KR100311689B1 - A METHOD FOR PREPARATION OF HIGH PURITY NiSO4 CRYSTAL - Google Patents
A METHOD FOR PREPARATION OF HIGH PURITY NiSO4 CRYSTAL Download PDFInfo
- Publication number
- KR100311689B1 KR100311689B1 KR1019990032752A KR19990032752A KR100311689B1 KR 100311689 B1 KR100311689 B1 KR 100311689B1 KR 1019990032752 A KR1019990032752 A KR 1019990032752A KR 19990032752 A KR19990032752 A KR 19990032752A KR 100311689 B1 KR100311689 B1 KR 100311689B1
- Authority
- KR
- South Korea
- Prior art keywords
- nickel
- high purity
- crystals
- solution
- sulfuric acid
- Prior art date
Links
- 239000013078 crystal Substances 0.000 title claims abstract description 43
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 title claims abstract description 42
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 141
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 69
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 58
- -1 iron ions Chemical class 0.000 claims abstract description 28
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052742 iron Inorganic materials 0.000 claims abstract description 25
- 239000007800 oxidant agent Substances 0.000 claims abstract description 25
- 239000002699 waste material Substances 0.000 claims abstract description 21
- 239000012535 impurity Substances 0.000 claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 claims abstract description 16
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims abstract description 10
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims abstract description 10
- 230000001590 oxidative effect Effects 0.000 claims abstract description 9
- 239000010802 sludge Substances 0.000 claims abstract description 9
- 238000001704 evaporation Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 235000014413 iron hydroxide Nutrition 0.000 claims abstract description 6
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 3
- XIKYYQJBTPYKSG-UHFFFAOYSA-N nickel Chemical compound [Ni].[Ni] XIKYYQJBTPYKSG-UHFFFAOYSA-N 0.000 claims abstract description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 42
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 15
- 229910017604 nitric acid Inorganic materials 0.000 claims description 15
- 238000000605 extraction Methods 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 239000003570 air Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 238000007747 plating Methods 0.000 abstract description 4
- 229910007567 Zn-Ni Inorganic materials 0.000 abstract description 2
- 229910007614 Zn—Ni Inorganic materials 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 241000080590 Niso Species 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000003472 neutralizing effect Effects 0.000 description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000005246 galvanizing Methods 0.000 description 1
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 1
- FLTRNWIFKITPIO-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe] FLTRNWIFKITPIO-UHFFFAOYSA-N 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000002156 mixing Methods 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
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/10—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
본 발명은 Zn-Ni 도금조업시 발생되는 폐니켈양극을 이용하여 고순도의 황산니켈 결정을 제조하는 방법에 관한 것으로,The present invention relates to a method for producing high purity nickel sulfate crystals using waste nickel anodes generated during Zn-Ni plating operation,
본 발명에 의하여,According to the present invention,
폐니켈양극을 가공하여 칩으로 제조하는 단계;Processing the nickel nickel anode to produce chips;
니켈칩을 폐니켈 1당량당 황산과 산화제의 당량비가 1:0.5∼1:1.5가 되도록 혼합한 황산과 산화제의 혼합물로 용해하여 니켈을 추출하는 단계;Extracting nickel by dissolving the nickel chip with a mixture of sulfuric acid and oxidant mixed so that the equivalent ratio of sulfuric acid and oxidant per equivalent of spent nickel is 1: 0.5 to 1: 1.5;
수득된 니켈 추출액을 증발, 농축, 냉각, 여과하여 1차 황산니켈 결정을 제조하는 단계;Evaporating, concentrating, cooling, and filtering the obtained nickel extract to prepare primary nickel sulfate crystals;
상기 1차 결정의 표면을 수세한 다음 재용해하고 이에 산화제를 첨가하여 2가 철이온을 3가 철이온으로 산화시키는 단계;Washing the surface of the primary crystals and then re-dissolving them to add an oxidizing agent to oxidize divalent iron ions to trivalent iron ions;
고순도의 탄산니켈 및/또는 수산화니켈을 투입하여 용액의 pH를 3∼6으로 조절하여 수산화철 슬러지를 형성하는 단계;Adding high purity nickel carbonate and / or nickel hydroxide to adjust the pH of the solution to 3 to 6 to form iron hydroxide sludge;
여과하여 상기 형성된 수산화철 슬러지 및 불순물을 제거하는 단계;Filtering to remove the formed iron hydroxide sludge and impurities;
상기 불순물이 제거된 황산니켈 용액을 증발, 농축 및 결정화하여 결정을 제조하는 단계; 및Preparing a crystal by evaporating, concentrating and crystallizing the nickel sulfate solution from which the impurities are removed; And
상기 제조된 결정을 건조하는 단계;Drying the prepared crystals;
를 포함하는 폐니켈양극을 이용한 고순도 황산니켈 결정 제조방법이 제공되며, 본 발명에 의한 방법으로 황산니켈을 제조하므로써 폐니켈 양극으로부터 고순도의 황산니켈이 제조된다.Provided is a method for producing high purity nickel sulfate crystals using a waste nickel anode comprising a, and by producing a nickel sulfate by the method according to the present invention, a high purity nickel sulfate is produced from the waste nickel anode.
