CN116601336A - 用于电解氯化过程的电解器和自清洁的电解氯化系统 - Google Patents
用于电解氯化过程的电解器和自清洁的电解氯化系统 Download PDFInfo
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- CN116601336A CN116601336A CN202180080235.4A CN202180080235A CN116601336A CN 116601336 A CN116601336 A CN 116601336A CN 202180080235 A CN202180080235 A CN 202180080235A CN 116601336 A CN116601336 A CN 116601336A
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- 238000005660 chlorination reaction Methods 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 18
- 238000004140 cleaning Methods 0.000 title claims abstract description 11
- 230000008569 process Effects 0.000 title description 4
- 238000005868 electrolysis reaction Methods 0.000 title description 2
- 239000011248 coating agent Substances 0.000 claims abstract description 34
- 238000000576 coating method Methods 0.000 claims abstract description 34
- 239000000758 substrate Substances 0.000 claims abstract description 28
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 22
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 19
- 239000010936 titanium Substances 0.000 claims abstract description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 230000003197 catalytic effect Effects 0.000 claims abstract description 15
- 239000012267 brine Substances 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims abstract description 14
- 239000010955 niobium Substances 0.000 claims abstract description 12
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 11
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000004659 sterilization and disinfection Methods 0.000 claims abstract description 11
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 11
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 10
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052718 tin Inorganic materials 0.000 claims abstract description 10
- 230000001404 mediated effect Effects 0.000 claims abstract description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 22
- 239000010410 layer Substances 0.000 claims description 17
- 238000011068 loading method Methods 0.000 claims description 13
- 239000011780 sodium chloride Substances 0.000 claims description 12
- 239000003792 electrolyte Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 3
- 229910001887 tin oxide Inorganic materials 0.000 claims description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
