such as molten salt chlorinated slag discharged at home and abroad. They are treated by lime mud mixing and wasteland stacking (foreign) or professional slag yard landfill (domestic), which has great environmental hazards and resources. Serious waste has become a limiting bottleneck in the development of the application of molten salt chlorination.
王祥等开展了熔盐渣破碎、溶浸、过滤、滤液碱化沉淀高价金属离子、粗盐水纳滤净化制取离子膜烧碱用盐水的技术研究；CN101381091A介绍了将熔盐氯化渣破碎、溶浸后过滤，滤饼填埋，滤液用石灰乳、Na2CO3处理制取NaCl并回用、滤饼填埋的处理工艺；CN101343070A介绍了将熔盐氯化渣破碎、溶浸后过滤，滤饼填埋，滤饼用NaOH处理制取离子膜烧碱原料—NaCl溶液、滤饼填埋的方法；曹大力等(CN103011203B)介绍了将熔盐氯化渣破碎、溶浸后过滤，滤饼填埋，滤液用碱(NaOH、Ca(OH)2、EDTA、还原剂保险粉)沉淀去除铁、锰、Cr离子，沉渣净化作为冶炼锰铁原料，清液用NaOH沉淀去除Ca、Mg制取NaCl盐水，含钙镁渣通CO2处理后的滤液用氨水制取阻燃剂Mg(OH)2的方法；攀钢研究院提出了将熔盐氯化渣溶解后重结晶制取再生熔盐氯化渣用于生产金红石型二氧化钛的方法；贵州铝镁设计研究院则开发了将熔盐氯化渣破磨后与收尘渣制浆、在空气与水蒸汽的条件下煅烧、制取盐酸和煅烧料、煅烧料破碎碱中和后利用的方法。Wang Xiang et al. carried out technical research on molten salt slag crushing, leaching, filtration, alkalization of filtrate to precipitate high-valent metal ions, and crude brine nanofiltration to obtain brine for ionic membrane caustic soda; CN101381091A introduced the crushing of molten salt chlorinated slag. After leaching and leaching, the filter cake is filled, the filtrate is treated with lime milk and Na 2 CO 3 to prepare NaCl and reused, and the filter cake is buried; CN101343070A introduces crushing, leaching and filtering of molten salt chlorinated slag , filter cake landfill, filter cake treated with NaOH to prepare ionic membrane caustic soda raw material - NaCl solution, filter cake landfill method; Cao Dali et al (CN103011203B) introduced the molten salt chloride slag crushed, leached and filtered, filtered The cake is landfilled, and the filtrate is precipitated with alkali (NaOH, Ca(OH) 2 , EDTA, reducing agent powder) to remove iron, manganese and Cr ions. The sediment is purified as smelting ferromanganese raw material, and the supernatant is precipitated with NaOH to remove Ca and Mg. Taking NaCl brine, the solution containing calcium and magnesium slag through CO 2 treatment to obtain the flame retardant Mg(OH) 2 by using ammonia water; Panzhihua Iron and Steel Research Institute proposed to dissolve the molten salt chloride residue and recrystallize to obtain regenerative melting Method for producing rutile titanium dioxide by salt chlorination slag; Guizhou Magnesium Design and Research Institute has developed a method for grinding molten salt chlorinated slag, grinding with slag, calcining under air and steam, preparing hydrochloric acid and calcined material, and calcining the crushed alkali. .
前三种方法，物料消耗大，处理成本高昂，迄今未有中试和产业化应用的报道，第四种未见中试和产业化应用的报道，第五种方法所制取的烧结料碱金属含量高，难以利用，迄今未在行业内推广应用。The first three methods, the material consumption is high, the processing cost is high, so far there has been no report of pilot and industrial application, the fourth has not been reported in the pilot and industrial application, and the sinter alkali prepared by the fifth method The metal content is high and difficult to use, and has not been promoted and applied in the industry.
