CN1072740A - 用电解法制备金属氧化物溶胶 - Google Patents
用电解法制备金属氧化物溶胶 Download PDFInfo
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- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 28
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 28
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 239000011833 salt mixture Substances 0.000 claims abstract description 7
- 230000007062 hydrolysis Effects 0.000 claims abstract description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 31
- 239000000243 solution Substances 0.000 claims description 21
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 229910052726 zirconium Inorganic materials 0.000 claims description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 239000004411 aluminium Substances 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- 150000001257 actinium Chemical class 0.000 claims description 2
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 2
- 150000002602 lanthanoids Chemical class 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000010955 niobium Substances 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 150000004703 alkoxides Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000000909 electrodialysis Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229910003088 Ti−O−Ti Inorganic materials 0.000 description 1
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910000457 iridium oxide Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000320 mechanical mixture Substances 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
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Abstract
本发明涉及通过在-20℃至50℃下直接电解使
金属盐水溶液或金属盐混合物的水溶液水解，制备单
组分或多组分金属氧化物溶胶。
Description
本发明涉及用电解法由金属盐的水溶液或金属盐混合溶液制备单组分或多组分金属氧化物溶胶。
文献中经常提到制备金属氧化物溶胶的方法。在大多数情况下，制备溶胶是先配制金属盐的水溶液，然后将其例如通过水解转化成溶胶状态，进行水解可通过加热和/或通过酸解胶和/或加碱。这些方法的缺点是常常产生沉淀而不形成溶胶，尤其是当使用贵重的金属盐（例如有机金属络合物）时，这是一个很大的缺点。因此，在配制盐溶液期间使用的金属盐常常限于低浓度。
制造这些胶体的一种改进方法是使用离子交换剂。但是，该方法的缺点是交换容量有限和反应器的容积小。在每一过程完成之后，离子交换剂必须更换和再生，于是该方法只能间歇式进行。
金属溶胶也可以通过电渗析得到，但是在电渗析中溶胶的形成和沉淀常常彼此竞争。
在苏联专利706468和929741 A和Kolloidn，Zh.第43卷第4期192-5和812-6页中，曾经公开了制备钛盐和锡盐胶体溶液的电解法。
但是，利用电解TiCl4溶液制备二氧化钛溶胶只能在有稳定剂存在下，例如在ZrCl4存在下进行。在纯金属盐溶液电解期间，溶胶形成过程中分解和沉淀越来越多。在文献中提到的电解方法中，使用由三个槽构成的电解装置，它的结构复杂，并且需要使用离子交换膜。
高纯度多组分金属氧化物溶胶的制备可用金属醇盐在低温进行水解，此方法的缺点是金属醇盐的价格非常高。
因此，有必要找到一种简单和比较不复杂的方法，可以用它以高产率制备稳定的金属氧化物溶胶，而无需加入稳定剂。
意想不到的是，现已发现了一种制备单组分或多组分金属氧化物溶胶的方法，在该方法中，常规方法的上述缺点不再存在，或是只有很小的程度的存在。
因此，本发明涉及一种制备单组分或多组分金属氧化物溶胶的方法，其特点在于，在-20℃到最高50℃的温度下，用电解法将金属盐的水溶液或金属盐混合物的溶液直接进行水解。
所用的金属盐特别是钛、铝、锆、铌、钽、钇、镧的化合物、锕系和/或镧系的化合物。
单组分或多组分金属氧化物溶胶是用简单的方式制备的：将金属盐或金属盐混合物溶于水中，将溶液电解几小时，同时将金属盐水溶液连续地通过电解槽进行再循环。溶胶形成过程即使在低温下也会发生。温度范围为-20℃至50℃，最好是0-15℃。
在制备本发明的单组分或多组分金属氧化物溶胶时，上述的先有技术的缺点不再存在或只在有限程度内发生，因为所选择的电解装置
a）利用再循环、搅动或向溶液中通入空气，避免了溶液中的不均匀性，
b）利用冷却，防止了温度上升。
在溶胶制备中电极材料也有影响。涂有氧化钌或氧化铱的钛金属栅状电极是特别合适的电极材料。
任何已知在阴极上实际上不可还原的金属盐，即，在反应条件下比H2/H+体系在该电极上的电极电势更正的金属盐，均适合用于本方法。最好是使用金属的卤化氧化物和卤化物，尤其是氯化物。金属盐混合物的溶液也可以利用本发明的方法转化成金属氧化物胶体溶液。含最多三种不同的金属盐的水溶液进行电解是优选选择的。