Description
본 발명은 Zn-Ni 도금조업시 발생되는 폐니켈양극을 이용하여 황산니켈 결정을 제조하는 방법에 관한 것이며, 보다 상세하게는 폐니켈양극을 이용하여 고순도의 황산니켈 결정을 제조하는 방법에 관한 것이다.The present invention relates to a method for producing nickel sulfate crystals using waste nickel anodes generated during Zn-Ni plating operation, and more particularly, to a method for producing high purity nickel sulfate crystals using waste nickel anodes. .
폐니켈 양극은 전기아연 도금조업시 사용하고 남은 폐양극을 의미하며, 가용성 양극을 사용할 경우 사용하는 양극은 50만을 사용하고 나머지 50는 사용이 불가능하여, 고순도를 요하지 않는 스테인레스 공장의 용해원료등으로 이용되기도 했다.Waste nickel anode means waste anode left after electrolytic galvanizing, and if soluble anode is used, only 50 is used and the remaining 50 cannot be used. It was also used.
이에 본 발명자들은 폐니켈 양극을 이용하여 고순도의 염화니켈 용액을 제조하는기술(1994년 특허출원 제29119호)을 기출원한바 있으며, 특허출원(1998년 특허출원 제57608)에서는 이러한 고순도의 염화니켈로부터 고순도의 수산화니켈을 제조하는 기술을 출원한 바 있으며, 본 발명자들은 또한, 이러한 폐니켈 양극을 이용하여 고순도의 황산니켈결정을 제조하는 방법을 발견하였으며, 이러한 황산니켈은 니켈플래쉬 전기도금시 황산염계 도금액 제조에 사용되는 약품으로 고순도를 요구하고 있다.Accordingly, the present inventors have filed an application for producing a high purity nickel chloride solution using a waste nickel anode (patent application No. 29119 in 1994), and the patent application (patent application No. 57608 in 1998) discloses such a high purity nickel chloride solution. Has applied for a technique for producing high purity nickel hydroxide from the inventors, and the present inventors have also found a method for producing high purity nickel sulfate crystals using such a waste nickel anode, and the nickel sulfate is sulfate during nickel flash electroplating. High purity is required for chemicals used in the manufacture of plating solutions.
종래 황산니켈 결정을 제조하는 방법으로 사용되어온 JP 10-218623에 언급되어 있는 방법은 도 1에 나타낸바와 같다.The method mentioned in JP 10-218623, which has been used as a method for preparing nickel sulfate crystals, is as shown in FIG.
즉, 도 1에 따라 종래의 방법을 살펴보면, 종래에는 니켈이 함유된 염용액에 중화제로서 수산화나트륨 또는 탄산나트륨을 이용하여 pH를 상승시켜 수산화니켈 또는 탄산니켈을 침전시키고 이 침전물을 수세, 여과를 거친후 여기에 황산을 투입하여 용해시킨 후 황산니켈 용액을 만들고 이를 결정화하여 황산니켈을 제조하여 왔다.That is, referring to the conventional method according to FIG. 1, conventionally, the pH is increased by using sodium hydroxide or sodium carbonate as a neutralizing agent in a salt solution containing nickel to precipitate nickel hydroxide or nickel carbonate, and the precipitate is washed with water and filtered. After adding sulfuric acid to dissolve it, a nickel sulfate solution was prepared and crystallized to prepare nickel sulfate.
하지만 이와 같은 종래방법에서는 수산화나트륨으로 염화니켈을 중화하는 경우, 침전생성물에 염소이온이 Ni(OH)2·NiCl2·nH2O형태로 공존하며, 불순물의 정제가 곤란하고, 중화제로 투입한 Na 이온을 완벽하게 제거하기 위하여 여러번의 수세를 거친후에 사용해야만 하는 문제가 있는 것이다.However, in such a conventional method, when neutralizing nickel chloride with sodium hydroxide, chlorine ions coexist in the form of Ni (OH) 2 · NiCl 2 · nH 2 O in the precipitate product, and it is difficult to purify impurities. There is a problem that must be used after several washings in order to completely remove Na ions.
또한 니켈원료로 전량 수산화니켈 또는 탄산니켈을 사용하기 때문에 상기에 언급한 수세과정이 완벽하지 않으면 침전 생성물중의 염소이온과 미수세된 나트륨 성분이 염화나트륨 형태로되어 최종적으로 황산니켈 결정제조시 결정이 함께 정출되어 황산니켈의 순도가 저하되는 문제점이 있다.Also, since nickel hydroxide or nickel carbonate is used as the nickel raw material, if the above-mentioned washing process is not perfect, chlorine ions and unwashed sodium components in the precipitated product are in the form of sodium chloride. There is a problem that the purity of nickel sulfate is reduced together.