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- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
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- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000008199 coating composition Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
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- 239000013535 sea water Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
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- 239000011149 active material Substances 0.000 description 1
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- 238000009835 boiling Methods 0.000 description 1
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- 150000003841 chloride salts Chemical class 0.000 description 1
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- 230000009849 deactivation Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
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- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 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
- 238000005488 sandblasting Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
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- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
- C02F1/4674—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation with halogen or compound of halogens, e.g. chlorine, bromine
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- C25B11/093—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one noble metal or noble metal oxide and at least one non-noble metal oxide
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Abstract
本发明涉及氯化电解器,包含提供有适合于盐水循环的入口和出口的壳体;至少一对彼此面对并置于所述壳体内的双极性电极。电解器特征在于所述至少一对的每个双极性电极包含:阀金属基材;在所述基材上设置的包含至少一个含钌和钛的催化组合物的层的活性涂层;置于所述活性涂层上方的顶涂层,其包含至少一个含钽、铌、锡的氧化物或其组合的组合物的层。本发明还涉及包含这样电解器的自清洁的电解氯化系统,其生产方法,其在次氯酸盐介导的水消毒的正常和低盐度池中的用途和次氯酸盐介导的水消毒的方法。
Description
技术领域
本发明涉及在极性反转条件下操作的氯化电解器,其生产方法和自清洁的电解氯化系统。
背景技术
电解氯化方法在于通过电解反应在盐水中生产次氯酸。所得次氯酸钠可用在涉及水消毒和氧化例如饮用水、游泳池的水处理或冷却塔中微生物控制的各种应用中。
次氯酸钠对细菌、病毒和真菌有效并具有微生物对其效果不可产生抗性的优势。
与可加入水以实现类似结果的氯气或片剂相反,在电解氯化方法中活性材料原位生产,因此避免运输、环境和/或储存问题。根据应用,通过向电解槽施加合适的电流来进行该方法,所述电解槽包含至少两个电极和含有盐水即盐和水以不同浓度的混合物的电解质。电化学反应的结果是产生次氯酸钠和氢气。
在过去,提供有含阀金属和贵金属(特别是来自铂族的稀有过渡金属)混合物的活性涂层组合物的钛电极已成功用作这些类型槽中的阳极。然而,随时间的推移,电极在其活性表面上出现锈皮,这不利地影响槽的次氯酸生产效率。
