CN110589856A - Method for recovering and separating potassium salt and sodium salt in waste incineration fly ash - Google Patents

Method for recovering and separating potassium salt and sodium salt in waste incineration fly ash Download PDF

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CN110589856A
CN110589856A CN201910941482.3A CN201910941482A CN110589856A CN 110589856 A CN110589856 A CN 110589856A CN 201910941482 A CN201910941482 A CN 201910941482A CN 110589856 A CN110589856 A CN 110589856A
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chloride
salt
potassium
sodium
fly ash
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谢巧玲
王丹丹
梁高杰
卢伟
秦舒浩
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Shenzhen Research Institute Tsinghua University
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01DCOMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D3/00Halides of sodium, potassium or alkali metals in general
    • C01D3/04Chlorides
    • C01D3/08Preparation by working up natural or industrial salt mixtures or siliceous minerals
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01FCOMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00Compounds of calcium, strontium, or barium
    • C01F11/20Halides
    • C01F11/24Chlorides
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/80Compositional purity

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

本发明涉及回收并分离垃圾焚烧飞灰中钾盐和钠盐的方法,包括:将石英砂与水从垃圾焚烧飞灰中提取钾盐、钠盐、钙盐,得高浓度含盐水,石英砂与飞灰分离后返回继续使用;高浓度含盐水用酸调pH为5~7,经蒸发浓缩得钾钠混盐及残余氯化钙饱和溶液;将钾钠混盐在饱和氯化钾、氯化钠溶液中浮选分离、过滤,泡沫产品为氯化钾,尾矿浆为氯化钠;浮选所得氯化钾和氯化钠分别用对应饱和盐水进行搅拌洗涤、过滤,得工业级氯化钾及氯化钠产品,洗涤液为饱和氯化钾、氯化钠混合液,返回浮选作为浮选介质补充液。本发明有效分离飞灰中可溶性盐:氯化钾、氯化钠及氯化钙,无需脱钙,得高纯度的或工业级氯化钾和氯化钠产品;极大提升处理工艺的效费比。

The invention relates to a method for recovering and separating potassium salt and sodium salt in waste incineration fly ash, comprising: extracting potassium salt, sodium salt and calcium salt from waste incineration fly ash with quartz sand and water to obtain high-concentration salt water, quartz sand After being separated from the fly ash, return to continue to use; the high-concentration brine contains acid to adjust the pH to 5-7, and evaporate and concentrate to obtain potassium-sodium mixed salt and residual calcium chloride saturated solution; mix potassium-sodium mixed salt in saturated potassium chloride, chloride Flotation separation and filtration in sodium chloride solution, the foam product is potassium chloride, and the tailings slurry is sodium chloride; the potassium chloride and sodium chloride obtained by flotation are stirred, washed and filtered with corresponding saturated brine respectively to obtain industrial grade chloride Potassium and sodium chloride products, the washing liquid is a mixture of saturated potassium chloride and sodium chloride, which is returned to the flotation as the supplementary liquid of the flotation medium. The present invention effectively separates soluble salts in fly ash: potassium chloride, sodium chloride and calcium chloride, and obtains high-purity or industrial-grade potassium chloride and sodium chloride products without decalcification; greatly improving the efficiency of the treatment process Compare.