이에 본 발명의 목적은 폐니켈양극을 이용하여 고순도의 황산니켈 결정을 제조하는 방법을 제공하는 것이다.Accordingly, it is an object of the present invention to provide a method for producing high purity nickel sulfate crystals using waste nickel anodes.
본 발명의 또 다른 목적은 여러번 수세하지 않고도 효과적으로 불순물이 제거된 고순도의 황산니켈 결정을 제조하는 방법을 제공하는 것이다.It is still another object of the present invention to provide a method for producing high purity nickel sulfate crystals from which impurities are effectively removed without washing with water several times.
도 1은 종래의 황산니켈 제조방법을 나타내는 도면이며,1 is a view showing a conventional nickel sulfate production method,
도 2는 본 발명의 황산니켈 제조방법을 나타내는 도면이다.2 is a view showing a nickel sulfate production method of the present invention.
본 발명에 있어서,In the present invention,
폐니켈양극을 가공하여 칩으로 제조하는 단계;Processing the nickel nickel anode to produce chips;
니켈칩을 폐니켈 1당량당 황산과 산화제의 당량비가 1:0.5∼1:1.5가 되도록 혼합한 황산과 산화제의 혼합물로 용해하여 니켈을 추출하는 단계;Extracting nickel by dissolving the nickel chip with a mixture of sulfuric acid and oxidant mixed so that the equivalent ratio of sulfuric acid and oxidant per equivalent of spent nickel is 1: 0.5 to 1: 1.5;
수득된 니켈 추출액을 증발, 농축, 냉각, 여과하여 1차 황산니켈 결정을 제조하는 단계;Evaporating, concentrating, cooling, and filtering the obtained nickel extract to prepare primary nickel sulfate crystals;
상기 1차 결정의 표면을 수세한 다음 재용해하고 이에 산화제를 첨가하여 2가 철이온을 3가 철이온으로 산화시키는 단계;Washing the surface of the primary crystals and then re-dissolving them to add an oxidizing agent to oxidize divalent iron ions to trivalent iron ions;
고순도의 탄산니켈 및/또는 수산화니켈을 투입하여 용액의 pH를 3∼6으로 조절하여 수산화철 슬러지를 형성하는 단계;Adding high purity nickel carbonate and / or nickel hydroxide to adjust the pH of the solution to 3 to 6 to form iron hydroxide sludge;
여과하여 상기 형성된 수산화철 슬러지 및 불순물을 제거하는 단계;Filtering to remove the formed iron hydroxide sludge and impurities;
상기 불순물이 제거된 황산니켈 용액을 증발, 농축 및 결정화하여 결정을 제조하는단계; 및Preparing a crystal by evaporating, concentrating and crystallizing the nickel sulfate solution from which the impurities are removed; And
상기 제조된 결정을 건조하는 단계;Drying the prepared crystals;
를 포함하는 폐니켈양극을 이용한 고순도 황산니켈 결정 제조방법이 제공된다.Provided is a method for producing high purity nickel sulfate crystals using a waste nickel anode comprising a.
이하, 본 발명에 대하여 상세히 설명한다.EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.
본 발명의 황산니켈제조방법은 도 2에 나타내었으며, 도시된 바와 같이 폐니켈 양극을 이용하여 고순도 황산니켈 결정을 제조하는 본 발명은 폐니켈을 칩으로 제조하는 단계, 니켈 추출단계, 1차 결정화단계, 산화단계, 슬러지 형성단계, 불순물 제거단계, 결정제조단계 및 건조단계를 포함하여 구성되는 것으로 이하 이들 각 단계에 대하여 설명한다.The method for producing nickel sulfate of the present invention is shown in FIG. 2, and the present invention for producing high purity nickel sulfate crystals using a waste nickel anode as shown is a process for preparing waste nickel into chips, nickel extraction, and primary crystallization. Each of these steps will be described below, including a step, an oxidation step, a sludge forming step, an impurity removal step, a crystal manufacturing step, and a drying step.
폐니켈 양극은 부피가 크기 때문에 비표면적이 작아 이를 직접 황산과 반응시키면 용해속도가 매우 낮다. 따라서 황산에 대한 용해속도를 증대시키기 위해 폐니켈 양극을 기계적으로 분쇄하여 높은 비표면적을 갖는 형태로 가공하는 것이 바람직하다. 즉, 폐니켈 양극을 황산과 반응시켜 니켈을 추출하기 위해서 밀링기등을 사용하여 가공함으로써 폐양극을 칩으로 형성한다. 이때 칩의 크기가 작을수록 비표면적이 증대됨으로 바람직한데 이는 칩의 크기가 작을수록 산용해시 반응성이 우수하기 때문이다.Since the waste nickel anode has a large volume, the specific surface area is small, and when it is directly reacted with sulfuric acid, the dissolution rate is very low. Therefore, in order to increase the dissolution rate for sulfuric acid, it is preferable to mechanically grind the waste nickel anode into a form having a high specific surface area. That is, the waste nickel anode is processed by using a milling machine to extract nickel by reacting the waste nickel anode with sulfuric acid to form the waste cathode into chips. At this time, the smaller the size of the chip is preferable because the specific surface area is increased, because the smaller the size of the chip is excellent in reactivity when dissolution.
