CN103602834A - Selective oxidation-reduction method for recycling arsenic and antimony from arsenic-antimony smoke - Google Patents
Selective oxidation-reduction method for recycling arsenic and antimony from arsenic-antimony smoke Download PDFInfo
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- 229910052787 antimony Inorganic materials 0.000 title claims abstract description 85
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 61
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 48
- 230000033116 oxidation-reduction process Effects 0.000 title claims abstract description 13
- DLISVFCFLGSHAB-UHFFFAOYSA-N antimony arsenic Chemical compound [As].[Sb] DLISVFCFLGSHAB-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 239000000779 smoke Substances 0.000 title description 4
- 238000004064 recycling Methods 0.000 title 1
- 239000000428 dust Substances 0.000 claims abstract description 21
- 239000003517 fume Substances 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 17
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 16
- 239000007789 gas Substances 0.000 claims abstract description 12
- 230000001590 oxidative effect Effects 0.000 claims abstract description 12
- 238000011084 recovery Methods 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 239000003245 coal Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 4
- 239000003546 flue gas Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000003921 oil Substances 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 2
- HJTAZXHBEBIQQX-UHFFFAOYSA-N 1,5-bis(chloromethyl)naphthalene Chemical compound C1=CC=C2C(CCl)=CC=CC2=C1CCl HJTAZXHBEBIQQX-UHFFFAOYSA-N 0.000 abstract description 4
- 238000003723 Smelting Methods 0.000 abstract description 4
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 abstract description 4
- AHBGXHAWSHTPOM-UHFFFAOYSA-N 1,3,2$l^{4},4$l^{4}-dioxadistibetane 2,4-dioxide Chemical compound O=[Sb]O[Sb](=O)=O AHBGXHAWSHTPOM-UHFFFAOYSA-N 0.000 abstract description 3
- 229910000411 antimony tetroxide Inorganic materials 0.000 abstract description 3
- 238000009856 non-ferrous metallurgy Methods 0.000 abstract description 2
- 238000002386 leaching Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- DJHGAFSJWGLOIV-UHFFFAOYSA-N Arsenic acid Chemical compound O[As](O)(O)=O DJHGAFSJWGLOIV-UHFFFAOYSA-N 0.000 description 1
- RMBBSOLAGVEUSI-UHFFFAOYSA-H Calcium arsenate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-][As]([O-])([O-])=O.[O-][As]([O-])([O-])=O RMBBSOLAGVEUSI-UHFFFAOYSA-H 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ZVQHJJXXEAGYOP-UHFFFAOYSA-N [Sb]=O.[As] Chemical compound [Sb]=O.[As] ZVQHJJXXEAGYOP-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229940000488 arsenic acid Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229940103357 calcium arsenate Drugs 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- ZODDGFAZWTZOSI-UHFFFAOYSA-N nitric acid;sulfuric acid Chemical compound O[N+]([O-])=O.OS(O)(=O)=O ZODDGFAZWTZOSI-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
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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
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Abstract
本发明涉及一种选择性氧化-还原法回收砷锑烟尘中砷、锑的方法，属于有色冶金技术领域。首先选择性氧化回收砷：向砷锑烟尘中通入氧化性气体，在温度为400～800℃反应20～90min，在此过程中对As2O3挥发烟气进行收集，反应完成后获得二次含锑物料；然后还原回收锑：向上述步骤获得的二次含锑物料中加入还原剂，在温度为800～1000℃条件下反应30～180min，即能获得粗锑。本发明充分利用低温下三氧化二砷易挥发、四氧化二锑不易挥发的特点，对砷锑烟尘进行选择性氧化，并挥发分离脱除砷，再进行还原熔炼获得粗锑，工艺简单，具有较好的工业应用前景。
The invention relates to a method for recovering arsenic and antimony in arsenic and antimony dust by a selective oxidation-reduction method, and belongs to the technical field of nonferrous metallurgy. First, selectively oxidize and recover arsenic: introduce oxidizing gas into the arsenic-antimony fume, react at a temperature of 400-800°C for 20-90 minutes, collect As 2 O 3 volatilized fumes during the process, and obtain two Secondary antimony-containing material; then reducing and recovering antimony: adding a reducing agent to the secondary antimony-containing material obtained in the above steps, and reacting at a temperature of 800-1000°C for 30-180 minutes to obtain crude antimony. The invention makes full use of the characteristics that arsenic trioxide is easy to volatilize and antimony tetroxide is not easy to volatilize at low temperature, and selectively oxidizes arsenic and antimony dust, and volatilizes and separates arsenic to remove arsenic, and then performs reduction smelting to obtain crude antimony. The process is simple and has good Industrial application prospects.