Description

Method for recovering and separating potassium salt and sodium salt in waste incineration fly ash
Technical Field
The invention relates to the technical field of environmental protection, in particular to a method for recovering and separating potassium salt and sodium salt in waste incineration fly ash.
Background
China is a country with relatively poor potassium resources, the production of potassium salt in China is mainly extracted from salt lakes and seawater, and most of the other parts need to be imported from abroad. Research results show that the content of potassium and sodium salts in the incineration fly ash is up to more than 20 percent, and if the potassium and sodium salts are not utilized, a huge 'salt mine' is wasted. The potassium and sodium salts in the fly ash mainly exist in the form of chloride, and the content of chloride ions reaches about 20 percent. According to the characteristics of the components of the waste fly ash, the method for effectively disposing the waste fly ash by using the cement as the raw material is adopted, but the waste fly ash has high chloride ion content, and the cement is directly used as the cement raw material to cause skinning and blockage, so that the normal operation of a cement kiln is influenced. Therefore, the potassium and sodium salts in the waste incineration fly ash are separated and recovered, the content of chloride ions can be greatly reduced, the requirement and the suitability for subsequent cement kiln treatment can be met, and the resource treatment of the fly ash can be realized.
Hangzhou xiu environmental protection science and technology limited company patent No. CN109396163A discloses a garbage fly ash treatment process for improving the dissolution rate of chloride ions, and the process effectively improves the dissolution rate of chloride ions in fly ash by combining wet grinding with a three-stage water washing process. Another patent No. CN109455738A discloses a process for preparing high-quality industrial salt from fly ash from waste incineration, which comprises the steps of washing fly ash with water, removing heavy metals, decoloring, removing calcium, evaporating for crystallization and separating potassium and sodium. In the process, sodium chloride is obtained by primary centrifugal separation during evaporation crystallization, separated liquid is subjected to secondary centrifugal separation after being cooled and crystallized, the liquid subjected to secondary centrifugal separation enters the heavy metal removal step again, the solid subjected to secondary centrifugal separation is refined by taking saturated potassium chloride solution as refined washing liquid, and potassium chloride is obtained after tertiary centrifugal separation, wherein the heavy metal content of the potassium chloride is within the national standard requirement.
Chinese Zhongji International engineering Co., Ltd, patent No. CN110040748A discloses a method for producing potassium salt and sodium salt by using waste incineration fly ash, which comprises the steps of leaching the waste incineration fly ash with water to obtain leaching solution, removing calcium ions and heavy metal impurities in the leaching solution by sodium carbonate, sodium sulfide and other medicaments in sequence, and evaporating and crystallizing the leaching solution in multiple steps after removing impurities to obtain high-purity or industrial sodium chloride and potassium chloride crystals.
Patent No. CN109354041A of Nanjing Nanhuan Water science and technology Limited discloses a method for extracting potassium from fly ash water washing liquid, which comprises the steps of carrying out front-stage filtration on the fly ash water washing liquid and removing suspended matters, sequentially adding sulfuric acid and sodium sulfate for clarification and sludge filtration, carrying out evaporative crystallization on the clarified liquid to separate out sodium chloride, adding sodium sulfate for freezing crystallization, obtaining glaserite solid, and further purifying by using potassium chloride regulating solution to obtain potassium sulfate crystal salt with higher value.