상기한 바와 같이 가공한 칩을 황산용액에 투입하여 용해시킬 경우, 니켈은 하기화학식과 같이 용출된다.When the chip processed as described above is added to the sulfuric acid solution to dissolve it, nickel elutes as shown in the following chemical formula.
상기 식과 같이 니켈과 황산은 동일한 당량비로 반응함으로, 황산의 농도가 묽을 경우에는 니켈이 충분히 용출되지 않아 그 침출량이 적다. 그러나, 황산을 니켈에 대하여 1당량 이상으로 첨가하더라도 더이상 반응이 진행되지 않음으로 경제적으로 바람직하지 않은 것이다.As described above, nickel and sulfuric acid react at the same equivalence ratio, so that when the sulfuric acid is diluted, the nickel is not sufficiently eluted, so that the amount of leaching is small. However, even when sulfuric acid is added in an amount of 1 equivalent or more based on nickel, the reaction does not proceed anymore, which is economically undesirable.
황산의 농도를 증가시킴에 따라 니켈은 NiSO3·nH2O 형태의 분말상태로 칩에서 떨어져 나오게 되며, 이 때 상기 NiSO3·nH2O 형태의 분말은 산 및 물에 대하여 불용성이므로 NiSO4형태로 산화시키기 위한 산화제를 필요로한다.As the concentration of sulfuric acid is increased, nickel is released from the chip in powder form of NiSO 3 · nH 2 O. At this time, the NiSO 3 · nH 2 O type powder is insoluble to acid and water, so NiSO 4 form Requires an oxidant to oxidize.
본 발명에서는 상기 산화제로서 질산 또는 과산화수소가 사용된다. 이 때 산화제는 니켈 1당량에 대하여 황산:질산의 비율을 1:0.5∼1:1.5당량비의 량이 되도록 사용한다.In the present invention, nitric acid or hydrogen peroxide is used as the oxidizing agent. At this time, the oxidizing agent is used so that the ratio of sulfuric acid: nitric acid to the equivalent of nickel is 1: 0.5 to 1: 1.5 equivalent ratio.
산화제를 니켈에 대하여 0.5당량비 이하로 사용하는 경우에는 NiSO3·nH2O 형태의 분말을 NiSO4형태로 충분히 산화시키지 못하며, 산화제를 니켈에 대하여 1.5당량비 이상으로 첨가하는 경우 또한 바람직하지 않다. 즉, 산화제로서 질산을 사용하는 경우, 질산을 니켈에 대하여 1.5당량비 이상으로 사용하면, 1차 결정을 제조하기 위하여 휘발시켜야 할 NO2또는 NO의 양이 많아지고 1차 황산니켈 결정 표면에 형성되는 유리산(free acid)의 양이 많아지므로 수세시 수세횟수를 늘여야 함으로 바람직하지 않은 것이다.When the oxidizing agent is used in an amount of 0.5 equivalent or less with respect to nickel, the powder of NiSO 3 · nH 2 O form is not sufficiently oxidized in the form of NiSO 4 , and it is also not preferable when the oxidizing agent is added in an amount of 1.5 equivalent or more with respect to nickel. That is, when nitric acid is used as the oxidizing agent, when nitric acid is used in an amount of 1.5 equivalent or more with respect to nickel, the amount of NO 2 or NO to be volatilized in order to prepare primary crystals increases and is formed on the surface of primary nickel sulfate crystals. Since the amount of free acid increases, the number of washes at the time of washing is not preferable.
한편, 산화제로서 과산화수소를 사용하는 경우, 과산화수소를 니켈에 대하여 1.5당량비 이상으로 사용하면, 과량의 과산화수소와 폭발적으로 반응함으로 위험하다.On the other hand, when hydrogen peroxide is used as the oxidizing agent, when hydrogen peroxide is used in an amount of 1.5 equivalent or more with respect to nickel, it is dangerous because it explosively reacts with excess hydrogen peroxide.
상기한 바와 같이 황산과 산화제를 사용하여 폐니켈양극으로부터 니켈을 용출한후, 니켈이 용출된 용액을 증발, 농축하여 용액속의 NO2또는 NO성분을 휘발시켜 제거하고, 냉각하여 1차 황산니켈 결정을 제조한다.As described above, after eluting nickel from the spent nickel anode using sulfuric acid and an oxidizing agent, the solution in which the nickel is eluted is evaporated and concentrated to remove volatilized NO 2 or NO components in the solution, and cooled to crystallize primary nickel sulfate. To prepare.
