WO2016019774A1 - Procédé de préparation d'un mélange de résidus alcalins d'élimination de chlore par utilisation de résidus alcalins par le biais d'un processus ammoniac-soude et son application - Google Patents

Procédé de préparation d'un mélange de résidus alcalins d'élimination de chlore par utilisation de résidus alcalins par le biais d'un processus ammoniac-soude et son application Download PDF

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Publication number
WO2016019774A1
WO2016019774A1 PCT/CN2015/083350 CN2015083350W WO2016019774A1 WO 2016019774 A1 WO2016019774 A1 WO 2016019774A1 CN 2015083350 W CN2015083350 W CN 2015083350W WO 2016019774 A1 WO2016019774 A1 WO 2016019774A1
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WIPO (PCT)
Prior art keywords
alkali
powder
mixture
returned
sand
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PCT/CN2015/083350
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English (en)
Chinese (zh)
Inventor
杨医博
郭文瑛
莫海鸿
王恒昌
Original Assignee
华南理工大学
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Application filed by 华南理工大学 filed Critical 华南理工大学
Priority to JP2016568449A priority Critical patent/JP6404948B2/ja
Publication of WO2016019774A1 publication Critical patent/WO2016019774A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • 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
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • 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
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
    • 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
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Definitions

  • the invention belongs to the field of industrial solid waste treatment, and particularly relates to an alkali alkali residue and a sand returning stone treatment method and an application method thereof.
  • soda ash As a basic chemical raw material, soda ash is mainly used in construction materials, chemicals, chemical pesticides, non-ferrous metals, textiles and other industries. It plays an important role in the national economy and is known as the “mother of chemical industry”. At present, the production of soda ash mainly includes the trona method, the ammonia-alkali method and the combined alkali method. The production of soda ash in China is mainly based on the ammonia-alkali method.
  • Alkali slag is an industrial waste residue produced during the process of producing soda ash by the ammonia-base method.
  • the main components of the alkali slag are calcium carbonate, calcium sulfate and oxides such as aluminum, iron and silicon, and contain a large amount of chloride.
  • the annual production of alkali slag in China exceeds 300. Ten thousand tons.
  • Alkali slag is a worldwide problem due to its high alkalinity and high chloride ion content.
  • the main methods of its use are to prepare engineering soil for land preparation, dam construction, roadbed and pavement base layer, etc.
  • soil improver and smoke are prepared by using alkali residue.
  • how to effectively reduce the chloride ion content in the alkali residue has not been broken, and the excessive chloride ion content in the alkali residue after treatment also affects its application in various fields.
  • the most effective method for dechlorination of alkali residue is water washing and dechlorination, but the washing efficiency is low, multiple washings are required, and a large amount of water is consumed, which also seriously affects its application.
  • the higher chloride ion content can be controlled.
  • the chloride ion content of the alkali residue is controlled at 1.5% after one water washing and pressure filtration. Left and right.
  • the high-efficiency dechlorination method of alkali slag has become a major problem that restricts the sustainable development of the soda ash industry.
  • the solid waste of the soda ash plant also has a returning sand returning stone, which is generated for each ton of soda ash produced.
  • the object of the present invention is to provide a chlorine removal alkali slag mixture by using an alkali-base alkali residue for good chlorine removal effect.
  • a method for preparing a mixture of chlor-alkali residues by using an alkali-base alkali residue comprising the steps of:
  • Step 1 First, returning the sand to the stone and crushing it into a sand returning powder;
  • Step 2 Soak the returning stone powder in water 0.5 to 14 After dissolving the calcined calcium oxide, the digested returning stone powder, alkali residue and water are mixed, and the ratio of the dry mass of the returned sand powder and the alkali residue after digestion is 2:8. To 5 : 5, the total mass of water is 1.5 to 8 times the total dry mass of the returned sand returning powder and alkali residue after digestion;
  • Step 3 Perform a pressure filtration treatment to obtain a dechlorination alkali residue mixture having a chloride ion content of 0.30% lower than the total mass of the solid in the mixture.
  • intermittent agitation is also performed during the step 2 in which the returning sand powder is immersed.
  • One or more of fly ash, limestone powder, slag powder, slag powder, steel slag powder and stone powder may be used to replace the returning sand powder of less than or equal to 50%.