Description
技术领域 technical field
本发明涉及一种选择性氧化-还原法回收砷锑烟尘中砷、锑的方法，属于有色冶金技术领域。 The invention relates to a method for recovering arsenic and antimony in arsenic and antimony dust by a selective oxidation-reduction method, and belongs to the technical field of nonferrous metallurgy.
背景技术 Background technique
在重金属冶炼回收贵金属过程中，产生的烟尘中常含有较高的砷锑，这是宝贵的二次资源。为了综合利用有价金属，减少环境污染，加大对砷锑分离技术的研究具有重大的意义。 In the process of heavy metal smelting and recovery of precious metals, the dust generated often contains high arsenic and antimony, which are valuable secondary resources. In order to comprehensively utilize valuable metals and reduce environmental pollution, it is of great significance to increase the research on the separation technology of arsenic and antimony.
目前关于砷锑分离的方法有火法和湿法两种。火法分离中，最常用的是真空蒸馏法，利用其沸点性质的不同而使砷锑分离，此法虽高效的分离砷、锑，但真空蒸馏技术条件要求高且对环境保护安全措施要求严，经济成本也较高。砷锑的湿法分离分为酸法和碱法两种。酸法以硫酸-硝酸混合溶液为浸出剂，其中的硝酸即使浸出剂，又是砷的氧化剂。喷入石灰乳，将砷酸沉淀为砷酸钙而脱除。碱法-电化浸出法是在碱性浸出槽内装入阳极、阴极，并通以直流电，强化砷的浸出。 At present, there are two methods for the separation of arsenic and antimony: fire method and wet method. In fire separation, the most commonly used method is vacuum distillation, which separates arsenic and antimony by using its different boiling point properties. Although this method can efficiently separate arsenic and antimony, it has high technical requirements for vacuum distillation and strict requirements for environmental protection and safety measures. , the economic cost is also higher. The wet separation of arsenic and antimony can be divided into acid method and alkali method. The acid method uses sulfuric acid-nitric acid mixed solution as the leaching agent, and the nitric acid is not only the leaching agent, but also the oxidant of arsenic. Spray milk of lime to remove arsenic acid by precipitation into calcium arsenate. The alkaline method-electrochemical leaching method is to put anode and cathode in the alkaline leaching tank, and pass direct current to strengthen the leaching of arsenic.
在高砷烟尘电热回转窑焙烧法脱砷工艺中，其工艺特点是利用了低温下三氧化二砷易挥发的性质，使As以As2O3的形式挥发脱除，As2O3在120℃时已开始升华，到500℃时便强烈挥发，而锑经氧化成Sb2O4后却难以挥发。不同温度下As2O3的蒸气压如下表1。 In the arsenic removal process of high-arsenic dust electric heating rotary kiln roasting method, the technological feature is to use the volatile nature of arsenic trioxide at low temperature, so that As can be volatilized and removed in the form of As 2 O 3 . It begins to sublimate and volatilizes strongly at 500°C, while antimony is difficult to volatilize after being oxidized to Sb 2 O 4 . The vapor pressure of As 2 O 3 at different temperatures is shown in Table 1.
