CN102031381A - Process for preparing sodium pyroantimonate from arsenic- and stibium-containing smoke ash - Google Patents

Process for preparing sodium pyroantimonate from arsenic- and stibium-containing smoke ash Download PDF

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Publication number
CN102031381A
CN102031381A CN2010105742067A CN201010574206A CN102031381A CN 102031381 A CN102031381 A CN 102031381A CN 2010105742067 A CN2010105742067 A CN 2010105742067A CN 201010574206 A CN201010574206 A CN 201010574206A CN 102031381 A CN102031381 A CN 102031381A
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arsenic
naoh
concentration
sodium
temperature
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CN102031381B (en
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谢兆凤
张圣南
季勇
马辉
曹永贵
曹永德
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Chengzhou City Jingui Silver Co Ltd
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Chengzhou City Jingui Silver Co Ltd
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    • 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

Abstract

The invention discloses a process for preparing sodium pyroantimonate from arsenic- and stibium-containing smoke ash and belongs to the field of wet-process metallurgy. The production process for preparing the sodium pyroantimonate is characterized by comprising the following steps of: using NaOH and Na2CO3 or mixing the NaOH and Na2CO3, and performing wet-process pretreatment to remove arsenic; precipitating arsenic in arsenic-containing leaching liquor by using Na2S to obtain an arsenic sulfide byproduct; leaching arsenic- and stibium-containing leaching residues by mixing the Na2S and NaOH, returning lead residue, smelting, and recovering lead, silver and other valuable metals; blowing oxygen-rich compressed air into stibium-containing leaching liquor to prepare a sodium pyroantimonate product; and concentrating and crystallizing oxidized liquor to prepare Na2S2O3. The process has the advantages of no environmental pollution, simple equipment, low investment, high comprehensive utilization rate, low cost, suitability for industrial production, and the like.