  • the first method further comprises the steps of separately separating and recovering calcium hydroxide in the re-returned stone powder after digestion, and using it for soda ash production.
  • Another object of the present invention is to provide an application of the above-described chlorine-removing alkali residue mixture, the scheme being as follows:
  • the chlorine-removing alkali residue mixture can be used as a mixed material of cement, mineral admixture of concrete and mortar, engineering soil, filler, flue gas desulfurizer, soil treatment agent , adsorbents and carriers.
  • the chlorinated alkali residue mixture is used as a mixed material of cement, a mineral admixture of concrete and mortar, a filler, a flue gas desulfurizer, a soil treatment agent, an adsorbent and a carrier, and is first dried, crushed, and ground. The mixture was treated to obtain a powdery chlorinated alkali residue mixture.
  • the dechlorination alkali residue mixture can replace 30% or less of the cementitious material.
  • the alkali slag particles are small, the particle size is between several micrometers and several tens of micrometers, and contains a large amount of pores, so the moisture content and chloride ion content of the alkali slag after pressure filtration are high.
  • the chloride ion in the alkali residue is mainly present in water, and the particle grading adjustment material may be added to reduce the porosity, thereby reducing the chloride ion content in the alkali residue after pressure filtration.
  • the returning sand powder after water digestion is selected as the particle grading adjustment material. Due to the dissolution of calcium oxide, the surface of the returned sand powder after water digestion is rough, which can reduce the chloride ion content more effectively.
  • the present invention has the following advantages:
  • the dechlorination effect of the invention is good, and the chlorine ion content (calculated as the total mass of the solid) can be made less than 0.30% by using a single water washing and pressure filtration treatment, which greatly reduces the chloride ion content compared with the conventional primary water washing pressure filtration.
  • a method for preparing a mixture of chlor-alkali residues by using an alkali-base alkali residue comprising the steps of:
  • Step 1 First, returning the sand to the stone and crushing it into a sand returning powder;
  • Step 2 Soak the returning stone powder in water 0.5 Days dissolve the burned calcium oxide, and intermittently stir when returning the sand to the stone powder, and then mix the returned sand returning powder, alkali residue and water after the digestion, based on the mass percentage of the material, the back-returned stone powder after digestion and The ratio of alkali residue is 2 : 8, the total mass of water is 8 times the total mass of returning stone powder and alkali residue after digestion;
  • Step 3 Perform a pressure filtration treatment to obtain a chlorinated alkali residue mixture having a chloride ion content of 0.28% of the total solid mass in the mixture.
  • one or more of fly ash, limestone powder, slag powder, slag powder, steel slag powder and stone powder may be replaced by no more than 50%. Returning sand to stone powder.
  • the calcium hydroxide in the re-returned stone powder after digestion is first separated and recovered, and used for soda ash production.
  • a method for preparing a mixture of chlor-alkali residues by using an alkali-base alkali residue comprising the steps of:
  • Step 1 First, returning the sand to the stone and crushing it into a sand returning powder;
  • Step 2 Soak the returning sand powder in water 3 Days dissolve the burned calcium oxide, and intermittently stir when returning the sand to the stone powder, and then mix the returned sand returning powder, alkali residue and water after the digestion, based on the mass percentage of the material, the back-returned stone powder after digestion and The ratio of alkali residue is 3 :7, the total mass of water is 7 times of the total mass of returning stone powder and alkali residue after digestion;
  • Step 3 Perform a pressure filtration treatment to obtain a chlorinated alkali residue mixture having a chloride ion content of 0.08% of the total solid mass in the mixture.
  • one or more of fly ash, limestone powder, slag powder, slag powder, steel slag powder and stone powder may be replaced by no more than 50%. Returning sand to stone powder.
  • the calcium hydroxide in the re-returned stone powder after digestion is first separated and recovered, and used for soda ash production.
  • a method for preparing a mixture of chlor-alkali residues by using an alkali-base alkali residue comprising the steps of:
  • Step 1 First, returning the sand to the stone and crushing it into a sand returning powder;
  • Step 2 Soak the returning stone powder in water 7 Days dissolve the burned calcium oxide, and intermittently stir when returning the sand to the stone powder, and then mix the returned sand returning powder, alkali residue and water after the digestion, based on the mass percentage of the material, the back-returned stone powder after digestion and The ratio of alkali residue is 5 : 5, the total mass of water is 3 times the total mass of returning stone powder and alkali residue after digestion;
