CN103288133A - Method for preparing arsenic trioxide from black copper sludge - Google Patents
Method for preparing arsenic trioxide from black copper sludge Download PDFInfo
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- 239000010949 copper Substances 0.000 title claims abstract description 68
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 53
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 51
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 19
- HJTAZXHBEBIQQX-UHFFFAOYSA-N 1,5-bis(chloromethyl)naphthalene Chemical compound C1=CC=C2C(CCl)=CC=CC2=C1CCl HJTAZXHBEBIQQX-UHFFFAOYSA-N 0.000 title abstract description 41
- 239000010802 sludge Substances 0.000 title 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 75
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000007787 solid Substances 0.000 claims abstract description 19
- 238000002386 leaching Methods 0.000 claims abstract description 12
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 10
- KTTMEOWBIWLMSE-UHFFFAOYSA-N diarsenic trioxide Chemical compound O1[As](O2)O[As]3O[As]1O[As]2O3 KTTMEOWBIWLMSE-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 229960002594 arsenic trioxide Drugs 0.000 claims 2
- 230000005587 bubbling Effects 0.000 claims 1
- 239000004927 clay Substances 0.000 claims 1
- 238000001704 evaporation Methods 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 31
- 229910052785 arsenic Inorganic materials 0.000 abstract description 27
- 239000002244 precipitate Substances 0.000 abstract description 20
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 abstract description 12
- 239000002699 waste material Substances 0.000 abstract description 7
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 abstract description 6
- 239000002893 slag Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 2
- 229910052787 antimony Inorganic materials 0.000 description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 17
- 229910052742 iron Inorganic materials 0.000 description 16
- 239000000706 filtrate Substances 0.000 description 14
- 238000001914 filtration Methods 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000006722 reduction reaction Methods 0.000 description 7
- 239000002184 metal Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 125000000223 arsonoyl group Chemical group [H][As](*)(*)=O 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- DJHGAFSJWGLOIV-UHFFFAOYSA-N Arsenic acid Chemical compound O[As](O)(O)=O DJHGAFSJWGLOIV-UHFFFAOYSA-N 0.000 description 2
- 229940000488 arsenic acid Drugs 0.000 description 2
- 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
- 230000002378 acidificating effect Effects 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- CUGMJFZCCDSABL-UHFFFAOYSA-N arsenic(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[As+3].[As+3] CUGMJFZCCDSABL-UHFFFAOYSA-N 0.000 description 1
- GCPXMJHSNVMWNM-UHFFFAOYSA-N arsenous acid Chemical compound O[As](O)O GCPXMJHSNVMWNM-UHFFFAOYSA-N 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229940103357 calcium arsenate Drugs 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005363 electrowinning Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- -1 metallurgy Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- Manufacture And Refinement Of Metals (AREA)
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
Abstract
用黑铜泥制备三氧化二砷的方法，其目的是避免黑铜泥制备三氧化二砷产生大量的含砷硫酸钙废渣对环境造成二次污染以及简化工艺流程、降低生产成本；其步骤为：(1)将黑铜泥用氢氧化钠做浸出剂，氢氧化钠溶液的浓度为1～2mol/L，按液固比ml/g为8∶1～12∶1的比例，向氢氧化钠溶液中放入黑铜泥，温度为80～95℃，通入空气量为0.5～0.8m3/h，搅拌4～8小时；(2)将步骤(1)得到的浸出液用硫酸调节其pH为-1～1，通入二氧化硫气体还原，时间持续1～2小时，还原后溶液经蒸发浓缩结晶得到沉淀物；(3)将步骤(2)得到的沉淀物经洗涤、干燥，得到三氧化二砷产品。
The method for preparing diarsenic trioxide with black copper mud is aimed at avoiding secondary pollution caused by a large amount of arsenic-containing calcium sulfate waste slag produced by the preparation of diarsenic trioxide from black copper mud, simplifying the process flow, and reducing production costs; the steps are: (1) Sodium hydroxide is used as the leaching agent for copper mud. The concentration of the sodium hydroxide solution is 1-2mol/L, and the liquid-solid ratio ml/g is 8:1-12:1. Copper mud, the temperature is 80-95°C, the amount of air introduced is 0.5-0.8m 3 /h, and stirred for 4-8 hours; (2) The leachate obtained in step (1) is adjusted to a pH of -1-1 with sulfuric acid , pass through sulfur dioxide gas for reduction, and the time lasts for 1 to 2 hours. After the reduction, the solution is evaporated, concentrated and crystallized to obtain a precipitate; (3) the precipitate obtained in step (2) is washed and dried to obtain arsenic trioxide product.