表1As2O3的蒸气压与温度的关系 Table 1 Relationship between vapor pressure and temperature of As 2 O 3
砷和锑的氧化过程是逐级进行的，其反应如下： The oxidation process of arsenic and antimony is carried out step by step, and the reaction is as follows:
2As+3/2O2=2As2O3 (1) 2As+3/2O 2 =2As 2 O 3 (1)
As2O3+O2=As2O5 (2) As 2 O 3 +O 2 =As 2 O 5 (2)
2Sb+3/2O2=2Sb2O3 (3) 2Sb+3/2O 2 =2Sb 2 O 3 (3)
Sb2O3+1/2O2=Sb2O4 (4) Sb 2 O 3 +1/2O 2 =Sb 2 O 4 (4)
采用HSC计算软件可知，反应（1）~（4）的氧势lgPO2随温度变化的关系如下图1。 Using the HSC calculation software, it can be seen that the relationship between the oxygen potential lgPO2 of the reactions (1)~(4) changing with the temperature is shown in Figure 1.
由图1可知，在温度高于673K，lgPO2介于-4.87~5.87Pa时，可以实现使三氧化二锑氧化为Sb2O4，而As2O3不被氧化，即不会进一步氧化为As2O5。在上述条件下，砷氧化成As2O3而挥发脱除，锑氧化成难以挥发的Sb2O4，从而使砷锑分离。 It can be seen from Figure 1 that when the temperature is higher than 673K and lgPO2 is between -4.87~5.87Pa, antimony trioxide can be oxidized to Sb 2 O 4 , while As 2 O 3 is not oxidized, that is, it will not be further oxidized is As 2 O 5 . Under the above conditions, arsenic is oxidized to As 2 O 3 for volatilization and removal, and antimony is oxidized to Sb 2 O 4 which is difficult to volatilize, thereby separating arsenic and antimony.
发明内容 Contents of the invention
针对上述现有技术存在的问题及不足，本发明提供一种选择性氧化-还原法回收砷锑烟尘中砷、锑的方法。本发明充分利用低温下三氧化二砷易挥发、四氧化二锑不易挥发的特点，对砷锑烟尘进行选择性氧化，并挥发分离脱除砷，再进行还原熔炼获得粗锑，工艺简单，具有较好的工业应用前景，本发明通过以下技术方案实现。 Aiming at the problems and deficiencies in the above-mentioned prior art, the present invention provides a method for recovering arsenic and antimony in arsenic and antimony dust by selective oxidation-reduction. The invention makes full use of the characteristics that arsenic trioxide is easy to volatilize and antimony tetroxide is not easy to volatilize at low temperature, and selectively oxidizes arsenic and antimony dust, and volatilizes and separates arsenic to remove arsenic, and then performs reduction smelting to obtain crude antimony. The process is simple and has good Foreground of industrial application, the present invention is realized through the following technical solutions.
一种选择性氧化-还原法回收砷锑烟尘中砷、锑的方法，其具体步骤如下： A method for reclaiming arsenic and antimony in arsenic and antimony dust by selective oxidation-reduction method, the specific steps are as follows:
（1）选择性氧化回收砷：向砷锑烟尘中通入流量为0.01～0.5L/min的氧化性气体，在温度为400～800℃反应20～90min，在此过程中对As2O3挥发烟气进行收集，反应完成后获得二次含锑物料； (1) Selective oxidation recovery of arsenic: Introduce an oxidizing gas with a flow rate of 0.01 to 0.5 L/min into the arsenic and antimony dust, and react at a temperature of 400 to 800 ° C for 20 to 90 minutes. During this process, As 2 O 3 Volatile flue gas is collected, and the secondary antimony-containing material is obtained after the reaction is completed;
（2）还原回收锑：向步骤（1）获得的二次含锑物料按照二次含锑物料与还原剂的质量比为10：（1～3）加入还原剂，在温度为800～1000℃条件下反应30～180min，即能获得粗锑。 (2) Reduction and recovery of antimony: Add a reducing agent to the secondary antimony-containing material obtained in step (1) according to the mass ratio of the secondary antimony-containing material to the reducing agent: 10: (1~3), at a temperature of 800~1000°C The crude antimony can be obtained by reacting for 30-180 minutes under the conditions.