여과하여 상기 형성된 1차 황산니켈 결정을 분리한 후, 결정의 표면에 묻어 있는 유리산을 제거하기 위하여 간단히 물로 수세한 다음, 결정을 물에 재용해시킨다.The primary nickel sulfate crystal formed by filtration is separated, and then washed with water simply to remove free acid on the surface of the crystal, and then the crystal is redissolved in water.
상기와 같이 재용해한 용액중에는 수용성 철이온 또는 물불용성 실리콘 이온등의 불순물이 존재하는데 이들 이온은 니켈 양극을 제조하는 과정에서 안정제로 투입된 물질에 기인한 것이며, 따라서 고순도의 황산니켈을 제조하기 위해서 이러한 불순물이 제거되어야 한다.Impurities such as water-soluble iron ions or water-insoluble silicon ions are present in the re-dissolved solution as described above. These ions are due to the material introduced as a stabilizer in the process of manufacturing the nickel anode, and thus to prepare high purity nickel sulfate These impurities must be removed.
본 발명에서는 수용성 철이온 불순물은 불용성 슬러지로 전환하여 제거한다. 즉, 산화제를 투입하여 용액중의 2가 철이온을 3가 철이온으로 산화시킨다. 이때 산화제로는 과산화수소, 산소 또는 공기를 취입하여 철이온을 산화시킬수 있다. 과산화수소는 용액중의 철이온과 동일한 당량비로 첨가된다.In the present invention, the water-soluble iron ion impurities are removed by conversion to insoluble sludge. That is, an oxidant is added to oxidize divalent iron ions in the solution to trivalent iron ions. In this case, as the oxidant, hydrogen peroxide, oxygen or air may be blown to oxidize iron ions. Hydrogen peroxide is added in the same equivalence ratio as iron ions in the solution.
그 후 용액의 pH를 증가시키기 위하여 중화제로서 고순도의 수산화니켈 혹은 고순도의 탄산니켈을 투입하여 용액의 pH를 3∼6으로 조절한다. 이와 같이 용액의 증가시킴으로써 불순물을 정제할 수 있을 뿐만 아니라 결정화시 결정화기의 부식을 방지하게 된다. 즉, pH를 상승시킴으로써 2가 철이온의 산화에 의한 3가 철이온이 불용성 물질인 수산화철(Fe(OH)3) 슬러지를 형성하며 이는 실리콘 이온등 물불용성 불순물과 함께 여과함으로써 제거할 수 있으며, 강산성의 용액을 중화시킴으로써 후속공정인 증발, 농축등의 공정에서 기기가 강산에 의해 부식되는 것을 방지하게된다.Then, in order to increase the pH of the solution, a high purity nickel hydroxide or high purity nickel carbonate is added as a neutralizing agent to adjust the pH of the solution to 3-6. In this way, by increasing the solution, not only the impurities can be purified, but also the corrosion of the crystallizer during crystallization is prevented. That is, by raising the pH, trivalent iron ions due to oxidation of divalent iron ions form iron hydroxide (Fe (OH) 3 ) sludge, which is an insoluble substance, which can be removed by filtration with water insoluble impurities such as silicon ions. By neutralizing the strongly acidic solution, the device is prevented from being corroded by the strong acid in subsequent processes such as evaporation and concentration.
pH 조절시, pH 3이하에서는 상기 의도하는 목적을 달성할 수 없으며 pH 6이상으로 조절하기 위해서는 고순도의 수산화니켈 및 탄산니켈을 첨가하여야 하여, pH 증가를 위해 투입한 상기 분말들이 용해되지 못하고 미반응의 매우 미세한 입자상태로 용액속에 남아 여과시 여과막을 막게된다.When the pH is adjusted, the intended purpose cannot be achieved below pH 3, and in order to adjust the pH to 6 or higher, high purity nickel hydroxide and nickel carbonate should be added, so that the powders added to increase the pH are not dissolved and are not reacted. The very fine particles of the remaining in the solution to filter the membrane to block.
상기한 바와 같이 pH를 3∼6으로 조절함으로써 형성된 물불용성 불술물을 여과하여 제거한다.As described above, the water-insoluble impurities formed by adjusting the pH to 3 to 6 are removed by filtration.
그 후 분리된 여액을 증발, 농축, 결정화 및 건조하여 황산니켈 결정을 제조한다.The separated filtrate is then evaporated, concentrated, crystallized and dried to produce nickel sulfate crystals.
이하, 본 발명의 실시예에 대하여 상세히 설명한다.Hereinafter, embodiments of the present invention will be described in detail.
실시예 1Example 1
본 실시예에서는 폐니켈 양극을 가공한 칩을 산에 용해시키는 경우, 황산의 농도 및 황산과 질산의 비율에 따라 추출되는 니켈의 양과의 관계를 알아보기 위한 것이다.In this embodiment, when dissolving the chip processed the spent nickel anode in acid, it is to determine the relationship between the concentration of sulfuric acid and the amount of nickel extracted according to the ratio of sulfuric acid and nitric acid.