Description
技术领域 technical field
本发明涉及用含砷工业废渣制备三氧化二砷的方法。The invention relates to a method for preparing arsenic trioxide with arsenic-containing industrial waste residue.
背景技术 Background technique
黑铜泥为铜电解液净化电积脱铜脱杂时，在阴极上产出的泥状物，含有大量的Cu、As、Sb、Bi、Fe等有价金属。黑铜泥中金属的含量约为铜42～51％、砷17～28％、锑2～7％、铋1～3％、铁0.05～0.2％。目前，由于含砷废渣没有较好的处理方式，企业大多堆存，这样含砷废渣就会造成土壤、河流的污染，严重危害了人们的健康，同时还造成有价金属的流失。为了防止二次污染同时回收有价金属就要对含砷废渣进行综合利用。Black copper mud is the mud produced on the cathode when the copper electrolyte is purified and electrowinning to remove copper and impurities, and contains a large amount of valuable metals such as Cu, As, Sb, Bi, and Fe. The metal content in black copper mud is about 42-51% copper, 17-28% arsenic, 2-7% antimony, 1-3% bismuth, and 0.05-0.2% iron. At present, because there is no better way to deal with arsenic-containing waste residues, most enterprises stockpile them. Such arsenic-containing waste residues will pollute soil and rivers, seriously endanger people's health, and also cause the loss of valuable metals. In order to prevent secondary pollution and recover valuable metals, it is necessary to comprehensively utilize arsenic-containing waste residue.
三氧化二砷是一种非常重要的化工原料，广泛应用于半导体、冶金、玻璃、农药、制革、印染、医药等行业。有六项中国专利(94110979.8、94110976.3、201010615434.4、201010615435.9、201010615475.3、201010615479.1)公开了用硫化砷废渣制备三氧化二砷的方法。有三项中国专利(200710035704.2、201010615441.4、201010615442.9)公开了用含砷废水制备三氧化二砷的方法。有两项日本专利(3034552-B、特开昭58-113331)公开了黑铜泥酸性浸出制备三氧化二砷的方法。采用黑铜泥碱性浸出制备三氧化二砷，目前已报道方法是①空气+氢氧化钠选择性浸出砷；②苛化：浸出液中加入消石灰，将As(V)以砷酸钙沉淀析出；③酸分解：用硫酸分解砷酸钙，得到砷酸溶液和含砷石膏渣；④还原结晶：向砷酸溶液中通入SO2气体，发生还原反应：H3AsO4+SO2＝HAsO2+H2SO4生成的亚砷酸过饱和，结晶析出AS2O3。Arsenic trioxide is a very important chemical raw material, widely used in semiconductor, metallurgy, glass, pesticide, tanning, printing and dyeing, medicine and other industries. There are six Chinese patents (94110979.8, 94110976.3, 201010615434.4, 201010615435.9, 201010615475.3, 201010615479.1) disclosing methods for preparing arsenic trioxide from arsenic sulfide waste residue. There are three Chinese patents (200710035704.2, 201010615441.4, 201010615442.9) disclosing methods for preparing arsenic trioxide from arsenic-containing wastewater. There are two Japanese patents (3034552-B, JP-A-58-113331) disclosing a method for preparing arsenic trioxide by acidic leaching of black copper mud. Alkaline leaching of black copper mud is used to prepare arsenic trioxide. Currently, the reported methods are ① selective leaching of arsenic with air + sodium hydroxide; : Decompose calcium arsenate with sulfuric acid to obtain arsenic acid solution and arsenic-containing gypsum slag; ④ Reduction crystallization: Introduce SO 2 gas into the arsenic acid solution, and a reduction reaction occurs: H 3 AsO 4 +SO 2 =HAsO 2 +H 2 The arsenous acid generated by SO 4 is supersaturated, and AS 2 O 3 is crystallized.
该工艺生产三氧化二砷工艺流程冗长，成本较高。同时产生大量的含砷硫酸钙废渣，造成固体废弃物的二次污染。The process for producing arsenic trioxide is lengthy and costly. At the same time, a large amount of arsenic-containing calcium sulfate waste residue is produced, causing secondary pollution of solid waste.
发明内容Contents of the invention
本发明的目的是避免黑铜泥制备三氧化二砷产生大量的含砷硫酸钙废渣对环境造成二次污染以及简化工艺流程、降低生产成本。The purpose of the invention is to avoid secondary pollution to the environment caused by a large amount of arsenic-containing calcium sulfate waste residue produced by the preparation of arsenic trioxide from black copper mud, simplify the process flow and reduce the production cost.