所述砷锑烟尘包括以下质量百分比的组分：砷含量为5～20%，锑含量为30～60%。 The arsenic-antimony dust includes the following components in mass percentage: the content of arsenic is 5-20%, and the content of antimony is 30-60%.
所述氧化性气体为空气、富氧空气或氧气。 The oxidizing gas is air, oxygen-enriched air or oxygen.
所述步骤（1）中对As2O3挥发烟气的收集采用布袋收尘。 In the step (1), the As 2 O 3 volatilized flue gas is collected by bag dust collection.
所述还原剂为粉煤、油、焦炭粉中的一种或几种任意比例混合物。 The reducing agent is one or a mixture of several of pulverized coal, oil and coke powder in any proportion.
本发明的有益效果是：本方法充分利用低温下三氧化二砷易挥发、四氧化二锑不易挥发的特点，对砷锑烟尘进行选择性氧化，并挥发分离脱除砷，再进行还原熔炼获得粗锑，工艺简单，具有较好的工业应用前景。 The beneficial effects of the present invention are: the method makes full use of the characteristics that arsenic trioxide is easy to volatilize and antimony tetroxide is not easy to volatilize at low temperature, selectively oxidizes arsenic and antimony dust, and volatilizes and separates to remove arsenic, and then performs reduction smelting to obtain crude antimony. The process is simple and has good industrial application prospect.
附图说明 Description of drawings
图1是本发明砷锑氧化物的氧势随温度变化的关系图； Fig. 1 is the relation figure that the oxygen potential of arsenic-antimony oxide of the present invention changes with temperature;
图2是本发明工艺流程图。 Fig. 2 is a process flow diagram of the present invention.
具体实施方式 Detailed ways
下面结合附图和具体实施方式，对本发明作进一步说明。 The present invention will be further described below in combination with the accompanying drawings and specific embodiments.
实施例1 Example 1
如图2所示，该选择性氧化-还原法回收砷锑烟尘中砷、锑的方法，其具体步骤如下： As shown in Figure 2, this selective oxidation-reduction method reclaims the method for arsenic and antimony in the arsenic and antimony smoke dust, and its concrete steps are as follows:
（1）选择性氧化回收砷：向砷锑烟尘（砷锑烟尘包括以下质量百分比的组分：砷含量为5%，锑含量为30%）中通入流量为0.01L/min的氧化性气体，在温度为400℃反应20min，在此过程中对As2O3挥发烟气进行收集，反应完成后获得二次含锑物料，其中氧化性气体为空气，As2O3挥发烟气的收集采用布袋收尘； (1) Selective oxidation recovery of arsenic: Introduce an oxidizing gas with a flow rate of 0.01L/min into the arsenic-antimony fume (the arsenic-antimony fume includes the following components by mass percentage: the arsenic content is 5%, and the antimony content is 30%) , and reacted at a temperature of 400°C for 20 minutes. During this process, As 2 O 3 volatilized fumes were collected. After the reaction was completed, secondary antimony-containing materials were obtained, in which the oxidizing gas was air, and As 2 O 3 volatilized fumes were collected. Use cloth bag to collect dust;
（2）还原回收锑：向步骤（1）获得的二次含锑物料中按照二次含锑物料与还原剂的质量比为10：1加入还原剂，在温度为800℃条件下反应30min，即能获得粗锑，其中还原剂为粉煤。 (2) Recover antimony: Add reducing agent to the secondary antimony-containing material obtained in step (1) according to the mass ratio of secondary antimony-containing material to reducing agent is 10:1, and react at a temperature of 800°C for 30 minutes. That is, crude antimony can be obtained, wherein the reducing agent is pulverized coal.