锆/钛、锆/铝、锆/铈、锆/钇、锆/铈/镧和钛/铝特别适于混合金属盐水溶液的电解。
多组分金属氧化物溶胶也可以将两个或多个单组分金属氧化物溶胶分别制取后混合在一起来制备，但这是费力并且耗费高的方法。
在用两种或多种不同的金属盐溶液进行电解制备多组分金属氧化物溶胶时，异极键（即如Zr-O-Ti键）已以溶胶颗粒存在，其大小约为20纳米（nm），它是与含如Zr-O-Zr和Ti-O-Ti键的不同单组分金属氧化物溶胶混合物的情况不相同的。
在本发明的方法中，对于所用的金属盐溶液的浓度没有限制。通常，对所形成的金属氧化物而言，反应在0.5%至40%重量的浓度范围内进行。
因此，本发明还涉及到浓度范围对形成的金属氧化物而言处在0.5%至40%重量之间的金属盐溶液或金属盐混合物溶液的使用。
电流强度、电压和电解时间可以改变。每个电解槽施加的电压在2伏（水的分解电压）和20伏之间，最好是在5伏和10伏之间。形成的电流密度处在0.01至0.5安培/平方厘米之间，并且在电解过程中连续下降。
因此，本发明还涉及在电解期间在2到20伏的电压和0.01-0.5安培/平方厘米的电流密度下操作。
电解时间与金属盐的量和电流强度之比有关;例如，1升含约350克TiCl4的TiCl4溶液在各为100平方厘米的阳极或阴极区的转化（在恒定的5伏电压下初始电流强度为15安）需要25-30小时。
本发明的方法依照以下反应式进行
Me＝金属
X＝常用的阴离子。
根据本发明得到的金属氧化物溶胶以其高度透明性和粒度为特征。溶胶粒子的平均粒度在5至1000纳米之间，尤其是15至100纳米之间。
溶胶的浓度与所用的盐溶液的浓度有关，相当于0.5%到40%的金属氧化物。
令人惊奇的是，我们发现在本发明的方法中不需要用添加剂来进行稳定。这大概是由于几乎完全不存在干扰性的影响，例如，外加的膜、浓度差别和高温等。
因此，这种金属氧化物溶胶由于高度透明和浓度可变，就已认可的而言，特别适合用在化妆品制品和在陶瓷中作为虹彩釉及彩饰物。根据本发明制备的TiO2溶胶尤其适合在陶瓷中作为紫外线保护剂。在陶瓷中使用二氧化钛溶胶是因为由二氧化钛溶胶形成的二氧化钛涂层由于折射率高而产生特别明亮和美学上吸引人的相干色彩。溶胶在陶瓷中的应用可参见例如德国专利4105235，在化妆品中的应用可参见德国专利4119719。
多组分金属氧化物溶胶可以容易地用喷雾、冷冻或微波干燥法转变成无定形粉末，再于适合的温度下煅烧，便可得到不同组成的多品的混合氧化物粉末。
这种类型的混合金属氧化物最好是在陶瓷（例如，钛酸锆（Zr-TiO4）、钛酸铝（AlTiO5）、铈或钇稳定的ZrO2）中用作催化剂，作为催化物质的支承材料，以及在色谱法中应用。
因此，本发明还涉及含有根据本发明制备的含单组分或多组分的金属氧化物溶胶的制品。
以下实施例是用来说明本发明而不是对本发明的限制。
实施例1
在配有双夹套并装有温度计和pH电极的玻璃烧瓶中装入1升TiCl4溶液（290克TiCl4溶在1升水中），冷却到10℃。将此溶液连续地循环通过电解槽。在施加5伏的电压和15安/平方分米的电流密度之后，进行电解30小时，在此期间电流密度下降到1安/平方分米。所得的二氧化钛溶胶的pH为1.8。溶胶是水一样透明的粘性液体。
实离例2
与实施例1相似，在20℃电解1升AlCl3溶液（284克AlCl3溶在1升水中）25小时，初始电压为15伏，电流密度7安/平方分米，电解时间25小时。在溶胶形成期间，电流密度降到0.3安/平方分米。所得的无色透明粘性液体的pH为3.0。
实施例3
在实施例1所述的仪器中，将1升之ZrOCl2溶液（260克ZrO2·8H2O溶于1升水）冷却至5℃。施加5伏电压和6.5安/平方分米的电流密度后，将电解进行20小时，最后的电流密度为0.2安/平方分米。所得的无色透明溶胶的pH为2.6。
实施例4
与实施例1相似，在5℃下电解ZrOCl2/TiCl4溶液（158.2克ZrOCl2·8H2O和262ml TiCl4溶液（357克TiCl4溶于1升水）溶于1升水），初始电压为5伏，电流密度为13.7安/平方分米，电解时间18小时。在溶胶形成过程中，电流密度降至1安/平方分米。
使用已知的干燥方法可将所得到的水清钛酸锆溶胶转变成白色可倾性粉末。
对比实施例
将实施例1和3分别制取的等摩尔量的氧化钛和氧化锆溶胶混合，然后将此机械混合物干燥。
类似于实施例4，自400℃以上形成了结晶钛酸锆。
Claims (6)
1、制备单组分或多组分金属氧化物溶胶的方法，其特点在于，通过在-20℃至50℃直接电解，使金属盐水溶液或金属盐混合物水溶液水解。
2、根据权利要求1的方法，其特征在于，金属盐是铝、钛、锆、铪、铌、钽、钇、镧的化合物、锕系和镧系的化合物。
3、根据权利要求1的方法，其特点在于，电解期间施加的电压在2-20伏之间，电流强度在0.01-0.5安/平方厘米之间。
4、根据权利要求1的方法，其特点在于，使用对于所形成的金属氧化物而言浓度为0.5%至40%重量的金属盐溶液或金属盐混合物的溶液。
5、用权利要求1的方法制备的单组分或多组分金属氧化物溶胶，其特点在于，所得金属氧化物溶胶的粒度在5到1000纳米之间，尤其是在10到100纳米之间。
6、使用根据权利要求5的单元组分或多组分金属氧化物溶胶的制品。
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| Application Number | Priority Date | Filing Date | Title |
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| DE4139579 | 1991-11-30 | ||
| DEP4139579.4 | 1991-11-30 |
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| CN1072740A true CN1072740A (zh) | 1993-06-02 |
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| US (1) | US5378400A (zh) |
| EP (1) | EP0545135B1 (zh) |
| JP (1) | JP3242169B2 (zh) |
| CN (1) | CN1072740A (zh) |
| CA (1) | CA2084024A1 (zh) |
| CZ (1) | CZ351792A3 (zh) |
| DE (1) | DE59209378D1 (zh) |
| FI (1) | FI925416A (zh) |
| MX (1) | MX9206846A (zh) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100342060C (zh) * | 2004-09-16 | 2007-10-10 | 黑龙江科技学院 | 电解法制备超细金属氧化物 |