本发明是用黑铜泥制备三氧化二砷的方法，其步骤为：The present invention is the method for preparing arsenic trioxide with black copper mud, and its steps are:
(1)将黑铜泥用氢氧化钠做浸出剂，氢氧化钠溶液的浓度为1～2mol/L，按液固比ml/g为8∶1～12∶1的比例，向氢氧化钠溶液中放入黑铜泥，温度为80～95℃，通入空气量为0.5～0.8m3/h，搅拌4～8小时；(1) The black copper mud is made leaching agent with sodium hydroxide, the concentration of sodium hydroxide solution is 1～2mol/L, is the ratio of 8:1～12:1 by liquid-solid ratio ml/g, to sodium hydroxide Put black copper mud into the solution, the temperature is 80-95°C, the air volume is 0.5-0.8m 3 /h, and stir for 4-8 hours;
(2)将步骤(1)得到的浸出液用硫酸调节其pH为1，通入二氧化硫气体还原，时间持续1～2小时，还原后溶液经蒸发浓缩结晶得到沉淀物；(2) adjusting the pH of the leachate obtained in step (1) to 1 with sulfuric acid, passing through sulfur dioxide gas for reduction, the time continued for 1 to 2 hours, and after reduction, the solution was evaporated, concentrated and crystallized to obtain a precipitate;
(3)将步骤(2)得到的沉淀物经洗涤、干燥，得到三氧化二砷产品。(3) washing and drying the precipitate obtained in step (2) to obtain the arsenic trioxide product.
本发明与现有技术比较具有工艺流程短、易操作、对设备要求低、金属回收率高、生产成本低、处理过程中不产生二次污染的优点。Compared with the prior art, the present invention has the advantages of short technological process, easy operation, low equipment requirement, high metal recovery rate, low production cost and no secondary pollution during the process.
附图说明 Description of drawings
图1是本发明的工艺流程图。Fig. 1 is a process flow diagram of the present invention.
具体实施方法Specific implementation method
如图1所示，本发明是用黑铜泥制备三氧化二砷的方法，其步骤为：As shown in Figure 1, the present invention is the method for preparing diarsenic trioxide with black copper mud, and its steps are:
(1)将黑铜泥用氢氧化钠做浸出剂，在通入空气条件下搅拌浸出。(1) Use sodium hydroxide as the leaching agent for the black copper mud, and stir and leaching it under the condition of feeding air.
2Cu3As+4NaOH+4O2＝2Na2HAsO4+3Cu2O+H2O2Cu 3 As+4NaOH+4O 2 =2Na 2 HAsO 4 +3Cu 2 O+H 2 O
2Cu3As+2NaOH+4O2+H2O＝2NaH2AsO4+3Cu2O2Cu 3 As+2NaOH+4O 2 +H 2 O＝2NaH 2 AsO 4 +3Cu 2 O
砷以五价形式进入溶液，Sb、Bi、Cu等主要留在渣中。渣中铜主要以Cu2O形式存在，可回收铜。Arsenic enters the solution in the form of pentavalent, and Sb, Bi, Cu, etc. are mainly left in the slag. Copper in the slag mainly exists in the form of Cu 2 O, and copper can be recovered.
(2)将步骤(1)得到的浸出液用硫酸调节其pH，通入二氧化硫气体还原(2) the leaching solution that step (1) obtains is adjusted its pH with sulfuric acid, feeds sulfur dioxide gas reduction
H3AsO4+SO2＝HAsO2+2H2SO4 H 3 AsO 4 +SO 2 =HAsO 2 +2H 2 SO 4
还原后溶液经蒸发浓缩结晶得到沉淀物After reduction, the solution is evaporated, concentrated and crystallized to obtain a precipitate
2HAsO2＝As2O3+H2O2HAsO 2 ＝As 2 O 3 +H 2 O
(3)将步骤(2)得到的沉淀物经洗涤、干燥，得到三氧化二砷产品。(3) washing and drying the precipitate obtained in step (2) to obtain the arsenic trioxide product.
所述的浸出的工艺条件为：氢氧化钠溶液浓度为1～2mol/L，液固比(液体体积与固体质量之比，单位为ml/g)为8∶1～12∶1，温度80～95℃，通空气量为0.5～0.8m3/h，搅拌4～8小时。The process conditions of the leaching are: the concentration of the sodium hydroxide solution is 1-2mol/L, the liquid-solid ratio (the ratio of the liquid volume to the solid mass, in ml/g) is 8:1-12:1, and the temperature is 80 ~95°C, the air volume is 0.5~0.8m 3 /h, and stirred for 4~8 hours.
所述用硫酸调节浸出液的pH＝-1～1，通入二氧化硫还原时间为1～2小时。The sulfuric acid is used to adjust the pH of the leaching solution to be -1 to 1, and the reduction time of passing through the sulfur dioxide is 1 to 2 hours.