经取样检测知，粗锑中含锑91.4%，含砷0.39%，锑的回收率为86.5%。 After sampling and detection, the crude antimony contained 91.4% antimony and 0.39% arsenic, and the recovery rate of antimony was 86.5%.
实施例2 Example 2
如图2所示，该选择性氧化-还原法回收砷锑烟尘中砷、锑的方法，其具体步骤如下： As shown in Figure 2, this selective oxidation-reduction method reclaims the method for arsenic and antimony in the arsenic and antimony smoke dust, and its concrete steps are as follows:
（1）选择性氧化回收砷：向砷锑烟尘（砷锑烟尘包括以下质量百分比的组分：砷含量为20%，锑含量为60%）中通入流量为0.5L/min的氧化性气体，在温度为800℃反应90min，在此过程中对As2O3挥发烟气进行收集，反应完成后获得二次含锑物料，其中氧化性气体为富氧空气，对As2O3挥发烟气的收集采用布袋收尘；
(1) Selective oxidation recovery of arsenic: Introduce an oxidizing gas with a flow rate of 0.5L/min into the arsenic-antimony fume (the arsenic-antimony fume includes the following mass percentage components: the arsenic content is 20%, and the antimony content is 60%) , and reacted at a
（2）还原回收锑：向步骤（1）获得的二次含锑物料中按照二次含锑物料与还原剂的质量比为10：3加入还原剂，在温度为1000℃条件下反应180min，即能获得粗锑，其中还原剂为质量1：1：1的粉煤、油和焦炭粉混合物。 (2) Recovering antimony: add a reducing agent to the secondary antimony-containing material obtained in step (1) according to the mass ratio of the secondary antimony-containing material to the reducing agent is 10:3, and react for 180 minutes at a temperature of 1000°C. That is, crude antimony can be obtained, wherein the reducing agent is a mixture of pulverized coal, oil and coke powder with a mass ratio of 1:1:1.
经取样检测知，粗锑中含锑90.2%，含砷0.35%，锑的回收率为88.2%。 After sampling and detection, the crude antimony contained 90.2% antimony and 0.35% arsenic, and the recovery rate of antimony was 88.2%.
实施例3 Example 3
如图2所示，该选择性氧化-还原法回收砷锑烟尘中砷、锑的方法，其具体步骤如下： As shown in Figure 2, this selective oxidation-reduction method reclaims the method for arsenic and antimony in the arsenic and antimony smoke dust, and its concrete steps are as follows:
（1）选择性氧化回收砷：向砷锑烟尘（砷锑烟尘包括以下质量百分比的组分：砷含量为15%，锑含量为40%）中通入流量为0.4L/min的氧化性气体，在温度为600℃反应70min，在此过程中对As2O3挥发烟气进行收集，反应完成后获得二次含锑物料，其中氧化性气体为氧气，对As2O3挥发烟气的收集采用布袋收尘； (1) Selective oxidation recovery of arsenic: Introduce an oxidizing gas with a flow rate of 0.4L/min into the arsenic-antimony fume (the arsenic-antimony fume includes the following components by mass percentage: the arsenic content is 15%, and the antimony content is 40%) , reacted at a temperature of 600°C for 70 minutes, during which the As 2 O 3 volatile fumes were collected, and after the reaction was completed, secondary antimony-containing materials were obtained, in which the oxidizing gas was oxygen, and the As 2 O 3 volatile fumes The collection adopts bag dust collection;
（2）还原回收锑：向步骤（1）获得的二次含锑物料中按照二次含锑物料与还原剂的质量比为10：2加入还原剂，在温度为900℃条件下反应120min，即能获得粗锑，其中还原剂为质量比1：1的粉煤和焦炭粉混合物。 (2) Recovering antimony: add a reducing agent to the secondary antimony-containing material obtained in step (1) according to the mass ratio of the secondary antimony-containing material to the reducing agent is 10:2, and react at a temperature of 900°C for 120 minutes. That is, crude antimony can be obtained, wherein the reducing agent is a mixture of pulverized coal and coke powder with a mass ratio of 1:1.