(발명예 1 및 2)(Invention Examples 1 and 2)
하기 표 1의 발명예 1 및 2에서는 폐니켈양극 칩을 용해하기 위하여 니켈칩 117. 4g에 대하여, 발명예 1에서는 니켈칩 1당량에 대하여 황산과 질산을 1:0.5 당량비로 투입하였으며 이때 사용한 물의 양은 480㎖로 하였다. 그리고 발명에 2에서는 황산과 질산의 비율을 1:1.5로 하였으며 물의 양은 발명예 1과 동일하게 하였다.In Inventive Examples 1 and 2 of Table 1, sulfuric acid and nitric acid were added in a 1: 0.5 equivalent ratio to 117. 4g of a nickel chip and 1 equivalent of a nickel chip in order to dissolve the waste nickel anode chip. The amount was 480 ml. In the invention 2, the ratio of sulfuric acid and nitric acid was 1: 1.5, and the amount of water was the same as that of Inventive Example 1.
상기와 같이 황산과 질산을 각각 혼합하고 이에 니켈칩을 용해시키기 시작한 후 2시간 경과시 니켈 추출율을 조사한 결과, 발명예 1 및 2는 각각 96와 100의 양호한 결과를 보였다.As a result of mixing sulfuric acid and nitric acid and dissolving the nickel chip thereafter, the nickel extraction rate was examined after 2 hours. Inventive Examples 1 and 2 showed good results of 96 and 100, respectively.
(비교예 1)(Comparative Example 1)
비교예 1에서는 폐니켈양극 칩을 용해하기 위하여 니켈칩 117.4g에 대하여 1당량비에 해당되는 황산을 투입하고 물은 발명예와 같이 480㎖를 사용하였으며 질산은 사용하지 않았다. 2시간 동안의 반응후 니켈 추출율은 10로 저조하여 바람직하지 않았다.In Comparative Example 1, sulfuric acid was added in an equivalent ratio to 117.4 g of nickel chip in order to dissolve the spent nickel anode chip, and 480 mL of water was used as in the invention example, but nitric acid was not used. The nickel extraction rate after the reaction for 2 hours was low at 10, which was not preferable.
(비교예 2)(Comparative Example 2)
비교예 1과 동일한 조건이지만 사용한 황산의 농도를 비교예 1의 4배에 해당되는 량으로 사용한 결과, 니켈칩은 분해하여 NiSO3·nH2O형태의 분말형 태로 되었다. 이 분말은 산 및 물에 불용성임으로 바람직하지 않은 것이다.The same conditions as in Comparative Example 1 but the concentration of sulfuric acid used was used in an amount corresponding to four times that of Comparative Example 1, whereupon the nickel chip was decomposed to form a powder form of NiSO 3 · nH 2 O. This powder is undesirable because it is insoluble in acids and water.
(비교예 3)(Comparative Example 3)
본 비교예에서는 황산과 질산의 비율을 1:0.2로 한 것을 제외하고 다른 사항은 발명예와 동일하게 하여 니켈을 추출하였으며, 니켈 추출율은 30로 저조하였다.In the present Comparative Example, except that the ratio of sulfuric acid and nitric acid was 1: 0.2, nickel was extracted in the same manner as the invention example, and the nickel extraction rate was low at 30.
(비교예 4)(Comparative Example 4)
본 비교예에서는 황산과 질산을 1:2당량비로한 것을 제외하고는 발명예와 동일하게 하여 니켈을 추출하였다. 추출결과 니켈추출율은 100로 양호하지만 황산과 질산의 비율이 1:1.5를 넘는 경우에는 1차 결정을 제조하기 위하여 휘발시켜야 할 NO2또는 NO의 량이 많아지는 문제가 있으며, 또한 1차 황산니켈 결정의 표면에 유리산의 양이 많아지므로 수세시 수세횟수를 늘여야 함으로 바람직하지 않은 것이다.In this comparative example, nickel was extracted in the same manner as in the invention example except that sulfuric acid and nitric acid were 1: 2 equivalents. As a result of extraction, the nickel extraction rate is good as 100, but when the ratio of sulfuric acid and nitric acid exceeds 1: 1.5, there is a problem of increasing the amount of NO 2 or NO to be volatilized to prepare primary crystals, and also primary nickel sulfate crystals. Since the amount of free acid increases on the surface of the washing is not desirable to increase the number of washes.
따라서, 상기 실시예 1에서와 같이 페니켈양극칩을 용해하기 위한 황산과 질산의 비율은 니켈칩 1당량 대비 황산과 질산의 비가 1:0.5∼1:1.5의 범위인 것이 바람직하다.Therefore, as in Example 1, the ratio of sulfuric acid and nitric acid for dissolving the nickel anode chip is preferably in the range of 1: 0.5 to 1: 1.5 in the ratio of sulfuric acid and nitric acid to 1 equivalent of the nickel chip.