以下结合实施例具体说明本发明。The present invention will be described in detail below in conjunction with the examples.
实施例1Example 1
取黑铜泥(含量为：Cu 41.92％、As 22.40％、Sb 6.60％、Fe 0.10％)30g，按液固比为8∶1，氢氧化钠溶液浓度为2mol/L，配制好溶液，待温度升至95℃，往溶液中加入黑铜泥，通入空气，控制通空气量为0.8m3/h，搅拌浸出6小时，过滤后向滤液中加入硫酸调节pH＝-1，向溶液中通入SO2反应2小时后将溶液蒸发浓缩结晶得到沉淀物，沉淀物经洗涤、干燥后得到三氧化二砷产品。三氧化二砷的纯度为95.78％，达到YS-T99-1997产品质量标准。Get black copper mud (content is: Cu 41.92%, As 22.40%, Sb 6.60%, Fe 0.10%) 30g, by liquid-solid ratio is 8: 1, and sodium hydroxide solution concentration is 2mol/L, prepares solution, waits for The temperature was raised to 95°C, black copper mud was added to the solution, air was introduced, and the air volume was controlled to be 0.8m 3 /h, stirred and leached for 6 hours, after filtration, sulfuric acid was added to the filtrate to adjust the pH=-1, and the solution was added to After 2 hours of reaction with SO 2 , the solution was evaporated, concentrated and crystallized to obtain a precipitate, which was washed and dried to obtain the arsenic trioxide product. The purity of arsenic trioxide is 95.78%, reaching the product quality standard of YS-T99-1997.
实施例2Example 2
取黑铜泥(含量为：Cu 41.92％、As 22.40％、Sb 6.60％、Fe 0.10％)30g，按液固比为8∶1，氢氧化钠溶液浓度为1.5mol/L，配制好溶液，待温度升至85℃，往溶液中加入黑铜泥，通入空气，控制通空气量为0.6m3/h，搅拌浸出8小时，过滤后向滤液中加入硫酸调节pH＝0，向溶液中通入SO2反应1小时后将溶液蒸发浓缩结晶得到沉淀物，沉淀物经洗涤、干燥后得到三氧化二砷产品。三氧化二砷的纯度为96.23％，达到YS-T99-1997产品质量标准。Get black copper mud (content is: Cu 41.92%, As 22.40%, Sb 6.60%, Fe 0.10%) 30g, by liquid-solid ratio is 8: 1, and sodium hydroxide solution concentration is 1.5mol/L, prepares the solution, When the temperature rises to 85°C, black copper mud is added to the solution, air is introduced, the air volume is controlled to be 0.6m 3 /h, stirred and leached for 8 hours, after filtration, sulfuric acid is added to the filtrate to adjust the pH=0, and the solution is After passing through SO 2 to react for 1 hour, the solution was evaporated, concentrated and crystallized to obtain a precipitate, which was washed and dried to obtain the arsenic trioxide product. The purity of arsenic trioxide is 96.23%, reaching the product quality standard of YS-T99-1997.
实施例3Example 3
取黑铜泥(含量为：Cu 41.92％、As 22.40％、Sb 6.60％、Fe 0.10％)30g，按液固比为8∶1，氢氧化钠溶液浓度为1.5mol/L，配制好溶液，待温度升至90℃，往溶液中加入黑铜泥，通入空气，控制通空气量为0.6m3/h，搅拌浸出8小时，过滤后向滤液中加入硫酸调节pH＝0，向溶液中通入SO2反应2小时后将溶液蒸发浓缩结晶得到沉淀物，沉淀物经洗涤、干燥后得到三氧化二砷产品。三氧化二砷的纯度为97.51％，达到YS-T99-1997产品质量标准。Get black copper mud (content is: Cu 41.92%, As 22.40%, Sb 6.60%, Fe 0.10%) 30g, by liquid-solid ratio is 8: 1, and sodium hydroxide solution concentration is 1.5mol/L, prepares the solution, When the temperature rises to 90°C, add black copper mud to the solution, let in air, control the air volume to 0.6m 3 /h, stir and leach for 8 hours, add sulfuric acid to the filtrate after filtration to adjust pH = 0, and add to the solution After 2 hours of reaction with SO 2 , the solution was evaporated, concentrated and crystallized to obtain a precipitate, which was washed and dried to obtain the arsenic trioxide product. The purity of arsenic trioxide is 97.51%, reaching the product quality standard of YS-T99-1997.