为了防止/减小锈皮的形成,可向电极施加周期性极性反转从而促进它们的自清洁。反转极性也减小电极之间的离子桥连,并可防止不均匀的电极磨损。
在极性反转条件下,其中每个电极交替工作作为阴极和作为阳极,在几个反转循环之后在活性涂层组合物中偶然使用的一些元素变得不稳定并溶解在电解质中,从而导致不足的电极寿命。
通常,极性反转对于电极的活性涂层是有害操作,快速引起了其由于分层而失活。
为了减少这些问题,需要提供在极性反转条件下以比每个电极仅作为阳极或阴极工作时高得多的涂层负载使用的双极性电极。通常,电极耐久性取决于极性反转频率和涂层负载。
提高涂层负载在材料量和冗长的生产过程方面不利地影响电极的成本。此外,因为许多活性涂层组合物依赖于呈现出稀缺可得性的稀有过渡金属,所以提高的负载量也使任何采购相关问题恶化。
期望具有自清洁电极用于电解氯化系统,其在广泛的可能应用和操作条件下表现出改进的寿命和效率,并可能维持减小的生产成本。此外,期望在正常和低盐度池即在盐水平等于或小于6g/l的池中(通常在低盐度应用中0.5–2.5g/l NaCl和在正常盐度应用中2.5-4g/l NaCl)使用这样的电解氯化系统。
国际专利申请WO 2019/215944 A1描述了用于产生臭氧的电解器,其配备有具有厚的介电表面层的电极以提高在中间层的集中的贵金属位点产生氧的过电势。这些电极既不适合于生产氯也不适合于在极性反转条件下操作。
发明内容
本发明涉及氯化电解器,包含壳体和至少一对彼此面对并置于所述壳体内的双极性电极,所述壳体提供有适合于盐水循环的入口和出口。每个双极性电极包含:(i)阀金属基材;(ii)在所述基材上设置的活性涂层,其包含至少一个含钌和钛的催化组合物的层;(iii)顶涂层,其包含至少一个含钽、铌、锡的氧化物或其组合的组合物的层并置于所述活性涂层上方。
在另一方面,本发明涉及自清洁的电解氯化系统,包含:(i)以上描述的氯化电解器;(ii)在所述电解器内循环的电解质,其包含1-30g/l NaCl盐水溶液;(iii)用于将与其电连接并置于电解器的壳体外部的双极性电极对的极性进行周期性反转的电子系统。
在另一方面,本发明涉及制造根据本发明的氯化电解器的方法。
在另一方面,本发明涉及以上描述的氯化电解器用于次氯酸盐介导的水消毒的正常和低盐度池中的用途。
在又一方面,本发明涉及在极性反转条件下使用以上描述的氯化电解器用于次氯酸盐介导的水消毒方法。
具体实施方式
在一方面,本发明涉及氯化电解器,其包含:
壳体,其提供有适合于盐水循环的入口和出口以及至少一对彼此面对并置于所述壳体内的双极性电极,其中所述一对中的每个双极性电极包含:(i)阀金属基材;(ii)在所述基材上方设置的活性涂层,其包含至少一个含钌和钛的催化组合物的层;(iii)置于所述活性涂层上方的顶涂层,其包含至少一个含钽、铌、锡的氧化物或其组合的组合物的层。
至少一个包含钌和钛的催化组合物的层在其电性质方面是基本上均匀的层。至少一个催化组合物的层也在其形态性质方面是均匀的并基本上构成包含钌和钛的固溶体,优选均匀固溶体,其中金属主要是氧化物,即氧化钌和氧化钛。
根据本发明的氯化电解器可用于各种应用中的次氯酸盐介导的水消毒,例如池塘、废水消毒(例如城市水处理、黑水和灰水处理、海水氯化…)。
其可有利地在极性反转条件下操作,由此确保电极的自清洁并避免锈皮的形成。
所述对中的每个电极可在一侧或两侧上涂覆。按照惯例,应布置两个相对的电极从而具有彼此面对的涂覆侧。
氯化电解器可包含多个双极性电极对,从而产生基本上彼此平行布置的涂覆电极的堆叠。
应设计壳体从而允许(一个或多个)双极性电极对与外部发电机电连接。如本领域公知的,发电机可有利地配备有以预设频率(通常在30min-10小时的范围内,其取决于应用和操作条件例如水污染物和水硬度)反转电极极性的系统。
阀金属基材可具有本领域通常使用的任何几何形状,例如但不限于:板坯、穿孔板、网、百叶窗。优选地,出于其耐久性、成本和容易表面制备,由钛制成基材。
在施涂活性涂层之前,应优选清洁、喷砂和蚀刻基材以确保适当的附着。
活性涂层可使用辊涂布器、刷涂和喷射技术直接设置在阀金属基材上方。或者,要求保护的发明允许中间涂层插在基材和活性涂层之间,例如以改进活性涂层的附着。在这种情况下,后者应仍考虑被设置在基材上方,尽管是间接的。
在一种实施方案中,根据本发明的氯化电解器的催化组合物包含25%-45%钌和55%-75%钛,关于元素以重量百分比表示。
在另一实施方案中,催化组合物可任选包含2%-5%的选自以下的掺杂元素:钪、锶、铪、铋、锆、铝、铜、铑、铱、铂、钯和它们的相互组合。这些掺杂剂可有利地有助于改进的寿命和氯化电解器的游离可得氯效率。
在根据任何以上实施方案的活性涂层上(组合或单独地)施涂钽、铌或锡氧化物的绝缘顶涂层对于电极的给定寿命目标而言允许减小Ru的负载至多38%,而没有影响效率。
Ru负载的减少提供显著优势,因为其稀缺性和随之而来的采购和成本问题,尤其是与本发明的顶涂层组合物中使用的金属氧化物相比。
发明人发现了氧化锡的顶涂层在实施本发明中工作特别好,因为相比Ta或Nb,Sn看起来形成使Cl-离子更好扩散至活性层的氧化物。Sn顶涂层还由于其较不倾向形成位错而形成较少开裂的表面,所述位错引起可例如在氧化钽表面上观察到的典型裂纹。较少开裂的表面防止电解质溶解活性层的不稳定部分。
在另外的实施方案中,顶涂层优选足够薄,在0.5-7微米之间,因为其可有助于保持活性层的游离可得氯(FAC)效率。
在任何以上实施方案中,活性涂层可具有1-30g/m2的钌负载,这可对于具有盐度大于6g/l(但优选小于30g/l)的应用例如海水氯化器的应用和对于具有盐度小于6g/l例如在池塘中发现的0.5-4g/l的应用起作用。