随着环保要求的不断提高，熔盐氯化渣经济有效处理技术的开发日显重要和迫切。 本发明在此背景下产生。With the continuous improvement of environmental protection requirements, the development of cost-effective treatment technology for molten salt chlorinated slag is becoming more and more important. The invention is produced in this context.
发明内容Summary of the invention
本发明克服了现有技术的不足，提供一种熔盐氯化渣资源化处理方法，以期望可以解决钛渣熔盐氯化渣处理时物料消耗大、成本高、难以产业化应用的问题。The invention overcomes the deficiencies of the prior art, and provides a method for recycling molten salt chlorinated slag, which is expected to solve the problem of large material consumption, high cost and difficult industrial application when the titanium slag molten salt chlorinated slag is treated.
为解决上述的技术问题，本发明的一种实施方式采用以下技术方案：In order to solve the above technical problem, an embodiment of the present invention adopts the following technical solutions:
一种熔盐氯化渣资源化处理方法，它是利用钛渣熔盐氯化尾气净化所产生的强氧化性、碱性废盐水或氯碱化工尾气吸收废液来处理熔盐氯化渣的浸出液，从而回收NaCl、结晶氯化镁、铁锰渣，实现熔盐氯化渣低成本资源化处理。该尾气吸收废液呈碱性。A method for recycling molten salt chlorinated slag, which is a leaching solution for treating molten salt chlorinated slag by using strong oxidizing, alkaline waste brine or chlor-alkali chemical tail gas absorption waste liquid produced by titanium slag molten salt chlorination tail gas purification In order to recover NaCl, crystalline magnesium chloride and iron-manganese slag, low-cost resource treatment of molten salt chlorinated slag is realized. The exhaust gas absorption waste liquid is alkaline.
根据本发明的一种实施方式，上述熔盐氯化渣资源化处理方法具体包括以下步骤：According to an embodiment of the present invention, the method for recycling a molten salt chlorination slag specifically includes the following steps:
(1)将熔盐氯化渣或废熔盐溶浸得到浆料，然后过滤得到浸出液和溶浸残渣；(1) leaching the molten salt chlorinated slag or waste molten salt to obtain a slurry, and then filtering to obtain a leaching solution and a leaching residue;
(2)将所述浸出液与熔盐氯化尾气净化所产生的强氧化性、碱性废盐水或氯碱化工尾气吸收废液按照体积比1:0.6～0.9的比例混合，充分反应后，过滤得到氧化滤饼和合格盐水；(2) mixing the leaching liquid and the molten salt chlorination tail gas to produce a strong oxidizing, alkaline waste brine or chlor-alkali chemical tail gas absorption waste liquid according to a volume ratio of 1:0.6 to 0.9, fully reacted, and filtered. Oxidized filter cake and qualified brine;
(3)用水洗涤所述氧化滤饼得到铁锰渣；(3) washing the oxidized filter cake with water to obtain iron-manganese slag;
(4)将所述合格盐水分步结晶制取NaCl和MgCl2·6H2O。(4) The qualified brine is subjected to stepwise crystallization to obtain NaCl and MgCl 2 ·6H 2 O.
上述熔盐氯化渣资源化处理方法中，溶浸残渣用水洗涤至含盐量小于1.0％，即为终渣。终渣符合一般固体废弃物排放标准。In the above method for recycling molten salt chlorinated slag, the leaching residue is washed with water until the salt content is less than 1.0%, that is, the final slag. The final slag meets the general solid waste discharge standards.
上述熔盐氯化渣资源化处理方法中，洗涤产生的洗涤水循环回用于熔盐氯化渣或废熔盐溶浸。In the above-mentioned molten salt chlorination slag resource treatment method, the washing water produced by the washing is recycled back to the molten salt chlorinated slag or the waste molten salt to be immersed.
上述熔盐氯化渣资源化处理方法中，用水洗涤至铁锰渣的主要成分为铁、锰的氢氧化物或碳酸盐，Cl含量≤0.5％，Mn为4价，作为冶金原料使用。In the above-mentioned molten salt chlorination slag resource treatment method, the main component of the iron-manganese slag is washed with water to be iron or manganese hydroxide or carbonate, the Cl content is ≤0.5%, and the Mn is tetravalent, which is used as a metallurgical raw material.
