CN1198723A - 次磷酸镍的制备方法 - Google Patents
次磷酸镍的制备方法 Download PDFInfo
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- CN1198723A CN1198723A CN96197333A CN96197333A CN1198723A CN 1198723 A CN1198723 A CN 1198723A CN 96197333 A CN96197333 A CN 96197333A CN 96197333 A CN96197333 A CN 96197333A CN 1198723 A CN1198723 A CN 1198723A
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- Prior art keywords
- nickel
- hypophosphite
- resin
- ion exchange
- sodium
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Links
- XXSPKSHUSWQAIZ-UHFFFAOYSA-L 36026-88-7 Chemical compound [Ni+2].[O-]P=O.[O-]P=O XXSPKSHUSWQAIZ-UHFFFAOYSA-L 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title claims description 10
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims abstract description 9
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000005342 ion exchange Methods 0.000 claims abstract description 4
- 239000011347 resin Substances 0.000 claims description 15
- 229920005989 resin Polymers 0.000 claims description 15
- 150000002815 nickel Chemical class 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- -1 sodium carboxylic acid Chemical class 0.000 claims description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000003456 ion exchange resin Substances 0.000 claims description 3
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 36
- 229910052759 nickel Inorganic materials 0.000 abstract description 17
- 238000007747 plating Methods 0.000 abstract description 6
- 239000007864 aqueous solution Substances 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 4
- 150000003839 salts Chemical class 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 6
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910001453 nickel ion Inorganic materials 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 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 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910001382 calcium hypophosphite Inorganic materials 0.000 description 2
- 229940064002 calcium hypophosphite Drugs 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000005649 metathesis reaction Methods 0.000 description 2
- OFWQYFSMYVEOSZ-UHFFFAOYSA-L nickel hypophosphite hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]P=O.[O-]P=O OFWQYFSMYVEOSZ-UHFFFAOYSA-L 0.000 description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- CNALVHVMBXLLIY-IUCAKERBSA-N tert-butyl n-[(3s,5s)-5-methylpiperidin-3-yl]carbamate Chemical compound C[C@@H]1CNC[C@@H](NC(=O)OC(C)(C)C)C1 CNALVHVMBXLLIY-IUCAKERBSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- YWMAPNNZOCSAPF-UHFFFAOYSA-N Nickel(1+) Chemical compound [Ni+] YWMAPNNZOCSAPF-UHFFFAOYSA-N 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910001378 barium hypophosphite Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000001175 calcium sulphate Substances 0.000 description 1