实施例4Example 4
取黑铜泥(含量为：Cu 41.92％、As 22.40％、Sb 6.60％、Fe 0.10％)30g，按液固比为8∶1，氢氧化钠溶液浓度为2mol/L，配制好溶液，待温度升至90℃，往溶液中加入黑铜泥，通入空气，控制通空气量为0.8m3/h，搅拌浸出6小时，过滤后向滤液中加入硫酸调节pH＝1，向溶液中通入SO2反应2小时后将溶液蒸发浓缩结晶得到沉淀物，沉淀物经洗涤、干燥后得到三氧化二砷产品。三氧化二砷的纯度为96.45％，达到YS-T99-1997产品质量标准。Get black copper mud (content is: Cu 41.92%, As 22.40%, Sb 6.60%, Fe 0.10%) 30g, by liquid-solid ratio is 8: 1, and sodium hydroxide solution concentration is 2mol/L, prepares solution, waits for The temperature was raised to 90°C, black copper mud was added to the solution, air was introduced, and the air volume was controlled to be 0.8m 3 /h, stirred and leached for 6 hours, after filtration, sulfuric acid was added to the filtrate to adjust the pH=1, and the solution was ventilated After adding SO 2 to react for 2 hours, the solution was evaporated, concentrated and crystallized to obtain a precipitate, which was washed and dried to obtain the arsenic trioxide product. The purity of arsenic trioxide is 96.45%, reaching the product quality standard of YS-T99-1997.
实施例5Example 5
取黑铜泥(含量为：Cu 41.92％、As 22.40％、Sb 6.60％、Fe 0.10％)30g，按液固比为10∶1，氢氧化钠溶液浓度为1mol/L，配制好溶液，待温度升至90℃，往溶液中加入黑铜泥，通入空气，控制通空气量为0.6m3/h，搅拌浸出8小时，过滤后向滤液中加入硫酸调节pH＝-1，向溶液中通入SO2反应2小时后将溶液蒸发浓缩结晶得到沉淀物，沉淀物经洗涤、干燥后得到三氧化二砷产品。三氧化二砷的纯度为96.02％，达到YS-T99-1997产品质量标准。Get black copper mud (content is: Cu 41.92%, As 22.40%, Sb 6.60%, Fe 0.10%) 30g, by liquid-solid ratio is 10: 1, and sodium hydroxide solution concentration is 1mol/L, prepares solution, waits for The temperature was raised to 90°C, black copper mud was added to the solution, air was introduced, and the air volume was controlled to be 0.6m 3 /h, stirring and leaching for 8 hours, after filtration, sulfuric acid was added to the filtrate to adjust the pH=-1, and the solution was After 2 hours of reaction with SO 2 , the solution was evaporated, concentrated and crystallized to obtain a precipitate, which was washed and dried to obtain the arsenic trioxide product. The purity of arsenic trioxide is 96.02%, reaching the product quality standard of YS-T99-1997.
实施例6Example 6
取黑铜泥(含量为：Cu 41.92％、As 22.40％、Sb 6.60％、Fe 0.10％)30g，按液固比为10∶1，氢氧化钠溶液浓度为1mol/L，配制好溶液，待温度升至95℃，往溶液中加入黑铜泥，通入空气，控制通空气量为0.8m3/h，搅拌浸出8小时，过滤后向滤液中加入硫酸调节pH＝0，向溶液中通入SO2反应1小时后将溶液蒸发浓缩结晶得到沉淀物，沉淀物经洗涤、干燥后得到三氧化二砷产品。三氧化二砷的纯度为96.41％，达到YS-T99-1997产品质量标准。Get black copper mud (content is: Cu 41.92%, As 22.40%, Sb 6.60%, Fe 0.10%) 30g, by liquid-solid ratio is 10: 1, and sodium hydroxide solution concentration is 1mol/L, prepares solution, waits for The temperature was raised to 95°C, black copper mud was added to the solution, air was introduced, the air volume was controlled to be 0.8m 3 /h, stirred and leached for 8 hours, after filtration, sulfuric acid was added to the filtrate to adjust the pH=0, and the solution was ventilated After adding SO 2 to react for 1 hour, the solution was evaporated, concentrated and crystallized to obtain a precipitate, which was washed and dried to obtain the arsenic trioxide product. The purity of arsenic trioxide is 96.41%, reaching the product quality standard of YS-T99-1997.