上述熔盐氯化渣资源化处理方法中，分步结晶产生的冷凝水作为氧化滤饼和溶浸残渣的洗涤水回用。In the above-described molten salt chlorination slag resource treatment method, the condensed water produced by the stepwise crystallization is reused as the wash water of the oxidized filter cake and the leaching residue.
本发明资源化处理得到的NaCl干燥后回用于熔盐氯化，结晶氯化镁作为化工原料销售或深加工原料。The NaCl obtained by the resource treatment of the present invention is dried and used for smelting of molten salt, and the crystalline magnesium chloride is sold as a raw material for chemical raw materials or deep processing.
下面对本发明的技术方案进行进一步的说明。The technical solution of the present invention will be further described below.
本发明不外加碱，采用熔盐氯化炉尾气净化产生的碱性废盐水或氯碱化工尾气吸收废液来氧化沉淀熔盐氯化渣溶浸制取的混合盐水中的Fe、Mn、Ca等离子，碱性废盐水或氯碱化工尾气吸收废液中的强氧化性物质(NaClO、NaClO3)将二价铁氧化成三价铁、 二价锰氧化成四价猛，在较低pH完全沉淀，从而使MgCl2保留在溶液中，制得氯化镁、NaCl混合溶液，混合溶液经分步结晶制取NaCl和结晶氯化镁，NaCl循环回用于熔盐氯化，结晶氯化镁外销或作为无水氯化镁的生产原料。溶浸残渣洗涤脱盐后填埋，铁锰渣脱盐净化后作为冶金原料。The invention does not add alkali, adopts the alkaline waste brine produced by the purification of the tail gas of the molten salt chlorination furnace or the chlor-alkali chemical tail gas absorption waste liquid to oxidize and precipitate the Fe, Mn, Ca plasma in the mixed brine prepared by the molten salt chlorinated slag. Strong oxidizing substances (NaClO, NaClO 3 ) in alkaline waste brine or chlor-alkali chemical tail gas absorption waste liquid oxidize ferrous iron into ferric iron, divalent manganese is oxidized to tetravalent, and completely precipitates at a lower pH. Thus, MgCl 2 is retained in the solution to obtain a mixed solution of magnesium chloride and NaCl, and the mixed solution is subjected to fractional crystallization to obtain NaCl and crystalline magnesium chloride, and the NaCl is recycled for molten salt chlorination, crystalline magnesium chloride for export or as anhydrous magnesium chloride. raw material. The leaching residue is washed and desalted and then landfilled, and the iron-manganese slag is desalted and purified as a metallurgical raw material.
本发明以废治废，工艺简单，处理成本低廉。The invention adopts waste treatment and waste, has simple process and low treatment cost.
与现有技术相比，本发明的有益效果是：本发明利用熔盐氯化尾气净化或氯碱化工尾气净化过程中产生的废液处理熔盐氯化渣浸出液，以废治废，不仅解决了熔盐氯化渣的污染问题，还回收利用了熔盐渣中的NaCl、MgCl2及铁锰原料，具有良好的经济效益，对消除钛渣熔盐氯化制取TiCl4技术应用发展瓶颈意义重大，可广泛应用于国内外熔盐氯化—镁热电解海绵钛企业和熔盐氯化海绵钛企业中，推广前景广阔。Compared with the prior art, the invention has the beneficial effects that the present invention utilizes the waste liquid chlorinated tail gas purification or the waste liquid generated in the chlor-alkali chemical exhaust gas purification process to treat the molten salt chlorinated slag leaching solution, thereby eliminating waste treatment, thereby not only solving the problem. The problem of contamination of molten salt chlorinated slag, recycling of NaCl, MgCl 2 and iron-manganese raw materials in molten salt slag, has good economic benefits, and has the bottleneck significance of eliminating the application of TiCl 4 in the smelting of titanium slag molten salt. It is widely used in the domestic and international molten salt chlorination-magnesium thermal electrolytic sponge titanium enterprises and molten salt chlorinated sponge titanium enterprises, and has broad prospects for promotion.