在池塘应用中,顶涂层具有2-6g/m2的优选总负载。
在本发明不限于特定理论的情况下,根据本发明的顶涂层形成网而不是阻挡层:其减小由于气泡的摩擦所致的活性涂层表面的机械磨损并在极性反转发生时保持材料部分溶解,从而防止涂层的分层和钌与其它任选掺杂剂溶解在电解质中。与此同时,顶涂层的多孔和薄度允许电解质到达活性涂层的催化中心。
在另一方面,本发明涉及自清洁的电解氯化系统,包含:(i)以上描述的氯化器电解器;(ii)在所述电解器内循环的包含1-30g/l NaCl盐水溶液的电解质;(iii)用于将电解器的双极性电极的极性进行周期性反转的电子系统,该电子系统优选位于电解器的壳体外部并与双极性电极电连接。
将双极性电极的极性进行周期性反转的电子系统配备有内部时钟,其允许以预设时间间隔(在30min-10小时的范围内)反转双极性电极的极性。
在池塘应用中,在电子系统以1-4小时的预设间隔将双极性电极对的极性进行反转时,发明人观察到根据本发明的自清洁电解氯化系统表现特别好。
已发现,包含并联连接的5-15个双极性电极对的堆叠有利于实施本发明。
根据本发明的电子系统可有利地在约200-600A/m2、优选200-400A/m2的电流密度下操作。
在另一方面,本发明涉及用于生产上文描述的氯化电解器的方法,包括按照以下顺序阶段制造至少一对双极性电极中的每个电极的步骤:
a)向阀金属基材施涂包含钌和钛前体的活性涂层溶液从而获得涂覆的基材;
b)在450-550℃的温度下烘焙涂覆的基材2-10分钟;
c)重复步骤a)和b)直至实现钌的期望负载;
d)向涂覆的基材施涂包含钽、铌、锡或其组合的前体的顶涂层溶液;
e)在450-550℃的温度下烘焙涂覆的基材2-10分钟;
f)重复步骤d)和e)直至实现钽、铌、锡或其组合的期望负载;
g)在450-550℃范围内的温度下进行最终热处理。
钌和钛的前体以及钽、铌或锡的前体是选自以下的化合物:金属的甲醇盐、乙醇盐、丙醇盐、丁醇盐、氯化物、硝酸盐、碘化物、溴化物、硫酸盐或乙酸盐和它们的混合物。
任选地,在步骤a)之后和/或步骤d)之后,可在20-80℃的温度下空气干燥该涂覆的基材2-10分钟。
通常,根据本发明的氯化电解器,特别是关于双极性电极结构,可成功地用于次磷酸盐生产的全部应用中,其经受极性反转,以减小活性涂层的贵金属负载,或如果应用相同负载则表现出延长的寿命,而没有损害FAC效率。
发明人发现了氯化电解器在以0.5-4g/l的盐度下操作的池塘应用中工作特别好。
在另外方面,本发明涉及根据本发明的氯化电解器在次氯酸盐介导水消毒的正常和低盐度池中的用途,即用于在盐水平等于或小于6g/l(通常在低盐度应用中0.5–2.5g/lNaCl和在正常盐度应用中2.5-4g/l NaCl)下操作的池中使用。
包括以下实例来说明将本发明付诸实践的具体方式,其实用性在要求保护的值范围内进行了巨大程度的验证。
本发明也涉及次氯酸盐介导的水消毒的方法,包括以下步骤
a)在至少一个如以上限定的氯化电解器内,使包含1-30g/l NaCl盐水溶液的电解质循环,所述氯化电解器包含一个或多个双极性电极对;
b)将电流施加至所述双极性电极对上以在所述NaCl盐水溶液中产生次氯酸盐;
c)在施加所述电流期间将该至少一对双极性电极的极性进行周期性反转。
根据本发明的一种实施方案,所述至少一对双极性电极的极性以选自以下范围的时间间隔反转:一分钟至20小时、优选30min至10小时和特别优选1至4小时。
在本发明的优选实施方案中,将电流以选自200至600A/m2的范围、优选选自200至400A/m2的范围的电流密度施加至所述至少一对双极性电极上。
本领域技术人员应理解,以下公开的设备、组成和技术代表发明人发现的在发明实施中很好起作用的设备、组成和技术;然而,本领域技术人员鉴于本公开内容应理解,可在公开的具体实施方案中进行许多改变并仍然获得相同或相似的结果,而没有脱离本发明的范围。
实验准备
在以下实施例和反例中使用的全部电极样品中,如此制造双极性电极对的阀金属基材:从100mm×100mm×1mm尺寸的1级钛板开始,在超声浴中使用丙酮脱脂,并随后经受喷砂和在22%浓度下全沸HCl蚀刻。
通过将钌和钛的氯盐以Ru:Ti之比等于28:72(以元素的重量比计)溶解在10%水性HCl中而获得用于制备电极样品E1、E2a、E2b和样品C1-C3的催化溶液,其中每一催化溶液中钌的最终浓度等于45g/l。
搅拌如此制备的溶液30分钟。
在全部电极样品E1、E2a、E2b、C1-C3中,使用刷涂,以0.8g/m2的钌获得率,用以上描述的催化溶液涂覆钛基材。
在每一涂层施涂之后,在500-550℃的温度下烘焙样品10分钟。
对于每个样品E1、E2a、E2b、C1-C3重复以上涂覆工序,直至实现根据以下表1的总钌负载。
表1
实施例1
用由使用乙酸稀释直至达到40g/l的最终浓度的Sn乙酸盐溶液获得的顶涂层溶液进一步涂覆由实验准备得到的样品E1。通过刷子施涂4层的顶涂层溶液,总Sn负载为4.5g/m2。在每层之后,在500-550℃的温度下随后烘焙样品10分钟。
在最后一层之后,使样品经受500-550℃的温度下的烘焙后处理3小时。
根据以下加速测试工序测试样品电极E1:
在25℃下,将一对相同电极样品置于壳体中,该壳体提供有入口和出口且特征为3mm的电极间间隙并含有1l的4g/l NaCl和70g/l Na2SO4的水溶液。