However, in the above technical achievement, patent CN109396163A discloses a waste fly ash treatment process for improving the dissolution rate of chloride ions, which adopts a wet grinding combined with a three-stage water washing process to effectively improve the dissolution rate of chloride ions in fly ash. As the fly ash is from waste incineration, a certain proportion of aggregation particles which are difficult to disperse can be formed in the fly ash production process, the fly ash is directly mixed with water and is not uniform, soluble salts in the fly ash particles are difficult to dissolve out, and meanwhile, the fly ash particles are easy to agglomerate and agglomerate while the fly ash is stirred and washed, so that the soluble salts are difficult to dissolve out, therefore, the fly ash particles after wet grinding are finer and are easy to agglomerate and agglomerate, and the difficulty in subsequent filtration is increased. The fly ash is washed by water to obtain high-concentration salt water, mainly comprising potassium chloride, sodium chloride and calcium chloride, the contents of the potassium chloride, the sodium chloride and the calcium chloride are close to each other, decalcification and heavy metal removal treatment are required before an evaporation crystallization process is adopted, a large amount of sodium carbonate or sodium sulfate is required to be added in the decalcification process, the dosage of a medicament is large, the disposal cost is high, and a large amount of calcium mud is generated at the same time. The potassium and sodium salts are separated by an evaporative crystallization process, crystallization separation needs to be carried out in multiple steps, and washing water with approximate potassium and sodium contents cannot be effectively separated, so that the method is narrow in applicability.
Disclosure of Invention
The technical problem solved by the invention is to overcome the defects in the prior art, and provide a method for effectively separating soluble salt from fly ash, which comprises the following steps: potassium chloride, sodium chloride and calcium chloride, without decalcification, and obtaining high-purity or industrial-grade potassium chloride and sodium chloride products; the method has the advantages of high potassium-sodium salt extraction rate in the fly ash, high potassium-sodium mixed salt separation efficiency, greatly reduced operation cost, and greatly improved efficiency-cost ratio of the treatment process, and can be used for recovering and separating potassium salt and sodium salt in the waste incineration fly ash.
The technical scheme of the invention is that the method for recovering and separating the potassium salt and the sodium salt in the waste incineration fly ash is characterized by comprising the following steps:
(1) quartz sand and water are used for extracting soluble salts of potassium, sodium and calcium from waste incineration fly ash to obtain high-concentration salt-containing water, and the quartz sand and the fly ash are separated and then return to the process for continuous use;
(2) adjusting the pH value of the high-concentration salt-containing water obtained in the step (1) to 5-7 with acid, and evaporating and concentrating to obtain potassium-sodium mixed salt and residual calcium chloride saturated solution;
(3) carrying out flotation separation on the potassium-sodium mixed salt obtained in the step (2) in a saturated potassium chloride and sodium chloride solution, and filtering to obtain a foam product, namely potassium chloride and tailing slurry, namely sodium chloride;
(4) and (4) respectively stirring and washing the potassium chloride salt and the sodium chloride salt obtained by the flotation separation in the step (3) by using corresponding saturated saline water, filtering to obtain industrial potassium chloride and sodium chloride products, wherein the washing liquid is a mixed liquid of saturated potassium chloride and sodium chloride, and returning to the flotation process as a flotation medium supplementary liquid.
Preferably, the step (1) further comprises: the waste incineration fly ash mainly refers to fly ash with low heavy metal content, and soluble salts of potassium salt, sodium salt and calcium salt mainly include potassium chloride, sodium chloride and calcium chloride.
Preferably, the step (1) further comprises: the mass ratio of the quartz sand to the fly ash is 1: 2-2: 1, the granularity of the quartz sand is 40-60 meshes, the mass ratio of the fly ash to water is 1: 1-1: 4, the stirring speed is 200-500 r.min < -1 >, the stirring time is 10-60 min, and the scrubbing times are 2-5 times.
Preferably, the step (1) further comprises: the quartz sand and fly ash are separated by adopting a cyclone classifier, and the quartz sand is separated firstly and then the solid and the liquid are separated.
Preferably, the step (2) further comprises: the acid is hydrochloric acid, and the preferable evaporation pH range is 5-5.5.