  • Step 3 Perform a pressure filtration treatment to obtain a chlorinated alkali residue mixture having a chloride ion content of 0.05% of the total solid mass in the mixture.
  • one or more of fly ash, limestone powder, slag powder, slag powder, steel slag powder and stone powder may be replaced by no more than 50%. Returning sand to stone powder.
  • the calcium hydroxide in the re-returned stone powder after digestion is first separated and recovered, and used for soda ash production.
  • a method for preparing a mixture of chlor-alkali residues by using an alkali-base alkali residue comprising the steps of:
  • Step 1 First, returning the sand to the stone and crushing it into a sand returning powder;
  • Step 2 soak in water 14 Days dissolve the burned calcium oxide, and intermittently stir when returning the sand to the stone powder, and then mix the returned sand returning powder, alkali residue and water after the digestion, based on the mass percentage of the material, the back-returned stone powder after digestion and The ratio of alkali residue is 5 : 5, the total mass of water is 1.5 times the total mass of returning stone powder and alkali residue after digestion;
  • Step 3 Perform a pressure filtration treatment to obtain a chlorinated alkali residue mixture having a chloride ion content of 0.09% of the total solid mass in the mixture.
  • one or more of fly ash, limestone powder, slag powder, slag powder, steel slag powder and stone powder may be replaced by no more than 50%. Returning sand to stone powder.
  • the calcium hydroxide in the re-returned stone powder after digestion is first separated and recovered, and used for soda ash production.
  • a method for preparing a mixture of chlor-alkali residues by using an alkali-base alkali residue comprising the steps of:
  • Step 1 First, returning the sand to the stone and crushing it into a sand returning powder;
  • Step 2 Soak the returned sand powder, alkali residue and water, and soak 0.5
  • the calcined calcium oxide is dissolved in days, and the ratio of the mass of the returned sand powder to the alkali residue is 2:8, and the total mass of the water is 8 times the total dry mass of the returned sand powder and the alkali residue;
  • Step 3 Perform a pressure filtration treatment to obtain a chlorinated alkali residue mixture having a chloride ion content of 0.28% of the total solid mass in the mixture.
  • one or more of fly ash, limestone powder, slag powder, slag powder, steel slag powder and stone powder may be replaced by no more than 50%. Returning sand to stone powder.
  • a method for preparing a mixture of chlor-alkali residues by using an alkali-base alkali residue comprising the steps of:
  • Step 1 First, returning the sand to the stone and crushing it into a sand returning powder;
  • Step 2 Soak the returned sand powder, alkali residue and water, and soak 3
  • the calcined calcium oxide is dissolved in days, and the ratio of the mass of the returned sand powder to the alkali residue is 3:7, and the total mass of the water is 7 times the total dry mass of the returned sand powder and the alkali residue;
  • Step 3 Perform a pressure filtration treatment to obtain a chlorinated alkali residue mixture having a chloride ion content of 0.08% of the total solid mass in the mixture.
  • one or more of fly ash, limestone powder, slag powder, slag powder, steel slag powder and stone powder may be replaced by no more than 50%. Returning sand to stone powder.
  • the chlor-alkali residue mixture is used as a mineral admixture for concrete, and the chlor-alkali residue is formulated to have a water content of 250%.
  • the suspension is used to replace 10% of the cement with chlor-alkali slag (dry basis).
  • the concrete strength is basically unchanged and does not cause corrosion of the steel in the structure.
  • the powdered dechlorination alkali residue mixture after drying and crushing and grinding the dechlorination alkali residue mixture is used as a mixed material of cement, wherein the powdery dechlorination alkali residue mixture has a particle size of 80
  • the micron sieve residue is less than 5%, the amount is 30%, the amount of slag powder is 22%, the amount of cement clinker is 45%, and the amount of gypsum is 3%.
  • Cement performance meets masonry cement 12.5 Grade requirements, and high water retention, water retention rate of 96.5%.
  • the powdered dechlorination alkali residue mixture after drying and crushing and grinding the dechlorination alkali residue mixture is classified according to different particle sizes, wherein less than 3 Micron powdered chlorinated alkali residue mixture used as rubber filler, greater than or equal to 3 A micron powdered chlor-alkali residue mixture is used as a flue gas desulfurizer.
  • the porosity of the mixture of dechlorination alkali slag is utilized to improve the mechanical properties of the rubber and the efficiency of the flue gas desulfurizer. When used as a flue gas desulfurizer, it can replace the limestone powder originally used, saving energy and environmental protection.
  • the chlor-alkali residue mixture When used in engineering soil, it can be directly used for earthwork filling, and the chlorine ion content is low, and it will not cause harm to the environment.