| CN107032398A (zh) * | 2017-06-07 | 2017-08-11 | 合肥汇之新机械科技有限公司 | 一种金属氧化锆溶胶的制备工艺 |
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| DE19828231C2 (de) * | 1997-08-16 | 2000-09-07 | Merck Patent Gmbh | Verfahren zur Abscheidung poröser optischer Schichten |
| US6464765B1 (en) * | 2000-09-29 | 2002-10-15 | Ferro Corporation | Saturated soluble salt slurries for coloring ceramics |
| EP1580164A4 (en) | 2002-11-13 | 2010-12-29 | Nippon Soda Co | M TAL-OXYGEN BINDING DISPERSO, M TALLIC OXIDE FILM AND MONOMOL CULAR FILM |
| DE102005041242A1 (de) * | 2005-08-31 | 2007-03-01 | Merck Patent Gmbh | Verfahren zur Strukturierung von Oberflächen von Substraten |
| DE102005041243A1 (de) * | 2005-08-31 | 2007-03-01 | Merck Patent Gmbh | Verfahren zur Herstellung einer strukturierten Sol-Gel-Schicht |
| US8801909B2 (en) * | 2006-01-06 | 2014-08-12 | Nextchem, Llc | Polymetal hydroxychloride processes and compositions: enhanced efficacy antiperspirant salt compositions |
| US7846318B2 (en) * | 2006-01-06 | 2010-12-07 | Nextchem, Llc | Polyaluminum chloride and aluminum chlorohydrate, processes and compositions: high-basicity and ultra high-basicity products |
| US9162901B2 (en) * | 2013-03-14 | 2015-10-20 | Ppg Industries Ohio, Inc. | Electrolytic production of metal oxides |
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| SU715643A1 (ru) * | 1978-02-20 | 1980-02-15 | Предприятие П/Я В-8602 | Способ получени зол гидратированного окисла металла |
| US4801399A (en) * | 1986-02-25 | 1989-01-31 | University Of Florida | Inorganic salts as peptizing agents in the preparation of metal oxide sol-gel compositions |
-
1992
- 1992-11-17 EP EP92119595A patent/EP0545135B1/de not_active Expired - Lifetime
- 1992-11-17 DE DE59209378T patent/DE59209378D1/de not_active Expired - Fee Related
- 1992-11-26 JP JP31718692A patent/JP3242169B2/ja not_active Expired - Fee Related
- 1992-11-27 MX MX9206846A patent/MX9206846A/es unknown
- 1992-11-27 FI FI925416A patent/FI925416A/fi not_active Application Discontinuation
- 1992-11-27 CA CA002084024A patent/CA2084024A1/en not_active Abandoned
- 1992-11-28 CN CN92113469A patent/CN1072740A/zh active Pending
- 1992-11-30 CZ CS923517A patent/CZ351792A3/cs unknown
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100342060C (zh) * | 2004-09-16 | 2007-10-10 | 黑龙江科技学院 | 电解法制备超细金属氧化物 |
| CN107032398A (zh) * | 2017-06-07 | 2017-08-11 | 合肥汇之新机械科技有限公司 | 一种金属氧化锆溶胶的制备工艺 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05222562A (ja) | 1993-08-31 |
| CA2084024A1 (en) | 1993-05-31 |
| EP0545135A1 (de) | 1993-06-09 |
| DE59209378D1 (de) | 1998-07-23 |
| FI925416A0 (fi) | 1992-11-27 |
| MX9206846A (es) | 1993-05-01 |
| US5378400A (en) | 1995-01-03 |
| FI925416A (fi) | 1993-05-31 |
| EP0545135B1 (de) | 1998-06-17 |
| JP3242169B2 (ja) | 2001-12-25 |
| CZ351792A3 (en) | 1993-06-16 |
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