Description

With containing the technology that arsenic antimony cigarette ash prepares sodium pyroantimoniate
Technical field
The present invention relates to a kind of usefulness and contain the technology that arsenic antimony cigarette ash prepares sodium pyroantimoniate, belong to the hydrometallurgy field.
Technical background
At present, rare precious metal products such as China's most of precious metal smelting silver that enterprise produces, bismuth, very major part reclaims from copper, lead anode slurry.My company produces a large amount of arsenic antimony cigarette ashes that contain, and contains valuable metals such as a certain amount of lead, silver when reclaiming silver from lead anode slurry in the process of bessemerizing.Wherein, contain Sb:30%～40%, As:5%～10%, Pb:20%～25%, Ag:1%～2%; As, Sb mainly exist with the oxidation form.If can not be used effectively, not only influence production efficiency, and easily environment has been caused secondary pollution, the valuable metal utilization ratio is low, has influenced the economic benefit of company.It is a great problem that nonferrous smelting producer faces that the processing that contains arsenic antimony cigarette ash that the silver converter is produced is reclaimed, and now domestic report seldom and is failed to accomplish to separate more completely with comprehensive and reclaimed.About containing the wet method extract technology of arsenic antimony cigarette ash, relevant report is not arranged as yet yet at present in relevant document.
Summary of the invention
Technical problem to be solved by this invention is: develop a kind of usefulness and contain the technology that arsenic antimony cigarette ash prepares sodium pyroantimoniate, by cigarette ash is handled, As and Sb in the Separation and Recovery cigarette ash, the comprehensive valuable element that reclaims, and the sodium pyroantimoniate product of preparation high added value, reduce the soot amount of Returning smelting, the economical efficiency so that height is produced solves second environmental pollution.
Technical scheme of the present invention is: a kind of usefulness contains the technology that arsenic antimony cigarette ash prepares sodium pyroantimoniate, is finished by following technological process.
A, pre-treatment dearsenification:
To contain arsenic antimony cigarette ash and NaOH solution and Na 2CO 3Solution is stirring heating in reactor together, reacts after 0.5～4 hour, filters; Processing condition are: solid-to-liquid ratio 1: 3～8; 80～100 ℃ of temperature; NaOH concentration 40～120g/L; Na 2CO 3Concentration 10～40g/L;
B, heavy arsenic:
The filtrate stirring of A step is added Na 2S sinks arsenic, filter the red arsenic product, filtrate is returned pretreatment process; Heavy arsenic processing condition are: 50～80 ℃ of temperature, and 0.5～2 hour time, the sodium sulphite add-on is 1～2 times that solution contains the arsenic quality;
C, Sodium Sulphide soak:
The crystalline mother solution that A step gained filter residue is added water or uses the back operation to be returned is sized mixing, and uses Na 2S, NaOH mixing solutions leach, and are incubated 2～5 hours after-filtration; Processing condition are: solid-to-liquid ratio 1: 4～10; 80～100 ℃ of temperature; PH value 10～11; Na 2S concentration 80～150g/L; NaOH concentration 10～50g/L;
D, send smelting system, further reclaim lead, silver-colored valuable element with common process with the leached mud of C step;
E, oxidation:
C step leach liquor is fed the oxygen enrichment compressed air oxidation 0.5～5 hour, produce crystallization; Oxygen containing concentration of volume percent is 30%～60% in the oxygen enrichment pressurized air; The compressed-air actuated pressure 0.4～0.6Mp of oxygen enrichment; 60～80 ℃ of temperature of reaction; Filtration makes solid-liquid separation, with crystallizing and washing, drying and obtain the sodium pyroantimoniate product;
F, condensing crystal:
With liquid condensing crystal behind the E stage oxidation, obtain purer Sulfothiorine product, crystalline mother solution returns C step Sodium Sulphide and soaks operation and do adjusting slurry and use.
Technical thought of the present invention is: the present invention is handled to be contained in the arsenic antimony cigarette ash, and arsenic, antimony major part exist with trivalent, and plumbous major part exists with the plumbous oxide form.Make full use of the difference of the chemical property of three's oxide compound, accomplish to separate to greatest extent the three, realize the efficient recovery of valuable element.The pretreatment stage alkaline purification utilizes white arsenic more to be soluble in the characteristic of alkaline solution than antimonous oxide, plumbous oxide, realizes preliminary dearsenification.Arsenic containing solution is if directly make sodium arseniate, then energy consumption height; If it is be prepared into Tricalcium arsenate, then uneconomical; The present invention utilizes antimonous oxide to be soluble in the character of sodium sulfide solution, soaks separation of lead antimony with Sodium Sulphide.Leach liquor CONTROL PROCESS condition prepares the sodium pyroantimoniate product with oxygen enrichment pressurized air.The oxidated solution crystallization prepares Sulfothiorine.By the enforcement of this invented technology, the control proper technical conditions, thoroughly separation of lead, arsenic, antimony valuable element are realized effectively comprehensive the recovery, obtain good economic benefit.
Relevant reaction in the invention is as follows:
The pre-treatment dearsenification:
As 2O 3+6NaOH＝2Na 3AsO 3+3H 2O
Heavy arsenic:
2Na 3AsO 3+5Na 2S+8H 2O+O 2＝As 2S 5↓+16NaOH
Sodium Sulphide soaks:
As 2O 3+6Na 2S+3H 2O＝2Na 3AsS 3+6NaOH
PbO+Na 2S+H 2O＝PbS+2NaOH
Sb 2O 3+6Na 2S+3H 2O＝2Na 2SbS 3+6NaOH
Oxidation:
2Na 3SbS 3+7O 2+2NaOH+5H 2O＝2NaSbO 3·3H 2O↓+3Na 2S 2O 3
In the process implementing process of the present invention, by the CONTROL PROCESS condition, during the pre-treatment dearsenification, arsenic decreasing ratio＞95%, and plumbous, antimony leaching yield＜10%.When Sodium Sulphide soaks,, can make the Sulfothiorine product of follow-up condensing crystal preparation very pure by control pH value of solution value.
The enforcement of this invented technology, output byproducts such as sodium pyroantimoniate, red arsenic, Sulfothiorine, realized effective separation of each valuable element.Whole process does not have waste water, waste gas to efflux, and does not produce solid waste yet and need stack processing, has solved this well and has contained the handling problem of arsenic converter cigarette ash.In addition, this processing unit requires simply, investment is low, be easy to realize industrialization.
Description of drawings
Fig. 1: process flow sheet of the present invention
Embodiment
Embodiment 1:
Get cigarette ash 200g, contain As:9.4%, Sb:33.8%, Pb:22.3%.During the pre-treatment dearsenification, pressed solid-to-liquid ratio 1: 5, NaOH concentration 80g/L, Na 2CO 3Concentration 20g/L, 85～90 ℃ of temperature, 2 hours reaction times control reaction conditions.Reach As leaching yield 95.42%, Pb leaching yield 6.36%, the treatment effect of Sb leaching yield 4.87%.When leach liquor sodium sulphite sank arsenic, temperature was 70 ℃, and the sodium sulphite dosage is 1.5 times that solution contains the arsenic quality, the deposition rate 89.73% of arsenic, and red arsenic contain As:51.82%.When Sodium Sulphide soaks the pre-treatment leached mud, solid-to-liquid ratio 1: 8, Na 2S concentration 120g/L, NaOH concentration 20g/L, 95 ℃ of temperature, 3 hours reaction times.The antimony leaching yield is 95.37%, lead is gone into slag rate 99.65%.When feeding the oxygen-rich air oxidation, oxygen concentration of volume percent 43%, pressure 0.4Mp, oxidization time 3 hours, filtration, washing, the dry sodium pyroantimoniate product that gets, the antimony percent crystallization in massecuite reaches 99.53%, contains Sb 2O 5: 64.90%, Na 2O:12.84%, As:0.0037%, Pb:0.0009%, Fe:0.0042%, Cu:0.0009%, Sulfothiorine percent crystallization in massecuite 91%, Na 2S 2O 3% 〉=93%.