Preferably, the step (3) further comprises: the flotation separation adopts a collecting agent which is self-made water-soluble amine, the amine comprises one or a mixture of ethylenediamine, dodecylamine, octadecylamine, eicosylamine and mixed amine, the inhibitor mainly comprises one or any two of citric acid, sodium citrate and carboxymethyl cellulose, and the waste brine generated after the flotation is filtered and then returns to the flow for continuous use.
Preferably, the step (4) further comprises: the amount of saturated salt water adopted for stirring and washing potassium chloride and sodium chloride is 2-5 times of the impurity content, the stirring and washing time is 10-60 min, and the saturated salt water after washing and separation returns to the flotation process to be used as flotation medium supplementary liquid.
Compared with the prior art, the invention has the beneficial effects that:
the method has the advantages that the quartz sand is adopted for scrubbing the fly ash, so that the dissolution rate of soluble salt in the fly ash can be effectively improved, high-concentration salt-containing water is obtained, the energy consumption during evaporative crystallization is greatly reduced, and the production cost is reduced;
the decalcification process is not needed, so that the consumption cost of the agent is reduced;
the evaporation process is effectively reduced, and the evaporation cost is reduced;
and the flotation process can effectively separate potassium-sodium mixed salt in any proportion, the adaptability is strong, flotation wastewater can be recycled, and secondary pollution is avoided.
Drawings
FIG. 1 is a simplified process flow diagram of the present invention;
FIG. 2 is a detailed process flow diagram of the present invention.
Detailed Description
The invention will be further described in detail with reference to the following examples:
example 1:
(1) stirring and scrubbing quartz sand and fly ash with the granularity of 40-60 meshes according to the mass ratio of 0.5:1, stirring and scrubbing fly ash and water according to the mass ratio of 1:4, wherein the stirring speed is 300 r.min < -1 >, the stirring time is 30min, filtering and then repeatedly scrubbing are carried out for 2 times, scrubbing liquid returns to the previous stage for repeated use until the salt content in high-concentration salt-containing water obtained by the first stage of scrubbing reaches 20-30%, and the fly ash is separated from the quartz sand by a cyclone after the last stage of scrubbing and then returns to the process for continuous use;
(2) adjusting the pH value of the high-concentration salt water obtained in the step (1) to 5 by using hydrochloric acid, and performing evaporation concentration to obtain a potassium-sodium mixed salt and a residual calcium chloride saturated solution, wherein the content of calcium chloride in the potassium-sodium mixed salt is 6.15%, and the content of calcium chloride in the residual calcium chloride saturated solution is 89.17%;
(3) taking water-soluble amines prepared by taking octadecylamine as a main raw material as a collecting agent, taking carboxymethyl cellulose as an inhibitor, taking saturated potassium chloride and sodium chloride solution as a flotation medium, carrying out flotation separation on the potassium-sodium mixed salt obtained in the step (2), and filtering waste brine generated after flotation and returning the filtered waste brine to the flow for continuous use;
wherein the potassium chloride content in the separated potassium salt is 93.12%, and the recovery rate is 89.14%; the sodium chloride content in the sodium salt is 86.23 percent, and the recovery rate is 90.00 percent;
(4) respectively using potassium chloride saturated solution and sodium chloride saturated solution as washing solutions, respectively stirring and washing potassium chloride salt and sodium chloride salt obtained by flotation separation in the step (3), filtering to obtain industrial-grade potassium chloride and sodium chloride products, and mixing the washed potassium chloride and sodium chloride saturated solutions with each other to return to the process as flotation medium replenishing solution when the impurity content reaches a certain degree in the mixed solution of the potassium chloride and the sodium chloride;
the saturated brine for stirring and washing is 3 times of the impurity content, and the stirring and washing time is 30 min. After stirring and washing, the potassium chloride content in the sylvite is more than or equal to 95 percent, and the effective sodium chloride content in the sodium salt is more than or equal to 92 percent.
The above-mentioned embodiments are only preferred embodiments of the present invention, and all equivalent changes and modifications made within the scope of the claims of the present invention should be covered by the claims of the present invention.