- 235000011132 calcium sulphate Nutrition 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- GQZXNSPRSGFJLY-UHFFFAOYSA-N hydroxyphosphanone Chemical compound OP=O GQZXNSPRSGFJLY-UHFFFAOYSA-N 0.000 description 1
- 229940005631 hypophosphite ion Drugs 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229940006444 nickel cation Drugs 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000008237 rinsing water Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/165—Hypophosphorous acid; Salts thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemically Coating (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Treatment Of Water By Ion Exchange (AREA)
- Removal Of Specific Substances (AREA)
Abstract
次磷酸镍是用羧酸型树脂通过硫酸镍和次磷酸之间的离子交换制备的。这样得到呈水溶液或结晶盐的产品盐是特别适用于制备化学镀镍浴液的。
Description
发明的技术领域
本发明是次磷酸镍制备方法的发明。
现有技术
次磷酸镍是至少自1828年(Rose，Ann.Physik，[12-87-1828]以来已被证实的的一种无机盐。它从其含水溶液中以六水合物形式Ni(H2PO2)2·6H2O结晶出来。它在化学文摘的Registry文件中已登录，登录号为RN 13477-97-9。它的组成基本成分，一方面次磷酸阴离子，另一方面镍阳离子，是人们熟知的化学镀镍方法的活性物种，该方法利用下述的自催化氧化/还原反应：
而其浴液是由次磷酸钠和可溶性镍盐，通常是硫酸盐制备的。可能会想到为这一目的使用次磷酸镍是有利的，明显的优点是不用无用地加入有钠离子和硫酸根的浴液，即这些离子因硫酸钠结晶而成为事故之源。
由Paul Pascal所著的Nouveau Traitéde Chimie Minérale|NewTreatise On Inorganic Chemistry|引用了两种制备次磷酸镍的方法，一种方法是硫酸镍与次磷酸钡的复分解，另一种方法是将氢氧化镍溶解在次磷酸中。为了将这种复分解方法转化为工业规模，提出使用次磷酸钙作为次磷酸盐的实际来源；由此得到了不适用于化学镀镍的次磷酸镍，因为它含有非常大量的由次磷酸钙本身带来的主要杂质——镁，和由于生成的硫酸钙具有不可忽略不计的溶解度而不能从反应介质中除去的钙。另一方面，正是这种原料提供了溶解方法中的镍，冶金氢氧化镍或碱式碳酸镍由于提供重金属或镁而成为污染物的来源。由于缺乏一种经济上可接受的生产方法，化学镀镍中使用次磷酸镍还受到很大的限制。
发明内容
本发明的方法克服了这些缺点。本方法在于将一种可溶性镍盐水溶液中的镍吸留在一种离子交换树脂上，再用一种次磷酸水溶液将其洗脱。因此可能得到经分析为30-35克/升镍的次磷酸溶液，这种次磷酸溶液能够直接用于制备或再生化学镀镍浴液，或由其溶液结晶出六水合次磷酸镍。
用于本发明的树脂是一种钠型羧酸型树脂(弱酸)。该类树脂是用浓的强酸溶液可再生的。因此可能从中得到浓的含交换离子的再生溶液。再生后，该树脂呈不利于吸附镍离子的酸的形式：由于用一种强碱处理，在这种情况下是氢氧化钠，又使其树脂呈羧酸盐的形式，优选的是羧酸钠的形式。这是一个高度放热的反应(大约80千卡/摩尔)。该树脂的化学性质并不很重要，但它的组成必须是这样的，它令人满意地经受住在操作中由柱内一种接一种各种反应物浓度差而产生的渗透冲击、由于酸性树脂中和放热而产生的热冲击，和在非常浓的溶液中树脂漂浮而造成的物理作用。
所有的可溶于水的镍盐都适用于本发明。硫酸镍是优选的，因为通过使该阳离子沉淀的盐例如钙盐，很容易从流出液中除去硫酸根。为了不使树脂因为过量的H+离子而使容量受到损失，镍盐溶液的pH必须尽可能地接近6。因此要避免添加酸，有时为了防止氢氧化镍沉淀和加速该盐的溶解而这样做。
本发明的次磷酸盐离子源是次磷酸。次磷酸钠在萃取固定的镍离子，至少流出液中镍离子达到可接受的浓度水平方面并不有效。
操作温度部分地由溶液浓度(镍盐、次磷酸、氢氧化钠)和它们加入柱的速度决定：有必要防止树脂受到由于过高浓度和流量的作用而使温度升得过高所带来的有害影响。而且，如果流量过高，离子交换会变得不完全。本技术领域的技术人员能够在他能达到的条件下实现正确的平衡。应努力不超过80℃或降到25℃以下，并且为了防止次磷酸盐在柱内沉淀，在任何情况下都要在用次磷酸洗脱镍的阶段中避免过低的温度。
本方法在镍方面是定量的。它提供了浓度为1-35克/升镍的次磷酸镍水溶液。这些溶液可以直接被镀镍工人用于制备他们的化学镍浴液。为了防止冷却时高浓度溶液(大于30克/升NiSO4)结晶，加入配位剂是可能的。还可能为了从这些溶液中除去六水合次磷酸镍而使其结晶，例如为了防止氧化，通过在真空下适当温度(＜50℃)时蒸发，然后通过控制冷却而结晶。
由本发明方法得到的次磷酸镍具有镀镍的明显的优点，其优点是非常显著地限制了由次磷酸盐和镍离子的反应物带入浴液中的杂质。这可以通过研究传统反应物(一方面是次磷酸钠和硫酸镍，另一方面本发明的次磷酸镍的对比含量而得到证实：