Embodiment 2:
The cigarette ash 200g of present embodiment contains As:6.08%, Sb:35.46%, Pb:21.39%.During the pre-treatment dearsenification, by solid-to-liquid ratio 1: 4, NaOH concentration 100g/L, Na 2CO 3Concentration 10g/L, 90～95 ℃ of temperature, 4 hours reaction times control reaction conditions.Reach the treatment effect of As leaching yield 98.35%, Pb leaching yield 7.12%, Sb leaching yield 5.25%.When leach liquor sodium sulphite sank arsenic, temperature was 60 ℃, and the sodium sulphite dosage is 2 times that solution contains the arsenic quality, the deposition rate 93.74% of arsenic, and red arsenic contain As:48.68%.When Sodium Sulphide soaks the pre-treatment leached mud, solid-to-liquid ratio 1: 10, Na2S concentration 110g/L, NaOH concentration 10g/L, 90 ℃ of temperature, 4 hours reaction times.The antimony leaching yield is 96.18%, lead is gone into slag rate 99.43%.When feeding the oxygen-rich air oxidation, oxygen concentration of volume percent 52%, pressure 0.4Mp, oxidization time 2 hours, filtration, washing, the dry sodium pyroantimoniate product that gets, the antimony percent crystallization in massecuite reaches 99.52%, contains Sb 2O 5: 64.85%; Na 2O:12.87%; As:0.0040%; Pb:0.0010%; Fe:0.0045%; Cu:0.0010%.Sulfothiorine percent crystallization in massecuite 90%, Na 2S 2O 3% 〉=95%.
Embodiment 3:
Get cigarette ash 200g, contain As:9%, Sb:35.2%, Pb:21.2%.During the pre-treatment dearsenification, pressed solid-to-liquid ratio 1: 3; NaOH concentration 40g/L, Na 2CO 3Concentration 40g/L, 80～90 ℃ of temperature, 0.5 hour reaction times control reaction conditions.Reach the treatment effect of As leaching yield 95.42%, Pb leaching yield 6.36%, Sb leaching yield 4.87%.When leach liquor sodium sulphite sank arsenic, temperature was 50 ℃, and the sodium sulphite dosage is 1 times that solution contains the arsenic quality, the deposition rate 89.73% of arsenic, and red arsenic contain As:51.82%.When Sodium Sulphide soaks the pre-treatment leached mud, solid-to-liquid ratio 1: 4, Na 2S concentration 80g/L, NaOH concentration 50g/L, 80 ℃ of temperature, 2 hours reaction times.The antimony leaching yield is 95.37%, lead is gone into slag rate 99.65%.When feeding the oxygen-rich air oxidation, oxygen concentration of volume percent 30%, pressure 0.6Mp, oxidization time 0.5 hour, filtration, washing, the dry sodium pyroantimoniate product that gets, the antimony percent crystallization in massecuite reaches 99.53%, contains Sb 2O 5: 64.90%, Na 2O:12.84%, As:0.0037%, Pb:0.0010%, Fe:0.0057%, Cu:0.0008%, Sulfothiorine percent crystallization in massecuite 90%, Na 2S 2O 3% 〉=92%.
Embodiment 4:
Get cigarette ash 250g, contain As:10.1%, Sb:30%, Pb:24.6%.During the pre-treatment dearsenification, pressed solid-to-liquid ratio 1: 8; NaOH concentration 120g/L; Na 2CO 3Concentration 40g/L, 85～100 ℃ of temperature, 2 hours reaction times control reaction conditions.Reach the treatment effect of As leaching yield 95.8%, Pb leaching yield 6.56%, Sb leaching yield 4.77%.When leach liquor sodium sulphite sank arsenic, temperature was 80 ℃, and the sodium sulphite dosage is 1.5 times that solution contains the arsenic quality, the deposition rate 89.73% of arsenic, and red arsenic contain As:51.82%.When Sodium Sulphide soaks the pre-treatment leached mud, solid-to-liquid ratio 1: 4, Na 2S concentration 150g/L, NaOH concentration 50g/L, 100 ℃ of temperature, 5 hours reaction times.The antimony leaching yield is 94.55%, lead is gone into slag rate 98.74%.When feeding the oxygen-rich air oxidation, oxygen concentration of volume percent 60%, pressure 0.6Mp, oxidization time 5 hours, filtration, washing, the dry sodium pyroantimoniate product that gets, the antimony percent crystallization in massecuite reaches 99.60%, contains Sb 2O 5: 68.11%, Na 2O:11.95%, As:0.00267%, Pb:0.0008%, Fe:0.0033%, Gu:0.00028%, Sulfothiorine percent crystallization in massecuite 94%, Na 2S 2O 3% 〉=93%.