Claims (7)

1.一种回收并分离垃圾焚烧飞灰中钾盐和钠盐的方法,其特征在于,包括以下步骤:1. a method of reclaiming and separating potassium salt and sodium salt in the waste incineration fly ash, is characterized in that, comprises the following steps: (1)将石英砂与水从垃圾焚烧飞灰中提取钾盐、钠盐、钙盐,得到高浓度含盐水,石英砂与飞灰分离后返回流程继续使用;(1) Quartz sand and water are used to extract potassium salt, sodium salt, and calcium salt from waste incineration fly ash to obtain high-concentration salt water, and the quartz sand and fly ash are separated and returned to the process for continued use; (2)将步骤(1)所得高浓度含盐水用酸调pH为5~7,通过蒸发浓缩得到钾钠混盐及残余氯化钙饱和溶液;(2) adjusting the pH of the high-concentration brine obtained in step (1) to 5 to 7 with an acid, and concentrating by evaporation to obtain a potassium-sodium mixed salt and a saturated solution of residual calcium chloride; (3)将步骤(2)所得钾钠混盐在饱和氯化钾、氯化钠溶液中进行浮选分离,过滤,泡沫产品为氯化钾,尾矿浆为氯化钠;(3) Carry out flotation separation in saturated potassium chloride, sodium chloride solution by step (2) gained potassium sodium mixed salt, filter, and foam product is potassium chloride, and tailings slurry is sodium chloride; (4)将步骤(3)浮选分离所得氯化钾和氯化钠分别用对应的饱和盐水进行搅拌洗涤,过滤,得到工业级氯化钾及氯化钠产品,洗涤液为饱和氯化钾、氯化钠混合液,返回浮选流程作为浮选介质补充液。(4) Step (3) flotation separation gained potassium chloride and sodium chloride are stirred and washed with corresponding saturated brine respectively, filtered to obtain industrial grade potassium chloride and sodium chloride products, and the washing liquid is saturated potassium chloride , sodium chloride mixed solution, return to the flotation process as flotation medium replenishment liquid. 2.根据权利要求1所述回收并分离垃圾焚烧飞灰中钾盐和钠盐的方法,其特征在于,步骤(1)所述垃圾焚烧飞灰主要指重金属含量较低的飞灰,钾盐、钠盐、钙盐的可溶性盐主要是氯化钾、氯化钠、氯化钙。2. reclaiming according to claim 1 and separating the method for sylvite and sodium salt in the waste incineration fly ash, it is characterized in that, the described waste incineration fly ash of step (1) mainly refers to the fly ash with lower heavy metal content, potassium salt The soluble salts of , sodium, and calcium salts are mainly potassium chloride, sodium chloride, and calcium chloride. 3.根据权利要求1所述回收并分离垃圾焚烧飞灰中钾盐和钠盐的方法,其特征在于,步骤(1)所述石英砂与飞灰质量比为1:2~2:1,石英砂粒度为40~60目,飞灰与水质量比为1:1~1:4,搅拌速度为200~500r·min-1,搅拌时间为10~60min,擦洗次数为2~5次。3. according to claim 1, reclaim and separate the method for potassium salt and sodium salt in waste incineration fly ash, it is characterized in that, step (1) described quartz sand and fly ash mass ratio are 1:2~2:1, The particle size of quartz sand is 40-60 mesh, the mass ratio of fly ash to water is 1:1-1:4, the stirring speed is 200-500r·min-1, the stirring time is 10-60min, and the scrubbing frequency is 2-5 times. 4.根据权利要求1所述回收并分离垃圾焚烧飞灰中钾盐和钠盐的方法,其特征在于,步骤(1)所述石英砂与飞灰分离采用设备为旋流分级机,先分离石英砂后再固液分离。4. according to claim 1, reclaim and separate the method for sylvite and sodium salt in the waste incineration fly ash, it is characterized in that, step (1) described quartz sand and fly ash separation employing equipment is a cyclone classifier, separates first After the quartz sand is separated from the solid and liquid. 5.根据权利要求1所述回收并分离垃圾焚烧飞灰中钾盐和钠盐的方法,其特征在于,步骤(2)所述酸为盐酸,优选蒸发pH范围是5~5.5。5. The method for recovering and separating potassium salt and sodium salt in waste incineration fly ash according to claim 1, characterized in that the acid in step (2) is hydrochloric acid, and the preferred evaporation pH range is 5-5.5. 6.根据权利要求1所述回收并分离垃圾焚烧飞灰中钾盐和钠盐的方法,其特征在于,步骤(3)采用自制的水溶性胺类捕收剂进行浮选分离,胺类包括乙二胺、十二胺、十八胺、二十胺及混合胺中的一种或其混合物,抑制剂主要为柠檬酸、柠檬酸钠、羧甲基纤维素中的一种或任两种,浮选后产生的废盐水经过滤后返回流程继续使用。6. according to claim 1, reclaim and separate the method for potassium salt and sodium salt in waste incineration fly ash, it is characterized in that, step (3) adopts self-made water-soluble amine collector to carry out flotation separation, and amine comprises One of ethylenediamine, dodecylamine, octadecylamine, eicosylamine and mixed amines or a mixture thereof, and the main inhibitor is one or any two of citric acid, sodium citrate, and carboxymethyl cellulose , The waste brine generated after flotation is filtered and returned to the process for continued use. 7.根据权利要求1所述回收并分离垃圾焚烧飞灰中钾盐和钠盐的方法,其特征在于,步骤(4)对氯化钾、氯化钠进行搅拌洗涤所采用饱和盐水量为杂质含量的2~5倍,搅拌洗涤时间为10~60min,洗涤分离后饱和盐水返回浮选流程作为浮选介质补充液。7. reclaim and separate the method for potassium salt and sodium salt in the waste incineration fly ash according to claim 1, it is characterized in that, step (4) carries out stirring washing to potassium chloride, sodium chloride and adopts saturated brine amount to be impurity The content is 2 to 5 times, and the stirring and washing time is 10 to 60 minutes. After washing and separation, the saturated brine is returned to the flotation process as the flotation medium replenishment liquid.
CN201910941482.3A 2019-09-30 2019-09-30 Method for recovering and separating potassium salt and sodium salt in waste incineration fly ash Pending CN110589856A (en)