实施例7Example 7
取黑铜泥(含量为：Cu 41.92％、As 22.40％、Sb 6.60％、Fe 0.10％)30g，按液固比为10∶1，氢氧化钠溶液浓度为1.5mol/L，配制好溶液，待温度升至85℃，往溶液中加入黑铜泥，通入空气，控制通空气量为0.6m3/h，搅拌浸出6小时，过滤后向滤液中加入硫酸调节pH＝1，向溶液中通入SO2反应2小时后将溶液蒸发浓缩结晶得到沉淀物，沉淀物经洗涤、干燥后得到三氧化二砷产品。三氧化二砷的纯度为96.16％，达到YS-T99-1997产品质量标准。Get black copper mud (content is: Cu 41.92%, As 22.40%, Sb 6.60%, Fe 0.10%) 30g, by liquid-solid ratio is 10: 1, and sodium hydroxide solution concentration is 1.5mol/L, prepares a good solution, When the temperature rises to 85°C, add black copper mud to the solution, let in air, control the air volume to 0.6m 3 /h, stir and leach for 6 hours, add sulfuric acid to the filtrate after filtration to adjust the pH=1, and add to the solution After 2 hours of reaction with SO 2 , the solution was evaporated, concentrated and crystallized to obtain a precipitate, which was washed and dried to obtain the arsenic trioxide product. The purity of arsenic trioxide is 96.16%, reaching the product quality standard of YS-T99-1997.
实施例8Example 8
取黑铜泥(含量为：Cu 41.92％、As 22.40％、Sb 6.60％、Fe 0.10％)30g，按液固比为10∶1，氢氧化钠溶液浓度为1.5mol/L，配制好溶液，待温度升至85℃，往溶液中加入黑铜泥，通入空气，控制通空气量为0.6m3/h，搅拌浸出6小时，过滤后向滤液中加入硫酸调节pH＝0，向溶液中通入SO2反应2小时后将溶液蒸发浓缩结晶得到沉淀物，沉淀物经洗涤、干燥后得到三氧化二砷产品。三氧化二砷的纯度为97.0％，达到YS-T99-1997产品质量标准。Get black copper mud (content is: Cu 41.92%, As 22.40%, Sb 6.60%, Fe 0.10%) 30g, by liquid-solid ratio is 10: 1, and sodium hydroxide solution concentration is 1.5mol/L, prepares a good solution, When the temperature rises to 85°C, add black copper mud to the solution, let in air, control the air flow rate to 0.6m 3 /h, stir and leach for 6 hours, add sulfuric acid to the filtrate after filtration to adjust pH = 0, and add to the solution After 2 hours of reaction with SO 2 , the solution was evaporated, concentrated and crystallized to obtain a precipitate, which was washed and dried to obtain the arsenic trioxide product. The purity of the arsenic trioxide is 97.0%, reaching the product quality standard of YS-T99-1997.
实施例9Example 9
取黑铜泥(含量为：Cu 41.92％、As 22.40％、Sb 6.60％、Fe 0.10％)30g，按液固比为10∶1，氢氧化钠溶液浓度为2mol/L，配制好溶液，待温度升至80℃，往溶液中加入黑铜泥，通入空气，控制通空气量为0.7m3/h，搅拌浸出4小时，过滤后向滤液中加入硫酸调节pH＝0，向溶液中通入SO2反应2小时后将溶液蒸发浓缩结晶得到沉淀物，沉淀物经洗涤、干燥后得到三氧化二砷产品。三氧化二砷的纯度为97.11％，达到YS-T99-1997产品质量标准。Get black copper mud (content is: Cu 41.92%, As 22.40%, Sb 6.60%, Fe 0.10%) 30g, by liquid-solid ratio is 10: 1, and sodium hydroxide solution concentration is 2mol/L, prepares solution, waits for The temperature was raised to 80°C, black copper mud was added to the solution, air was introduced, and the air volume was controlled to be 0.7m 3 /h, stirred and leached for 4 hours, after filtration, sulfuric acid was added to the filtrate to adjust the pH=0, and the solution was ventilated After adding SO 2 to react for 2 hours, the solution was evaporated, concentrated and crystallized to obtain a precipitate, which was washed and dried to obtain the arsenic trioxide product. The purity of the arsenic trioxide is 97.11%, reaching the product quality standard of YS-T99-1997.
实施例10Example 10
取黑铜泥(含量为：Cu 41.92％、As 22.40％、Sb 6.60％、Fe 0.10％)30g，按液固比为10∶1，氢氧化钠溶液浓度为2mol/L，配制好溶液，待温度升至95℃，往溶液中加入黑铜泥，通入空气，控制通空气量为0.6m3/h，搅拌浸出4小时，过滤后向滤液中加入硫酸调节pH＝-1，向溶液中通入SO2反应1小时后将溶液蒸发浓缩结晶得到沉淀物，沉淀物经洗涤、干燥后得到三氧化二砷产品。三氧化二砷的纯度为96.34％，达到YS-T99-1997产品质量标准。Get black copper mud (content is: Cu 41.92%, As 22.40%, Sb 6.60%, Fe 0.10%) 30g, by liquid-solid ratio is 10: 1, and sodium hydroxide solution concentration is 2mol/L, prepares solution, waits for The temperature was raised to 95°C, black copper mud was added to the solution, air was introduced, and the air volume was controlled to be 0.6m 3 /h, stirred and leached for 4 hours, after filtration, sulfuric acid was added to the filtrate to adjust the pH=-1, and the solution was After passing through SO 2 to react for 1 hour, the solution was evaporated, concentrated and crystallized to obtain a precipitate, which was washed and dried to obtain the arsenic trioxide product. The purity of arsenic trioxide is 96.34%, reaching the product quality standard of YS-T99-1997.