실시예 2Example 2
본 실시예는 실시예 1의 발명예 2에서 용해한 황산니켈 용액을 증발, 농축시킨후 냉각하여 얻은 1차 황산니켈 결정을 출발원료로하고 하기 표 2에 나타낸 바와 같이 pH를 조절하고 과산화수소의 투입여부를 달리하여 용액내의 철이온 제거여부와 pH 및 산화제사용여부와의 관계를 알아보기 위한 것이다. 본 실시예에서 산화제로서 과산화수소를 사용한 경우 과산화수소는 용액중 철이온의 당량비와 동일한 당량비로 사용하였다.This Example is a primary nickel sulfate crystal obtained by evaporating, concentrating and cooling the nickel sulfate solution dissolved in Example 2 of Example 1 as a starting material and adjusting the pH as shown in Table 2 below whether or not hydrogen peroxide To determine the relationship between the removal of iron ions in the solution and the pH and the use of oxidants. In the present embodiment, when hydrogen peroxide was used as the oxidizing agent, hydrogen peroxide was used in the same ratio as the equivalent ratio of iron ions in the solution.
(발명예 3 및 발명예 4)(Invention Example 3 and Invention Example 4)
하기 표 2의 발명예 3 및 4와 같이 1차 황산니켈 결정을 용해한 후 과산화수소수를투입한 다음 고순도의 수산화니켈 및 탄산니켈을 투입하여 용액의 pH를 3 및 6으로 조절하는 경우에는 제조된 황산니켈 결정내에서 철이온이 검출되지 않았다.When the primary nickel sulfate crystals were dissolved as inventive examples 3 and 4 of Table 2, and then hydrogen peroxide solution was added thereto, and then the high purity nickel hydroxide and nickel carbonate were added to adjust the pH of the solution to 3 and 6. No iron ions were detected in the nickel crystals.
(비교예 5)(Comparative Example 5)
산화제로서 과산화수소를 투입하고 용액의 pH를 2로 조절한 비교예 5의 경우에는 제조된 결정내에 철이온이 0.023농도로 존재하였다. 이는 니켈 플래쉬용 도금용액내의 철이온 농도의 규제치가 0.01이하를 요구하므로 바람직하지 않은 것이다.In the case of Comparative Example 5 in which hydrogen peroxide was added as an oxidizing agent and the pH of the solution was adjusted to 2, iron ions were present at a concentration of 0.023 in the prepared crystal. This is undesirable because the regulation value of the iron ion concentration in the plating solution for nickel flash requires 0.01 or less.
(비교예 6)(Comparative Example 6)
과산화수소를 투입하지 않고 용액의 pH만을 3으로 조절하여 황산니켈결정을 제조하였다. 이 경우, 하기 표 2에서와 같이 철이온 농도가 0.016를 나타내고 있어 상기 비교예 5와 같이 바람직하지 않다.Nickel sulfate crystals were prepared by adjusting only the pH of the solution to 3 without adding hydrogen peroxide. In this case, as shown in Table 2 below, the iron ion concentration is 0.016, which is not preferable as in Comparative Example 5.
(비교예 7)(Comparative Example 7)
과산화수소를 첨가하고 용액의 pH를 7로 조절하여 황산니켈결정을 제조하였다. 결정내의 철이온 농도 측면에서는 수용가능하지만, 이와같이 1차 황산니켈결정을 용해후 고순도의 수산화니켈 및 고순도의 탄산니켈을 이용하여 pH를 7이상으로 높일 경우, pH 증가를 위해 투입한 상기 분말들이 용해하지 못하고, 미반응의 매우 미세한 입자상태로 용액속에 남기 때문에 여과가 잘 않되는 문제점이 있어 바람직하지 않다.Nickel sulfate crystals were prepared by adding hydrogen peroxide and adjusting the pH of the solution to 7. Although it is acceptable in terms of iron ion concentration in the crystal, when the primary nickel sulfate crystal is dissolved in this way and the pH is raised to 7 or more using high purity nickel hydroxide and high purity nickel carbonate, the powders added for pH increase are dissolved. It is not preferable because there is a problem that the filtration is not good because it remains in the solution in the form of unreacted very fine particles.
따라서 실시예 2에서와 같이 철이온등의 불순물을 제거하기 위하여 1차 황산니켈 결정에 고순도의 수산화니켈 및 고순도의 탄산니켈을 첨가할 경우에는 과산화수소수의 투입 및 용액의 pH를 3내지 6으로 조절하는 것이 바람직하다.Therefore, when high purity nickel hydroxide and high purity nickel carbonate are added to the primary nickel sulfate crystal to remove impurities such as iron ions as in Example 2, the hydrogen peroxide solution is added and the pH of the solution is adjusted to 3 to 6. It is desirable to.