Claims (1)

1. one kind with containing the technology that arsenic antimony cigarette ash prepares sodium pyroantimoniate, it is characterized in that being finished by following technological process:
A, pre-treatment dearsenification:
To contain arsenic antimony cigarette ash and NaOH solution and Na 2CO 3Solution is stirring heating in reactor together, reacts after 0.5～4 hour, filters; Processing condition are: solid-to-liquid ratio 1: 3～8; 80～100 ℃ of temperature; NaOH concentration 40～120g/L; Na 2CO 3Concentration 10～40g/L;
B, heavy arsenic:
The filtrate stirring of A step is added Na 2S sinks arsenic, filter the red arsenic product, filtrate is returned pretreatment process; Heavy arsenic processing condition are: 50～80 ℃ of temperature, and 0.5～2 hour time, the sodium sulphite add-on is 1～2 times that solution contains the arsenic quality;
C, Sodium Sulphide soak:
The crystalline mother solution that A step gained filter residue is added water or uses the back operation to be returned is sized mixing, and uses Na 2S, NaOH mixing solutions leach, and are incubated 2～5 hours after-filtration; Processing condition are: solid-to-liquid ratio 1: 4～10; 80～100 ℃ of temperature; PH value 10～11; Na 2S concentration 80～150g/L; NaOH concentration 10～50g/L;
D, send smelting system, further reclaim lead, silver-colored valuable element with common process with the leached mud of C step;
E, oxidation:
C step leach liquor is fed the oxygen enrichment compressed air oxidation 0.5～5 hour, produce crystallization; Oxygen containing concentration of volume percent is 30%～60% in the oxygen enrichment pressurized air; The compressed-air actuated pressure 0.4～0.6Mp of oxygen enrichment; 60～80 ℃ of temperature of reaction; Filtration makes solid-liquid separation, with crystallizing and washing, drying and obtain the sodium pyroantimoniate product;
F, condensing crystal:
With liquid condensing crystal behind the E stage oxidation, obtain purer Sulfothiorine product, crystalline mother solution returns C step Sodium Sulphide and soaks operation and do adjusting slurry and use.
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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103290221A (en) * 2012-02-28 2013-09-11 兰州理工大学 Method for recovering copper, arsenium and antimony from black copper sludge
CN103318959A (en) * 2013-07-15 2013-09-25 郴州市金贵银业股份有限公司 Production method for sodium pyroantimonate by using high-temperature high-pressure pure-oxygen oxidation
CN103849782A (en) * 2012-11-28 2014-06-11 湖南宇腾有色金属股份有限公司 High-pressure alkaline leaching arsenic-removal method for high-arsenic antimony white powder
CN104911364A (en) * 2015-06-26 2015-09-16 郴州市金贵银业股份有限公司 Environment-friendly and high-efficiency production method of antimony white by using Sb and As-containing ash
CN105063361A (en) * 2015-08-20 2015-11-18 江西铜业股份有限公司 Method for comprehensively recovering valuable metal from copper anode slime
CN106180138A (en) * 2016-07-15 2016-12-07 深圳市危险废物处理站有限公司 A kind of processing method of arsenic-containing waste
CN107354301A (en) * 2017-07-19 2017-11-17 中南大学 A kind of method for improving arsenic-containing material arsenic-removing rate
CN107523702A (en) * 2017-08-23 2017-12-29 中南大学 A kind of method that sodium salt system pressure oxidation prepares sodium pyroantimonate
CN107858521A (en) * 2017-12-07 2018-03-30 郴州市金贵银业股份有限公司 The method that cigarette ash containing antimony prepares sodium pyroantimonate
CN109182765A (en) * 2018-10-18 2019-01-11 郴州市金贵银业股份有限公司 A method of star metal is prepared with antimony cigarette ash
CN111118301A (en) * 2019-12-31 2020-05-08 焱鑫环保科技有限公司 Method for recycling arsenic slag resources by arsenic and alkali in freezing separation alkali slag water leaching solution
CN112375915A (en) * 2020-10-27 2021-02-19 西北矿冶研究院 Method for removing harmful elements arsenic and antimony in high-content bismuth-silver smelting slag
CN113371757A (en) * 2021-07-09 2021-09-10 中南大学 Method for preparing sodium pyroantimonate and regenerating and recycling mother liquor
CN114561558A (en) * 2022-02-23 2022-05-31 中南大学 Method for recovering antimony and solid arsenic from arsenic-containing crystal
CN116692941A (en) * 2023-07-06 2023-09-05 中南大学 Method for preparing high-quality sodium pyroantimonate through gradient purification and oxidation

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1046880A (en) * 1989-05-03 1990-11-14 中国有色金属工业总公司矿产地质研究院 The wet method preparation method of multiple antimony product
CN1312392A (en) * 2000-03-07 2001-09-12 株洲冶炼厂 Arsenic smoke dust treating method
CN1408646A (en) * 2001-09-25 2003-04-09 柳州市环东金属材料厂 Process for producing sodium pyroantimonate

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1046880A (en) * 1989-05-03 1990-11-14 中国有色金属工业总公司矿产地质研究院 The wet method preparation method of multiple antimony product
CN1312392A (en) * 2000-03-07 2001-09-12 株洲冶炼厂 Arsenic smoke dust treating method
CN1408646A (en) * 2001-09-25 2003-04-09 柳州市环东金属材料厂 Process for producing sodium pyroantimonate