Abstract

L'invention concerne un procédé de préparation d'un mélange de résidus alcalins d'élimination de chlore par utilisation de résidus alcalins par le biais d'un processus ammoniac-soude. Ce procédé comprend les étapes suivantes : étape 1, broyer du sable de rebut et des pierres de rebut pour obtenir de la poudre de sable de rebut et de pierres de rebut; étape 2, faire tremper la poudre de sable de rebut et de pierres de rebut dans l'eau pendant 0,5 à 14 jours, mettre en digestion de l'oxyde de calcium brûlé, puis mélanger la poudre de sable de rebut et de pierres de rebut digérée, des résidus alcalins et de l'eau, le rapport entre la masse sèche de cette poudre digérée et les résidus alcalins représentant de 2/8 à 5/5 du pourcentage massique des matériaux, et la masse totale de l'eau est de 1,5 à 8 fois égale à la masse totale sèche de ladite poudre de sable de rebut et de pierres de rebut digérée et des résidus alcalins; ou bien mélanger la poudre de sable de rebut et de pierres de rebut, les résidus alcalins et l'eau, puis faire tremper ce mélange pendant 0,5 à 14 jours, et mettre en digestion l'oxyde de calcium calciné; étape 3, exécuter un traitement de pressage-filtrage, puis obtenir le mélange de résidus alcalins d'élimination de chlore dont le contenu en ions chlore est inférieur à 0,30 % de la masse totale des solides dans le mélange. L'invention concerne également une application du mélange de résidus alcalins d'élimination de chlore. Ce procédé possède de bons effets d'élimination du chlore, est simple à mettre en œuvre, efficace du point de vue énergétique et sans danger pour l'environnement.
PCT/CN2015/083350 2014-08-06 2015-07-06 Procédé de préparation d'un mélange de résidus alcalins d'élimination de chlore par utilisation de résidus alcalins par le biais d'un processus ammoniac-soude et son application WO2016019774A1 (fr)

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JP2016568449A JP6404948B2 (ja) 2014-08-06 2015-07-06 アンモニアソーダ法による苛性スラッジから脱塩素苛性スラッジ混合物を調製する方法及びその応用

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CN201410383247.6A CN104190690B (zh) 2014-08-06 2014-08-06 一种利用氨碱法碱渣制备除氯碱渣混合物的方法及应用
CN201410383247.6 2014-08-06

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CN114768603A (zh) * 2022-05-27 2022-07-22 路德环境科技股份有限公司 应用于碱渣处理工艺的黄土化浆系统
CN116119999A (zh) * 2022-10-12 2023-05-16 东南大学 一种碱渣轻质土及其制备方法与应用

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