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CN115159554A (en) * 2022-06-30 2022-10-11 江苏天楹等离子体科技有限公司 Waste incineration fly ash recycling and calcium salt recycling system and method
CN115321558A (en) * 2022-03-31 2022-11-11 浙江大洋生物科技集团股份有限公司 Purification and comprehensive utilization method of fly ash washing byproduct potassium chloride
CN119794040A (en) * 2025-03-12 2025-04-11 苏州乔发环保科技股份有限公司 Garbage fly ash washing treatment method and system

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CN112391642A (en) * 2020-10-16 2021-02-23 浙江中陶环保科技集团有限公司 Method for preparing sodium hydroxide and potassium hydroxide by using municipal solid waste incineration fly ash
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CN114910470A (en) * 2021-02-09 2022-08-16 中国科学院青海盐湖研究所 Method for determining octadecylamine in potassium fertilizer flotation slurry
CN113955889A (en) * 2021-08-31 2022-01-21 江西盖亚环保科技有限公司 Resource recovery process of fly ash washing liquid
CN113955954A (en) * 2021-08-31 2022-01-21 江西盖亚环保科技有限公司 Carbon dioxide high pressure leaching and decalcification process of fly ash
CN113943011A (en) * 2021-09-17 2022-01-18 光大环保技术研究院(深圳)有限公司 Method for resource utilization of secondary fly ash after melting of hazardous waste plasma
CN113955772A (en) * 2021-10-21 2022-01-21 浙江工商大学 A kind of separation and purification method of fly ash washing soluble chloride salt
CN113830793A (en) * 2021-11-04 2021-12-24 河北工业大学 Method for recovering sodium salt and potassium salt in wastewater
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CN114455623A (en) * 2021-11-09 2022-05-10 陈彤 A kind of resource utilization method of waste incineration fly ash
CN114602926A (en) * 2022-03-07 2022-06-10 李晓清 Device and process for resourceful treatment of waste incineration fly ash
CN115321558A (en) * 2022-03-31 2022-11-11 浙江大洋生物科技集团股份有限公司 Purification and comprehensive utilization method of fly ash washing byproduct potassium chloride
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