附图说明DRAWINGS
图1为本发明熔盐氯化渣资源化处理方法流程框图。1 is a block diagram showing the flow of a method for recycling molten salt chlorinated slag according to the present invention.
具体实施方式detailed description
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。The present invention will be further described in detail below with reference to the accompanying drawings and embodiments. It is understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
本发明的熔盐氯化渣资源化处理方法如图1所示，首先将熔盐氯化渣溶浸、过滤，得到浸出液和溶浸残渣，浸出液用熔盐氯化尾气净化或氯碱化工尾气净化过程中产生的废液处理，得到合格盐水和氧化滤饼，合格盐水分步结晶得到氯化钠和结晶氯化镁，氧化滤饼洗涤后得到铁锰渣。熔盐氯化渣溶浸、过滤所得的残渣经过洗涤得到终渣，终渣属一般固体废弃物，运输至堆场填埋。The molten salt chlorination slag resource treatment method of the present invention is as shown in Fig. 1. First, the molten salt chlorinated slag is leached and filtered to obtain a leaching solution and a leaching residue, and the leaching solution is purified by molten salt chlorination tail gas or chlor-alkali chemical exhaust gas purification. The waste liquid generated in the process is treated to obtain qualified brine and oxidized filter cake, and the qualified brine is crystallized stepwise to obtain sodium chloride and crystalline magnesium chloride, and the oxidized filter cake is washed to obtain iron-manganese slag. The molten salt slag is leached and the residue obtained by filtration is washed to obtain a final slag. The final slag is a general solid waste and is transported to the yard for landfill.
下面通过具体的实施例来说明本发明的技术方案。The technical solution of the present invention will be described below by way of specific embodiments.
实施例1Example 1
本实施例要资源化处理的熔盐氯化渣破碎料组成成分如表1所示。The composition of the molten salt chlorinated slag crushing material to be resourced in this embodiment is shown in Table 1.
表1熔盐氯化渣成分分析结果Table 1 Analysis results of molten salt chlorinated slag
NaClNaCl FeCl2 FeCl 2 FeCl3 FeCl 3 MgCl2 MgCl 2 MnCl2 MnCl 2 CaCl2 CaCl 2 AlCl3 AlCl 3 TiO2 TiO 2 SiO2 SiO 2 CC 其它other
32.532.5 17.417.4 3.93.9 21.421.4 3.43.4 2.22.2 2.22.2 4.84.8 6.46.4 4.74.7 1.11.1
首先将熔盐氯化渣溶浸得到浆料，然后过滤得到浸出液和溶浸残渣。浸出液水质分析结果见表2。 First, the molten salt chlorinated slag is leached to obtain a slurry, which is then filtered to obtain a leaching solution and a leaching residue. The results of water quality analysis of the leachate are shown in Table 2.
表2浸出液水质分析结果Table 2 results of water quality analysis of leachate
Figure PCTCN2017079629-appb-000001
Figure PCTCN2017079629-appb-000001
将溶浸残渣用水洗涤至含盐量小于1.0％，洗涤时液固比约3.0:1。洗涤完成后得到终渣，将终渣填埋。终渣成分分析结果见表3。The leaching residue is washed with water until the salt content is less than 1.0%, and the liquid-solid ratio at the time of washing is about 3.0:1. After the washing is completed, the final slag is obtained, and the final slag is landfilled. The final slag composition analysis results are shown in Table 3.