经取样检测知，粗锑中含锑93.5%，含砷0.31%，锑的回收率为89.6%。 After sampling and detection, the crude antimony contained 93.5% antimony and 0.31% arsenic, and the recovery rate of antimony was 89.6%.
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| CN104294053A (en) * | 2014-11-01 | 2015-01-21 | 中南大学 | Method for reduction, volatilization and separation of arsenic from smoke dust containing arsenic |
| CN104451171A (en) * | 2014-12-18 | 2015-03-25 | 中南大学 | Method for removing arsenic from arsenic containing smoke under fluidization |
| CN104789786A (en) * | 2015-04-01 | 2015-07-22 | 郴州雄风环保科技有限公司 | Method for harmlessly treating arsenic-containing waste slag and comprehensively recycling valuable metals in arsenic-containing waste slag |
| CN105695742A (en) * | 2016-02-24 | 2016-06-22 | 锡矿山闪星锑业有限责任公司 | Smelting method for low-temperature antimony reduction through antimony oxide |
| CN106381396A (en) * | 2016-09-13 | 2017-02-08 | 昆明理工大学 | Method for separating arsenic from antimony as well as recovering antimony through roasting of high arsenic-antimony smoke by solid oxidant |
| CN106702170A (en) * | 2016-12-16 | 2017-05-24 | 昆明理工大学 | Method for separating arsenic and recycling arsenic and antimony through high-arsenic-antimony smoke oxidization-fixation method |
| CN107058746A (en) * | 2017-04-27 | 2017-08-18 | 郴州市金贵银业股份有限公司 | A kind of method that antimony is separated from silver-colored smelting ash |
| CN107130115A (en) * | 2017-04-27 | 2017-09-05 | 郴州市金贵银业股份有限公司 | It is a kind of that arsenic, the method for antimony are separated from silver-colored smelting ash |
| CN107828967A (en) * | 2017-10-20 | 2018-03-23 | 昆明理工大学 | A kind of copper anode mud reduction organic sulfide method separation arsenic and the method for reclaiming antimony, tin |
| CN109628761A (en) * | 2018-12-29 | 2019-04-16 | 焱鑫环保科技有限公司 | A method of stibium trioxide is produced using high antimony secondary smoke dearsenification |
| CN109762996A (en) * | 2019-03-07 | 2019-05-17 | 昆明理工大学 | A method for separating arsenic and recovering antimony by high antimony and low arsenic soot oxidation-sulfidation immobilization method |
| CN110398403A (en) * | 2019-07-29 | 2019-11-01 | 华北电力大学（保定） | A preparation method and device for a stable arsenic trioxide standard gas |
| CN113955799A (en) * | 2021-10-20 | 2022-01-21 | 山东恒邦冶炼股份有限公司 | Method for purifying antimony-containing arsenic trioxide |
| CN114086002A (en) * | 2021-11-24 | 2022-02-25 | 云南锡业研究院有限公司 | Method for efficiently separating arsenic and antimony from high-arsenic smoke dust |
| CN116514164A (en) * | 2023-04-23 | 2023-08-01 | 山东恒邦冶炼股份有限公司 | Method and equipment for improving whiteness and purity of refined arsenic trioxide |
| CN117025979A (en) * | 2023-08-01 | 2023-11-10 | 昆明理工大学 | Method for efficiently enriching antimonous oxide in vacuum by using crude antimonous oxide |
| CN117286341A (en) * | 2023-10-09 | 2023-12-26 | 昆明冶金研究院有限公司 | Method for preparing arsenic-antimony base alloy from arsenic-antimony smelting smoke dust and arsenic-antimony base alloy |
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| CN104294053A (en) * | 2014-11-01 | 2015-01-21 | 中南大学 | Method for reduction, volatilization and separation of arsenic from smoke dust containing arsenic |