电极对在1000A/m2的电流密度下工作,并在测试持续时间期间经受每1分钟的极性反转。将该电极对保持在测试条件下直至槽电压超过8.5伏特(“加速寿命”,对于催化组合物中每g/m2的钌以小时测量)。
结果记录于表2中。
以小时计的E1寿命性能(对应于145小时线上(HOL))被选择作为双极性电极的目标性能,如表2中报道的。
在25℃的温度下,在300A/m2下,在水中3g/l的NaCl中测量样品的FAC。
实施例2
用通过将80g的TaCl5溶解在1l的20%浓度HCl中并在室温下搅拌溶液30分钟获得的顶涂层溶液进一步涂覆由实验准备得到的样品E2,即E2a和E2b。对于每个E2样品,通过刷子施涂1层顶涂层溶液,总Ta负载为1g/m2。首先在300-350℃的温度下烘焙样品10分钟,然后在500-550℃的温度下烘焙10分钟。
根据实施例1中描述的相同测试工序测试样品E2。
分析样品E2的结果,满足E1的目标性能的唯一样品是E2b;它的性能在表2中表征。
反例1
使由实验准备得到的样品C即C1-C3在500-550℃的温度下经受烘焙后处理3小时,并根据实施例1中描述的测试工序测试。
分析样品C的结果,满足E1的目标性能的唯一样品是C3;它的性能在表2中表征。
表2
之前的描述不应意图为限制本发明,本发明可根据不同的实施方案使用而不偏离其范围,并且本发明的范围仅由所附权利要求书限定。
遍及本申请的说明书和权利要求书,术语“包含”及其变体例如“含”和“包含有”不意图排除其它元素、组分或额外方法步骤的存在。
对文献、法令、材料、装置、制品等的讨论包括在本说明书中,仅出于提供本发明背景的目的。不建议或表示在本申请的每个权利要求的优先权日之前,这些事项中的任何或全部形成现有技术基础的一部分或是本发明相关领域中的公知常识。
Claims (14)
1.氯化电解器,包含:
-提供有适合于盐水循环的入口和出口的壳体;
-彼此面对并置于所述壳体内的至少一对双极性电极;
特征在于所述至少一对中的每个双极性电极包含:
-阀金属基材;
-在所述基材上方设置的活性涂层,其包含至少一个含钌和钛的催化组合物的层;
-置于所述活性涂层上方的顶涂层,其包含至少一个含钽、铌、锡的氧化物或其组合的组合物的层。
2.根据权利要求1所述的氯化电解器,其中所述催化组合物包含25%-45%钌和55%-75%钛,关于元素以重量百分比表示。
3.根据权利要求2所述的氯化电解器,其中所述催化组合物还包含2%-5%的选自以下的掺杂元素:钪、锶、铪、铋、锆、铝、铜、铑、铱、铂、钯和它们的相互组合。
4.根据权利要求1-3中任一项所述的氯化电解器,其中所述活性涂层具有1-30g/m2的钌负载量。
5.根据权利要求1-4中任一项所述的氯化电解器,其中所述顶涂层由氧化锡组成。
6.根据权利要求1-5中任一项所述的氯化电解器,其中所述顶涂层具有0.5-7微米的厚度。
7.根据权利要求1-6中任一项所述的氯化电解器,其中所述顶涂层具有2-6g/m2的总负载量。
8.根据权利要求1-7中任一项所述的氯化电解器,其中所述阀金属基材是钛。
9.自清洁的电解氯化系统,包含:
-根据权利要求1-8中任一项的氯化电解器;
-在所述氯化电解器内循环的电解质,其包含1-30g/l NaCl盐水溶液;
-用于将至少一对双极性电极的极性进行周期性反转并与其电连接的电子系统。
10.用于生产根据权利要求1-8中任一项的氯化电解器的方法,包括按照以下顺序阶段制造至少一对双极性电极中的每个电极的步骤:
a)向阀金属基材施涂包含钌和钛的前体的活性涂层溶液从而获得涂覆的基材;
b)在450-550℃的温度下烘焙涂覆的基材2-10分钟;
c)重复步骤a)和b)直至实现钌的期望负载量;
d)向涂覆的基材施涂包含钽、铌、锡或其组合的前体的顶涂层溶液;
e)在450-550℃的温度下烘焙该涂覆的基材2-10分钟;
f)重复步骤d)和e)直至实现钽、铌、锡或其组合的期望负载量;
g)在450-550℃范围内的温度下进行最终热处理;
其中所述钌和钛的前体和所述钽、铌或锡的前体是选自以下的化合物:金属的甲醇盐、乙醇盐、丙醇盐、丁醇盐、氯化物、硝酸盐、碘化物、溴化物、硫酸盐或乙酸盐和它们的混合物。
11.根据权利要求1-8所述的氯化电解器在次氯酸盐介导的水消毒的正常和低盐度池中的用途。
12.次氯酸盐介导的水消毒的方法,包括以下步骤
a)在至少一个根据权利要求1-8中任一项的氯化电解器内使包含1-30g/l NaCl盐水溶液的电解质循环,所述氯化电解器包含一个或多个双极性电极对;
b)将电流施加至所述双极性电极对以在所述盐水溶液中产生次氯酸盐;
c)在施加所述电流期间将至少一对双极性电极的极性进行周期性反转。
13.根据权利要求12所述的方法,其中进行所述至少一对双极性电极的极性以选自一分钟至20小时的范围的时间间隔进行反转。
14.根据权利要求12或13之一所述的方法,其中将电流以选自200至600A/m2的范围的电流密度施加至所述至少一对双极性电极对上。
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PCT/EP2021/087127 WO2022136455A1 (en) | 2020-12-22 | 2021-12-21 | Electrolyser for electrochlorination processes and a self-cleaning electrochlorination system |
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