表3终渣成分分析结果Table 3 final slag composition analysis results
Figure PCTCN2017079629-appb-000002
Figure PCTCN2017079629-appb-000002
将浸出液与熔盐氯化尾气净化所产生的含NaCl、NaClO、Na2CO3的强氧化性、碱性废盐水按照体积比1:0.76的比例混合，充分反应后，待无气泡产生并沉淀澄清，浆料约为盐水体积的45％，过滤得到氧化滤饼和澄清透明的合格盐水。废盐水的水质分析结果见表4。合格盐水的水质分析见表5。The strong oxidizing and alkaline waste brine containing NaCl, NaClO, Na 2 CO 3 produced by purifying the leachate and molten salt chlorination tail gas are mixed according to a volume ratio of 1:0.76, and after fully reacting, no bubbles are generated and precipitated. Clarification, the slurry was about 45% of the volume of the brine, filtered to give an oxidized cake and a clear, clear, qualified brine. The water quality analysis results of the waste brine are shown in Table 4. The water quality analysis of qualified brine is shown in Table 5.
表4废盐水水质分析结果Table 4 Analysis results of waste brine water quality
Figure PCTCN2017079629-appb-000003
Figure PCTCN2017079629-appb-000003
表5合格盐水水质分析结果Table 5 results of qualified brine water quality analysis
Figure PCTCN2017079629-appb-000004
Figure PCTCN2017079629-appb-000004
用浆料体积2倍的水洗涤氧化滤饼至Cl含量≤0.5％，得到铁锰渣，其干基成分见表6，铁锰渣作为冶金原料使用。The oxidation cake was washed with water twice the volume of the slurry to a Cl content of ≤0.5% to obtain iron-manganese slag, the dry components of which are shown in Table 6, and the iron-manganese slag was used as a metallurgical raw material.
表6铁锰渣干基成分分析结果Table 6 Results of analysis of dry basis of iron-manganese slag
NaNa MgMg FeFe MnMn CaCa ClCl
0.080.08 3.123.12 27.6127.61 5.885.88 2.82.8 0.310.31
铁锰渣在600℃煅烧2h，烧损约44％，煅烧料中TFe48.2％，Mn7.64％。The iron-manganese slag was calcined at 600 ° C for 2 h, and the burned loss was about 44%. The calcined material had a TFE of 48.2% and a Mn of 7.64%.
将合格盐水分步结晶制取NaCl和MgCl2·6H2O。合格盐水分步结晶制取NaCl粗盐的纯度约96.8％，精盐的纯度约98.4％，收率约97.8％。结晶氯化镁收率约64.8％，其MgCl2含量约46.1％，符合白色工业氯化镁质量标准。 The qualified brine was crystallized in portions to prepare NaCl and MgCl 2 ·6H 2 O. The purity of the crude NaCl salt obtained by stepwise crystallization of qualified brine is about 96.8%, the purity of the refined salt is about 98.4%, and the yield is about 97.8%. The yield of crystalline magnesium chloride is about 64.8%, and the MgCl 2 content is about 46.1%, which is in line with the white industrial magnesium chloride quality standard.
上述流程中，洗涤产生的洗涤水循环回用于熔盐氯化渣或废熔盐溶浸，分步结晶产生的冷凝水作为氧化滤饼和溶浸残渣的洗涤水回用。In the above process, the washing water produced by the washing is recycled to the molten salt slag or the waste molten salt, and the condensed water produced by the stepwise crystallization is reused as the washing water for the oxidizing cake and the leaching residue.
实施例2Example 2
本实施例的熔盐氯化渣资源化处理具体方法与实施例1基本相同，但浸出液用表10所示的氯碱厂废液氧化，废液投加比为浸出液体积的0.87倍。The specific method for the resource treatment of the molten salt chlorinated slag of the present embodiment is basically the same as that of the first embodiment, but the leaching solution is oxidized by the chlor-alkali plant waste liquid shown in Table 10, and the waste liquid dosing ratio is 0.87 times the volume of the leachate.
本实施例要资源化处理的熔盐氯化渣破碎料组成成分如表7所示。The composition of the molten salt chlorinated slag crushing material to be resourced in this embodiment is shown in Table 7.