| CN104451171A (en) * | 2014-12-18 | 2015-03-25 | 中南大学 | Method for removing arsenic from arsenic containing smoke under fluidization |
| CN104789786A (en) * | 2015-04-01 | 2015-07-22 | 郴州雄风环保科技有限公司 | Method for harmlessly treating arsenic-containing waste slag and comprehensively recycling valuable metals in arsenic-containing waste slag |
| CN104789786B (en) * | 2015-04-01 | 2017-03-15 | 郴州雄风环保科技有限公司 | A kind of harmlessness disposing arsenic-containing waste residue and the method for synthetical recovery wherein valuable metal |
| CN105695742A (en) * | 2016-02-24 | 2016-06-22 | 锡矿山闪星锑业有限责任公司 | Smelting method for low-temperature antimony reduction through antimony oxide |
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| CN106702170A (en) * | 2016-12-16 | 2017-05-24 | 昆明理工大学 | Method for separating arsenic and recycling arsenic and antimony through high-arsenic-antimony smoke oxidization-fixation method |
| CN107130115B (en) * | 2017-04-27 | 2018-12-07 | 郴州市金贵银业股份有限公司 | A method of separating arsenic, antimony from silver-colored smelting ash |
| CN107058746A (en) * | 2017-04-27 | 2017-08-18 | 郴州市金贵银业股份有限公司 | A kind of method that antimony is separated from silver-colored smelting ash |
| CN107058746B (en) * | 2017-04-27 | 2018-12-07 | 郴州市金贵银业股份有限公司 | A method of separating antimony from silver-colored smelting ash |
| CN107130115A (en) * | 2017-04-27 | 2017-09-05 | 郴州市金贵银业股份有限公司 | It is a kind of that arsenic, the method for antimony are separated from silver-colored smelting ash |
| CN107828967A (en) * | 2017-10-20 | 2018-03-23 | 昆明理工大学 | A kind of copper anode mud reduction organic sulfide method separation arsenic and the method for reclaiming antimony, tin |
| CN107828967B (en) * | 2017-10-20 | 2019-12-03 | 昆明理工大学 | A kind of method that copper anode mud reduction-organic sulfide method separates arsenic and recycles antimony, tin |
| CN109628761B (en) * | 2018-12-29 | 2021-06-11 | 焱鑫环保科技有限公司 | Method for producing antimony white by using high-antimony secondary smoke dust to remove arsenic |
| CN109628761A (en) * | 2018-12-29 | 2019-04-16 | 焱鑫环保科技有限公司 | A method of stibium trioxide is produced using high antimony secondary smoke dearsenification |
| CN109762996A (en) * | 2019-03-07 | 2019-05-17 | 昆明理工大学 | A method for separating arsenic and recovering antimony by high antimony and low arsenic soot oxidation-sulfidation immobilization method |
| CN110398403A (en) * | 2019-07-29 | 2019-11-01 | 华北电力大学（保定） | A preparation method and device for a stable arsenic trioxide standard gas |
| CN113955799A (en) * | 2021-10-20 | 2022-01-21 | 山东恒邦冶炼股份有限公司 | Method for purifying antimony-containing arsenic trioxide |
| CN114086002A (en) * | 2021-11-24 | 2022-02-25 | 云南锡业研究院有限公司 | Method for efficiently separating arsenic and antimony from high-arsenic smoke dust |
| CN116514164A (en) * | 2023-04-23 | 2023-08-01 | 山东恒邦冶炼股份有限公司 | Method and equipment for improving whiteness and purity of refined arsenic trioxide |
| CN117025979A (en) * | 2023-08-01 | 2023-11-10 | 昆明理工大学 | Method for efficiently enriching antimonous oxide in vacuum by using crude antimonous oxide |
| CN117286341A (en) * | 2023-10-09 | 2023-12-26 | 昆明冶金研究院有限公司 | Method for preparing arsenic-antimony base alloy from arsenic-antimony smelting smoke dust and arsenic-antimony base alloy |
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