| 杂质 | 次磷酸钠 | 硫酸镍 | 次磷酸镍 |
| Ca | 20-40ppm | 11.5ppm | |
| Fe | ＜3ppm | 40ppm | ＜1ppm |
| Pb | ＜1ppm | 1ppm | ＜1ppm |
实施例
反应物
0.856摩尔/升硫酸镍溶液：225克(0.856摩尔)NiSO4·6H2O溶解在1升去离子水中。
2.5摩尔/升次磷酸溶液：用14升去离子水稀释6升50％H3PO2[d＝1.21]，即9.2摩尔。
30％氢氧化钠标准溶液。
大孔Amberlite IRC 76离子交换树脂。
操作方式
将1升树脂与770毫升0.856摩尔/升硫酸镍溶液，即38.7克Ni2+一起装入至少1125的柱中。用去离子水(大约1.5升)进行漂洗，直到漂洗水中不再有硫酸盐。用770毫升2.5摩尔/升次磷酸置换镍(在操作中，1升树脂缩小到770毫升)，然后用软化水进行漂洗。回收1060毫升含有38.7克Ni2+的洗脱液和漂洗水，呈含有0.622摩尔/升Ni2+和1.866摩尔/升H2PO2 -(次磷酸盐/镍摩尔比过量1.5)的溶液的形式。
通过装入230毫升30％氢氧化钠然后用去离子水漂洗直至中性pH的方法使树脂再生。
这样得到准备用于接收新加入硫酸镍的树脂。
Claims (3)
1.次磷酸镍的制备方法，其特征在于用离子交换柱，通过可溶于水的镍盐和次磷酸之间的离子交换进行制备。
2.根据权利要求1所述的方法，其特征在于离子交换树脂是钠型羧酸型树脂。
3.根据权利要求1或2所述的方法，其特征在于镍盐是硫酸镍。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR95/11445 | 1995-09-29 | ||
| FR9511445A FR2739372B1 (fr) | 1995-09-29 | 1995-09-29 | Procede de preparation d'hypophosphite de nickel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1198723A true CN1198723A (zh) | 1998-11-11 |
| CN1092600C CN1092600C (zh) | 2002-10-16 |
Family
ID=9483042
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96197333A Expired - Fee Related CN1092600C (zh) | 1995-09-29 | 1996-08-02 | 次磷酸镍的制备方法 |
Country Status (14)
| Country | Link |
|---|---|
| US (1) | US6030593A (zh) |
| EP (1) | EP0852566B1 (zh) |
| JP (1) | JPH11513350A (zh) |
| KR (1) | KR100450990B1 (zh) |
| CN (1) | CN1092600C (zh) |
| AT (1) | ATE179959T1 (zh) |
| AU (1) | AU6744696A (zh) |
| BR (1) | BR9610826A (zh) |
| CA (1) | CA2231065A1 (zh) |
| DE (1) | DE69602453T2 (zh) |
| EA (1) | EA000344B1 (zh) |
| FR (1) | FR2739372B1 (zh) |
| TW (1) | TW372933B (zh) |
| WO (1) | WO1997012836A1 (zh) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102786041A (zh) * | 2012-08-24 | 2012-11-21 | 南京师范大学 | 次磷酸铝的制备方法 |
| CN107313070A (zh) * | 2017-05-23 | 2017-11-03 | 西北矿冶研究院 | 一种利用脱铜终液制备次膦酸镍溶液的方法 |
| CN111892217A (zh) * | 2020-06-24 | 2020-11-06 | 南昌航空大学 | 一种化学镀镍废液中含镍化合物转化再利用的方法 |
| CN113981249A (zh) * | 2020-07-27 | 2022-01-28 | 中国石油化工股份有限公司 | 一种从废催化剂中回收钒的方法 |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2739372B1 (fr) * | 1995-09-29 | 1997-10-31 | Cesa Sa | Procede de preparation d'hypophosphite de nickel |
| US5897848A (en) * | 1997-09-19 | 1999-04-27 | Learonal Inc. | Process for producing hypophosphite compounds |
| US6965095B1 (en) * | 2004-09-20 | 2005-11-15 | Ronco Inventions, Llc | Rotisserie oven having horizontally and vertically oriented cooking elements |
| CN101942651B (zh) * | 2010-09-28 | 2012-07-25 | 蔡乐勤 | 一种无排放化学镀镍方法 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2125587C3 (de) * | 1971-05-24 | 1974-08-15 | Knapsack Ag, 5033 Huerth-Knapsack | Verfahren zur Herstellung von Hypophosphiten |