实例11Example 11
取黑铜泥(含量为：Cu 41.92％、As 22.40％、Sb 6.60％、Fe 0.10％)30g，按液固比为12∶1，氢氧化钠溶液浓度为2mol/L，配制好溶液，待温度升至85℃，往溶液中加入黑铜泥，通入空气，控制通空气量为0.7m3/h，搅拌浸出6小时，过滤后向滤液中加入硫酸调节pH＝-1，向溶液中通入SO2反应1小时后将溶液蒸发浓缩结晶得到沉淀物，沉淀物经洗涤、干燥后得到三氧化二砷产品。三氧化二砷的纯度为96.03％，达到YS-T99-1997产品质量标准。Get black copper mud (content is: Cu 41.92%, As 22.40%, Sb 6.60%, Fe 0.10%) 30g, by liquid-solid ratio is 12: 1, and sodium hydroxide solution concentration is 2mol/L, prepares solution, waits for The temperature was raised to 85°C, black copper mud was added to the solution, air was introduced, and the air volume was controlled to be 0.7m 3 /h, stirred and leached for 6 hours, after filtration, sulfuric acid was added to the filtrate to adjust the pH=-1, and the solution was added to After passing through SO 2 to react for 1 hour, the solution was evaporated, concentrated and crystallized to obtain a precipitate, which was washed and dried to obtain the arsenic trioxide product. The purity of arsenic trioxide is 96.03%, reaching the product quality standard of YS-T99-1997.
实施例12Example 12
取黑铜泥(含量为：Cu 41.92％、As 22.40％、Sb 6.60％、Fe 0.10％)30g，按液固比为12∶1，氢氧化钠溶液浓度为1.5mol/L，配制好溶液，待温度升至95℃，往溶液中加入黑铜泥，通入空气，控制通空气量为0.6m3/h，搅拌浸出8小时，过滤后向滤液中加入硫酸调节pH＝0，向溶液中通入SO2反应2小时后将溶液蒸发浓缩结晶得到沉淀物，沉淀物经洗涤、干燥后得到三氧化二砷产品。三氧化二砷的纯度为97.08％，达到YS-T99-1997产品质量标准。Get black copper mud (content is: Cu 41.92%, As 22.40%, Sb 6.60%, Fe 0.10%) 30g, by liquid-solid ratio is 12: 1, and sodium hydroxide solution concentration is 1.5mol/L, prepares a good solution, When the temperature rises to 95°C, add black copper mud to the solution, let in air, control the air volume to 0.6m 3 /h, stir and leach for 8 hours, add sulfuric acid to the filtrate after filtration to adjust the pH=0, and add to the solution After 2 hours of reaction with SO 2 , the solution was evaporated, concentrated and crystallized to obtain a precipitate, which was washed and dried to obtain the arsenic trioxide product. The purity of arsenic trioxide is 97.08%, reaching the product quality standard of YS-T99-1997.
实施例13Example 13
取黑铜泥(含量为：Cu 41.92％、As 22.40％、Sb 6.60％、Fe 0.10％)30g，按液固比为12∶1，氢氧化钠溶液浓度为1.5mol/L，配制好溶液，待温度升至90℃，往溶液中加入黑铜泥，通入空气，控制通空气量为0.7m3/h，搅拌浸出8小时，过滤后向滤液中加入硫酸调节pH＝1，向溶液中通入SO2反应2小时后将溶液蒸发浓缩结晶得到沉淀物，沉淀物经洗涤、干燥后得到三氧化二砷产品。三氧化二砷的纯度为96.38％，达到YS-T99-1997产品质量标准。Get black copper mud (content is: Cu 41.92%, As 22.40%, Sb 6.60%, Fe 0.10%) 30g, by liquid-solid ratio is 12: 1, and sodium hydroxide solution concentration is 1.5mol/L, prepares a good solution, When the temperature rises to 90°C, add black copper mud to the solution, let in air, control the air volume to 0.7m 3 /h, stir and leach for 8 hours, add sulfuric acid to the filtrate after filtration to adjust the pH=1, add to the solution After 2 hours of reaction with SO 2 , the solution was evaporated, concentrated and crystallized to obtain a precipitate, which was washed and dried to obtain the arsenic trioxide product. The purity of arsenic trioxide is 96.38%, reaching the product quality standard of YS-T99-1997.