表7熔盐氯化渣成分分析结果Table 7 Analysis results of molten salt chlorinated slag
NaClNaCl FeCl2 FeCl 2 FeCl3 FeCl 3 MgCl2 MgCl 2 MnCl2 MnCl 2 CaCl2 CaCl 2 AlCl3 AlCl 3 TiO2 TiO 2 SiO2 SiO 2 CC 其它other
31.531.5 15.415.4 2.92.9 24.424.4 2.92.9 2.02.0 3.23.2 4.64.6 6.66.6 4.44.4 1.91.9
浸出液水质分析结果见表8。The results of water quality analysis of the leachate are shown in Table 8.
表8浸出液水质分析结果Table 8 Leachate water quality analysis results
Figure PCTCN2017079629-appb-000005
Figure PCTCN2017079629-appb-000005
溶浸残渣用液固比3.0:1的自来水洗涤，终渣成分分析结果见表9。The leaching residue was washed with tap water having a liquid-solid ratio of 3.0:1, and the results of the final slag composition analysis are shown in Table 9.
表9终渣成分分析结果Table 9 final slag composition analysis results
Figure PCTCN2017079629-appb-000006
Figure PCTCN2017079629-appb-000006
浸出液用氯碱厂废液氧化，该废液的水质分析结果见表10。充分混匀，待无气泡产生并沉淀澄清，浆料约为盐水体积的40％。过滤得澄清透明的合格盐水，其水质分析见表11。The leachate was oxidized with the chlor-alkali plant waste liquid, and the water quality analysis results of the waste liquid are shown in Table 10. Mix well, wait until no bubbles are generated and precipitate to clarify. The slurry is about 40% of the volume of the brine. Filtered to obtain clear and transparent qualified brine, the water quality analysis is shown in Table 11.
表10氯碱厂废液水质分析结果Table 10 Water quality analysis results of chlor-alkali plant waste liquid
Figure PCTCN2017079629-appb-000007
Figure PCTCN2017079629-appb-000007
表11合格盐水水质分析结果Table 11 results of qualified brine water quality analysis
Figure PCTCN2017079629-appb-000008
Figure PCTCN2017079629-appb-000008
氧化滤饼用浆料体积2倍的水洗涤。铁锰渣干基成分见表12。 The oxidized cake was washed with 2 times the volume of the slurry. The dry basis of iron-manganese slag is shown in Table 12.
表12铁锰渣干基成分分析结果Table 12 Results of analysis of dry basis of iron-manganese slag
NaNa MgMg FeFe MnMn CaCa ClCl
0.090.09 0.120.12 34.6834.68 6.726.72 0.100.10 0.440.44
铁锰渣在600℃煅烧2h，烧损约28％，煅烧料中TFe54.6％，Mn10.77％。The iron-manganese slag was calcined at 600 ° C for 2 h, and the burned loss was about 28%. The calcined material had a TFE of 54.6% and a Mn of 10.77%.
合格盐水分步结晶，制取NaCl粗盐纯度约95.42％，精盐纯度约98.0％，收率约97.5％。结晶氯化镁收率约95.8％，其MgCl2含量约45.5％，符合普通工业氯化镁一级品质量标准。The qualified brine is crystallized step by step, and the purity of the crude salt of NaCl is about 95.42%, the purity of the refined salt is about 98.0%, and the yield is about 97.5%. The yield of crystalline magnesium chloride is about 95.8%, and the content of MgCl 2 is about 45.5%, which is in line with the quality standard of ordinary industrial magnesium chloride.
尽管这里参照本发明的解释性实施例对本发明进行了描述，但是，应该理解，本领域技术人员可以设计出很多其他的修改和实施方式，这些修改和实施方式将落在本申请公开的原则范围和精神之内。更具体地说，在本申请公开的范围内，可以对主题组合布局的组成部件和/或布局进行多种变型和改进。除了对组成部件和/或布局进行的变型和改进外，对于本领域技术人员来说，其他的用途也将是明显的。 Although the present invention has been described herein with reference to the preferred embodiments of the present invention, it is understood that many modifications and embodiments may be And within the spirit. More specifically, various variations and modifications can be made to the components and/or arrangements of the subject combination arrangement within the scope of the present disclosure. Other uses will be apparent to those skilled in the art, in addition to variations and modifications in the component parts and/or arrangements.