tr: 불검출tr: not detected
본 발명에 의한 방법으로 황산니켈을 제조하므로써 폐니켈 양극으로부터 고순도의 황산니켈이 제조된다.By producing nickel sulfate by the method according to the present invention, high purity nickel sulfate is produced from a waste nickel anode.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019990032752A KR100311689B1 (en) | 1999-08-10 | 1999-08-10 | A METHOD FOR PREPARATION OF HIGH PURITY NiSO4 CRYSTAL |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019990032752A KR100311689B1 (en) | 1999-08-10 | 1999-08-10 | A METHOD FOR PREPARATION OF HIGH PURITY NiSO4 CRYSTAL |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20010017305A KR20010017305A (en) | 2001-03-05 |
| KR100311689B1 true KR100311689B1 (en) | 2001-11-14 |
Family
ID=19606700
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1019990032752A KR100311689B1 (en) | 1999-08-10 | 1999-08-10 | A METHOD FOR PREPARATION OF HIGH PURITY NiSO4 CRYSTAL |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR100311689B1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101317297B1 (en) | 2013-03-08 | 2013-10-10 | 인천화학 주식회사 | Recycle process of high purity nickel from waste nickel sludge using ion exchange resin and reducing agent |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102075051B1 (en) * | 2018-06-22 | 2020-03-11 | 주식회사 우전지앤에프 | METHOD OF MANUFACTURING CRYSTAL OF HIGH PURITY NICKEL SULFATE HEXAHYDRATE FROM RAW MATERIAL COMPRISING NiSO4, NiOH, NiCO3, NiS AND Ni USING NiF AND SOLVENT EXTRACTION |
| CN109850958A (en) * | 2018-12-19 | 2019-06-07 | 浙江科菲科技股份有限公司 | A kind of discarded printed nickel net recovery and treatment method |
| CN111826523B (en) * | 2020-06-28 | 2022-07-15 | 广东邦普循环科技有限公司 | Method for refining nickel hydroxide cobalt |
| CN113772751B (en) * | 2021-07-29 | 2023-02-14 | 广东邦普循环科技有限公司 | Method for directly preparing nickel sulfate by using low-nickel matte, nickel sulfate and application thereof |
-
1999
- 1999-08-10 KR KR1019990032752A patent/KR100311689B1/en not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101317297B1 (en) | 2013-03-08 | 2013-10-10 | 인천화학 주식회사 | Recycle process of high purity nickel from waste nickel sludge using ion exchange resin and reducing agent |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20010017305A (en) | 2001-03-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR20110038769A (en) | Manufacture of high purity nickel sulfate crystal from ferronickel slug | |
| KR100586271B1 (en) | Chloride assisted hydrometallurgical extraction of nickel and cobalt from sulphide or laterite ores | |
| US8277633B2 (en) | Process for producing scorodite and recycling the post-scorodite-synthesis solution | |
| US20030086864A1 (en) | Production of pure molybdenum oxide from low grade molybdeniteconcentrates | |
| US20080233023A1 (en) | Method for manufacturing scorodite | |
| KR102451443B1 (en) | Method for preparing nickel precusor for cathod active material | |
| US4094753A (en) | Recovery of gallium from gallium compounds | |
| KR100311689B1 (en) | A METHOD FOR PREPARATION OF HIGH PURITY NiSO4 CRYSTAL | |
| CN111807414A (en) | Method for producing fluorine-free ultrapure manganese sulfate monohydrate by using basic salt method | |
| KR20090109733A (en) | Method for producing high purity cobalt carbonate | |
| GB2171686A (en) | Purification of molybdenum trioxide | |
| KR100345743B1 (en) | A method for preparation of high purity nickel sulfate crystal | |
| JP3369855B2 (en) | Method for producing high purity nickel aqueous solution | |
| EP0308175A1 (en) | Stripping and recovery of dichromate in electrolytic chlorate systems | |
| TWI811993B (en) | Manufacturing method of cobalt sulfate | |
| US4908462A (en) | Cobalt recovery method | |
| US4942024A (en) | Method for refining hydroxides of niobium and tantalum containing transition metals | |
| JP3722254B2 (en) | Manufacturing method of high purity nickel aqueous solution | |
| KR102075051B1 (en) | METHOD OF MANUFACTURING CRYSTAL OF HIGH PURITY NICKEL SULFATE HEXAHYDRATE FROM RAW MATERIAL COMPRISING NiSO4, NiOH, NiCO3, NiS AND Ni USING NiF AND SOLVENT EXTRACTION | |
| KR960005510B1 (en) | Process for the preparation of high purity nickel chloride form waste nickel anode | |
| CN111732133A (en) | Preparation method of tetraamminepalladium sulfate | |
| WO2003002460A1 (en) | Process for removing sodium sulfate from nickel hydroxide effluent streams | |
| JP4505951B2 (en) | Method for producing high purity ferric chloride aqueous solution | |
| JPH0375224A (en) | Method for purifying aqueous solution of indium | |
| CA1094328A (en) | Recovery of gallium from gallium compounds |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant | ||
| FPAY | Annual fee payment |
Payment date: 20130902 Year of fee payment: 13 |
|
| FPAY | Annual fee payment |
Payment date: 20140714 Year of fee payment: 14 |
|
| LAPS | Lapse due to unpaid annual fee |