实施例14Example 14
取黑铜泥(含量为：Cu 41.92％、As 22.40％、Sb 6.60％、Fe 0.10％)30g，按液固比为12∶1，氢氧化钠溶液浓度为2mol/L，配制好溶液，待温度升至85℃，往溶液中加入黑铜泥，通入空气，控制通空气量为0.5m3/h，搅拌浸出6小时，过滤后向滤液中加入硫酸调节pH＝-1，向溶液中通入SO2反应2小时后将溶液蒸发浓缩结晶得到沉淀物，沉淀物经洗涤、干燥后得到三氧化二砷产品。三氧化二砷的纯度为96.09％，达到YS-T99-1997产品质量标准。Get black copper mud (content is: Cu 41.92%, As 22.40%, Sb 6.60%, Fe 0.10%) 30g, by liquid-solid ratio is 12: 1, and sodium hydroxide solution concentration is 2mol/L, prepares solution, waits for The temperature was raised to 85°C, black copper mud was added to the solution, air was introduced, and the air volume was controlled to be 0.5m 3 /h, stirred and leached for 6 hours, after filtration, sulfuric acid was added to the filtrate to adjust the pH=-1, and the solution was After 2 hours of reaction with SO 2 , the solution was evaporated, concentrated and crystallized to obtain a precipitate, which was washed and dried to obtain the arsenic trioxide product. The purity of arsenic trioxide is 96.09%, reaching the product quality standard of YS-T99-1997.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105238939A (en) * | 2015-11-10 | 2016-01-13 | 李鹏飞 | Pyrogenic process arsenic removing method and device |
| CN107352581A (en) * | 2017-08-23 | 2017-11-17 | 中南大学 | A kind of method that antimony cigarette ash pressure reduction prepares arsenic trioxide |
| CN108570562A (en) * | 2017-03-13 | 2018-09-25 | 中国科学院过程工程研究所 | A kind of electrochemical process for treating of the melting waste slag containing arsenic |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58113311A (en) * | 1981-12-25 | 1983-07-06 | Kawasaki Steel Corp | Protecting method for tuyere for blowing oxidative gas for refining |
| CN101125682A (en) * | 2007-09-07 | 2008-02-20 | 中南大学 | Method for preparing arsenic trioxide from arsenic-containing wastewater |
| CN102115164A (en) * | 2010-12-31 | 2011-07-06 | 马艳荣 | A method for preparing arsenic trioxide from arsenic-containing wastewater |
| CN102115162A (en) * | 2010-12-31 | 2011-07-06 | 马艳荣 | A method for preparing arsenic trioxide from arsenic sulfide waste residue |
-
2012
- 2012-02-27 CN CN2012100458858A patent/CN103288133A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58113311A (en) * | 1981-12-25 | 1983-07-06 | Kawasaki Steel Corp | Protecting method for tuyere for blowing oxidative gas for refining |
| CN101125682A (en) * | 2007-09-07 | 2008-02-20 | 中南大学 | Method for preparing arsenic trioxide from arsenic-containing wastewater |
| CN102115164A (en) * | 2010-12-31 | 2011-07-06 | 马艳荣 | A method for preparing arsenic trioxide from arsenic-containing wastewater |
| CN102115162A (en) * | 2010-12-31 | 2011-07-06 | 马艳荣 | A method for preparing arsenic trioxide from arsenic sulfide waste residue |
Non-Patent Citations (2)
| Title |
|---|
| 王玉棉等: "黑铜泥碱性浸出工艺及机理探讨", 《兰州理工大学学报》, vol. 37, no. 2, 30 April 2011 (2011-04-30), pages 5 - 8 * |
| 郑雅杰等: "采用硫化砷渣制备三氧化二砷工艺", 《中南大学学报（自然科学版）》, vol. 39, no. 6, 31 December 2008 (2008-12-31), pages 1157 - 1163 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105238939A (en) * | 2015-11-10 | 2016-01-13 | 李鹏飞 | Pyrogenic process arsenic removing method and device |
| CN108570562A (en) * | 2017-03-13 | 2018-09-25 | 中国科学院过程工程研究所 | A kind of electrochemical process for treating of the melting waste slag containing arsenic |
| CN107352581A (en) * | 2017-08-23 | 2017-11-17 | 中南大学 | A kind of method that antimony cigarette ash pressure reduction prepares arsenic trioxide |
| CN107352581B (en) * | 2017-08-23 | 2018-10-09 | 中南大学 | A kind of method that antimony cigarette ash pressure reduction prepares arsenic trioxide |
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