Claims (6)

  1. 一种熔盐氯化渣资源化处理方法，其特征在于：它是利用钛渣熔盐氯化尾气净化所产生的强氧化性、碱性废盐水或氯碱化工尾气吸收废液来处理熔盐氯化渣的浸出液，从而回收NaCl、结晶氯化镁、铁锰渣，实现熔盐氯化渣低成本资源化处理。A method for recycling molten salt chlorinated slag, which is characterized in that it utilizes strong oxidizing, alkaline waste brine or chlor-alkali chemical tail gas absorption waste liquid produced by purifying titanium slag molten salt tail gas to treat molten salt chlorine The leaching solution of the slag is used to recover NaCl, crystalline magnesium chloride and iron-manganese slag to realize low-cost resource treatment of the molten salt chlorinated slag.
  2. 根据权利要求1所述的熔盐氯化渣资源化处理方法，其特征在于：该方法具体包括以下步骤：The method for processing a molten salt chlorinated slag according to claim 1, wherein the method comprises the following steps:
    (1)将熔盐氯化渣或废熔盐溶浸得到浆料，然后过滤得到浸出液和溶浸残渣；(1) leaching the molten salt chlorinated slag or waste molten salt to obtain a slurry, and then filtering to obtain a leaching solution and a leaching residue;
    (2)将所述浸出液与熔盐氯化尾气净化所产生的强氧化性、碱性废盐水或氯碱化工尾气吸收废液按照体积比1:0.6～0.9的比例混合，充分反应后，过滤得到氧化滤饼和合格盐水；(2) mixing the leaching liquid and the molten salt chlorination tail gas to produce a strong oxidizing, alkaline waste brine or chlor-alkali chemical tail gas absorption waste liquid according to a volume ratio of 1:0.6 to 0.9, fully reacted, and filtered. Oxidized filter cake and qualified brine;
    (3)用水洗涤所述氧化滤饼得到铁锰渣；(3) washing the oxidized filter cake with water to obtain iron-manganese slag;
    (4)将所述合格盐水分步结晶制取NaCl和MgCl2·6H2O。(4) The qualified brine is subjected to stepwise crystallization to obtain NaCl and MgCl 2 ·6H 2 O.
  3. 根据权利要求2所述的熔盐氯化渣资源化处理方法，其特征在于：所述溶浸残渣用水洗涤至含盐量小于1.0％即为终渣。The molten salt chlorination slag resource treatment method according to claim 2, wherein the leaching residue is washed with water until the salt content is less than 1.0%, that is, the final slag.
  4. 根据权利要求2或3所述的熔盐氯化渣资源化处理方法，其特征在于：所述洗涤产生的洗涤水循环回用于熔盐氯化渣或废熔盐溶浸。The molten salt chlorination slag resource treatment method according to claim 2 or 3, characterized in that the washing water produced by the washing is recycled back to the molten salt slag or the waste molten salt.
  5. 根据权利要求2所述的熔盐氯化渣资源化处理方法，其特征在于：所述铁锰渣的主要成分为铁、锰的氢氧化物或碳酸盐，Cl含量≤0.5％，作为冶金原料使用。The method for recycling molten salt chlorinated slag according to claim 2, wherein the main component of the iron-manganese slag is iron or manganese hydroxide or carbonate, and the Cl content is ≤0.5%, as metallurgy. Raw materials used.
  6. 根据权利要求2所述的熔盐氯化渣资源化处理方法，其特征在于：所述分步结晶产生的冷凝水作为氧化滤饼和溶浸残渣的洗涤水回用。 The molten salt chlorination slag resource treatment method according to claim 2, wherein the condensed water produced by the stepwise crystallization is reused as wash water for the oxidized filter cake and the leaching residue.
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