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
《湖南有色金属》 20050228 周红华 高砷锑烟灰综合回收工艺研究 21-22,53 1 第21卷, 第1期 *
《辽宁化工》 20091031 龙志娟 用锑砷烟灰制取焦锑酸钠和砷酸钠 738-740 1 第38卷, 第10期 *
罗庆文，等: "高砷锑多金属的锡烟尘的处理", 《有色金属 冶炼部分》, no. 1, 31 December 1989 (1989-12-31), pages 18 *
龙志娟: "用锑砷烟灰制取焦锑酸钠和砷酸钠", 《辽宁化工》, vol. 38, no. 10, 31 October 2009 (2009-10-31), pages 738 - 740 *

Cited By (20)

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Publication number Priority date Publication date Assignee Title
CN103290221A (en) * 2012-02-28 2013-09-11 兰州理工大学 Method for recovering copper, arsenium and antimony from black copper sludge
CN103849782A (en) * 2012-11-28 2014-06-11 湖南宇腾有色金属股份有限公司 High-pressure alkaline leaching arsenic-removal method for high-arsenic antimony white powder
CN103849782B (en) * 2012-11-28 2014-12-10 湖南宇腾有色金属股份有限公司 High-pressure alkaline leaching arsenic-removal method for high-arsenic antimony white powder
CN103318959A (en) * 2013-07-15 2013-09-25 郴州市金贵银业股份有限公司 Production method for sodium pyroantimonate by using high-temperature high-pressure pure-oxygen oxidation
CN104911364A (en) * 2015-06-26 2015-09-16 郴州市金贵银业股份有限公司 Environment-friendly and high-efficiency production method of antimony white by using Sb and As-containing ash
CN105063361A (en) * 2015-08-20 2015-11-18 江西铜业股份有限公司 Method for comprehensively recovering valuable metal from copper anode slime
CN105063361B (en) * 2015-08-20 2017-03-22 江西铜业股份有限公司 Method for comprehensively recovering valuable metal from copper anode slime
CN106180138A (en) * 2016-07-15 2016-12-07 深圳市危险废物处理站有限公司 A kind of processing method of arsenic-containing waste
CN107354301B (en) * 2017-07-19 2019-01-25 中南大学 A method of improving arsenic-containing material arsenic-removing rate
CN107354301A (en) * 2017-07-19 2017-11-17 中南大学 A kind of method for improving arsenic-containing material arsenic-removing rate
CN107523702A (en) * 2017-08-23 2017-12-29 中南大学 A kind of method that sodium salt system pressure oxidation prepares sodium pyroantimonate
CN107858521A (en) * 2017-12-07 2018-03-30 郴州市金贵银业股份有限公司 The method that cigarette ash containing antimony prepares sodium pyroantimonate
CN109182765A (en) * 2018-10-18 2019-01-11 郴州市金贵银业股份有限公司 A method of star metal is prepared with antimony cigarette ash
CN111118301A (en) * 2019-12-31 2020-05-08 焱鑫环保科技有限公司 Method for recycling arsenic slag resources by arsenic and alkali in freezing separation alkali slag water leaching solution
CN112375915A (en) * 2020-10-27 2021-02-19 西北矿冶研究院 Method for removing harmful elements arsenic and antimony in high-content bismuth-silver smelting slag
CN113371757A (en) * 2021-07-09 2021-09-10 中南大学 Method for preparing sodium pyroantimonate and regenerating and recycling mother liquor
CN113371757B (en) * 2021-07-09 2022-11-08 中南大学 Method for preparing sodium pyroantimonate and regenerating and recycling mother liquor
CN114561558A (en) * 2022-02-23 2022-05-31 中南大学 Method for recovering antimony and solid arsenic from arsenic-containing crystal
CN114561558B (en) * 2022-02-23 2023-08-29 中南大学 Method for recycling antimony and fixing arsenic from arsenic-containing crystal
CN116692941A (en) * 2023-07-06 2023-09-05 中南大学 Method for preparing high-quality sodium pyroantimonate through gradient purification and oxidation

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