| US4532737A (en) * | 1982-12-16 | 1985-08-06 | Rca Corporation | Method for lapping diamond |
| US4552737A (en) * | 1984-01-13 | 1985-11-12 | Stauffer Chemical Company | Method to improve yields of sodium hypophosphite |
| FR2739372B1 (fr) * | 1995-09-29 | 1997-10-31 | Cesa Sa | Procede de preparation d'hypophosphite de nickel |
-
1995
- 1995-09-29 FR FR9511445A patent/FR2739372B1/fr not_active Expired - Fee Related
-
1996
- 1996-08-02 CN CN96197333A patent/CN1092600C/zh not_active Expired - Fee Related
- 1996-08-02 EA EA199800349A patent/EA000344B1/ru not_active IP Right Cessation
- 1996-08-02 BR BR9610826A patent/BR9610826A/pt not_active IP Right Cessation
- 1996-08-02 DE DE69602453T patent/DE69602453T2/de not_active Expired - Fee Related
- 1996-08-02 JP JP9514001A patent/JPH11513350A/ja active Pending
- 1996-08-02 US US09/043,991 patent/US6030593A/en not_active Expired - Fee Related
- 1996-08-02 AU AU67446/96A patent/AU6744696A/en not_active Abandoned
- 1996-08-02 CA CA002231065A patent/CA2231065A1/fr not_active Abandoned
- 1996-08-02 EP EP96927732A patent/EP0852566B1/fr not_active Expired - Lifetime
- 1996-08-02 KR KR10-1998-0701978A patent/KR100450990B1/ko not_active IP Right Cessation
- 1996-08-02 AT AT96927732T patent/ATE179959T1/de not_active IP Right Cessation
- 1996-08-02 WO PCT/FR1996/001233 patent/WO1997012836A1/fr active IP Right Grant
-
1997
- 1997-03-26 TW TW086103831A patent/TW372933B/zh active
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102786041A (zh) * | 2012-08-24 | 2012-11-21 | 南京师范大学 | 次磷酸铝的制备方法 |
| CN107313070A (zh) * | 2017-05-23 | 2017-11-03 | 西北矿冶研究院 | 一种利用脱铜终液制备次膦酸镍溶液的方法 |
| CN111892217A (zh) * | 2020-06-24 | 2020-11-06 | 南昌航空大学 | 一种化学镀镍废液中含镍化合物转化再利用的方法 |
| CN113981249A (zh) * | 2020-07-27 | 2022-01-28 | 中国石油化工股份有限公司 | 一种从废催化剂中回收钒的方法 |
| CN113981249B (zh) * | 2020-07-27 | 2023-01-10 | 中国石油化工股份有限公司 | 一种从废催化剂中回收钒的方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| KR19990045737A (ko) | 1999-06-25 |
| CN1092600C (zh) | 2002-10-16 |
| JPH11513350A (ja) | 1999-11-16 |
| EP0852566A1 (fr) | 1998-07-15 |
| FR2739372A1 (fr) | 1997-04-04 |
| EP0852566B1 (fr) | 1999-05-12 |
| ATE179959T1 (de) | 1999-05-15 |
| CA2231065A1 (fr) | 1997-04-10 |
| EA199800349A1 (ru) | 1998-10-29 |
| AU6744696A (en) | 1997-04-28 |
| FR2739372B1 (fr) | 1997-10-31 |
| DE69602453T2 (de) | 1999-12-09 |
| EA000344B1 (ru) | 1999-04-29 |
| WO1997012836A1 (fr) | 1997-04-10 |
| US6030593A (en) | 2000-02-29 |
| BR9610826A (pt) | 1999-07-13 |
| DE69602453D1 (de) | 1999-06-17 |
| TW372933B (en) | 1999-11-01 |
| KR100450990B1 (ko) | 2004-11-16 |
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