CN112547087A - 一种铁/猛酸镧催化剂的制备方法及应用 - Google Patents
一种铁/猛酸镧催化剂的制备方法及应用 Download PDFInfo
- Publication number
- CN112547087A CN112547087A CN202011499511.4A CN202011499511A CN112547087A CN 112547087 A CN112547087 A CN 112547087A CN 202011499511 A CN202011499511 A CN 202011499511A CN 112547087 A CN112547087 A CN 112547087A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- iron
- solution
- lanthanum
- nitrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 24
- 229910052746 lanthanum Inorganic materials 0.000 title claims abstract description 21
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 title description 4
- 239000011572 manganese Substances 0.000 claims abstract description 40
- 239000002351 wastewater Substances 0.000 claims abstract description 39
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims abstract description 32
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims abstract description 21
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 19
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 19
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 17
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000012266 salt solution Substances 0.000 claims abstract description 16
- 239000003513 alkali Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000000243 solution Substances 0.000 claims abstract description 15
- 239000002360 explosive Substances 0.000 claims abstract description 14
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 239000007864 aqueous solution Substances 0.000 claims abstract description 9
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 9
- 239000011148 porous material Substances 0.000 claims abstract description 9
- 230000032683 aging Effects 0.000 claims abstract description 8
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000004065 wastewater treatment Methods 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 238000000967 suction filtration Methods 0.000 claims abstract description 5
- 230000002195 synergetic effect Effects 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims abstract description 4
- 239000002270 dispersing agent Substances 0.000 claims abstract description 3
- 238000009826 distribution Methods 0.000 claims abstract description 3
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 3
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 239000010842 industrial wastewater Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- KHVFLESJSJZMMW-UHFFFAOYSA-N [Mn].[Fe].[La] Chemical compound [Mn].[Fe].[La] KHVFLESJSJZMMW-UHFFFAOYSA-N 0.000 claims description 3
- 239000003377 acid catalyst Substances 0.000 claims description 3
- 238000010335 hydrothermal treatment Methods 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 12
- 229910000510 noble metal Inorganic materials 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000012153 distilled water Substances 0.000 description 15
- 230000003197 catalytic effect Effects 0.000 description 10
- 238000012512 characterization method Methods 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 229910002321 LaFeO3 Inorganic materials 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000006385 ozonation reaction Methods 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 229910002328 LaMnO3 Inorganic materials 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000002920 hazardous waste Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910017771 LaFeO Inorganic materials 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000010799 household hazardous waste Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- B01J35/612—
-
- B01J35/613—
-
- B01J35/633—
-
- B01J35/647—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- C—CHEMISTRY; METALLURGY
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
Abstract
本发明提供一种铁/锰酸镧催化剂的制备方法及应用,属于废水处理领域。本发明以聚乙二醇(PEG)为分散剂,与氨水共同溶解于水溶液中形成碱溶液A,将硝酸铁、硝酸锰中的一种或两种与硝酸镧共同溶解于水溶液中,得到盐溶液B,将碱溶液逐滴加入无机盐溶液形成溶液,再经过搅拌、水热老化处理,之后冷却、抽滤、洗涤、干燥、焙烧得到LaFe1‑xMnxO3催化剂,制得的LaFe1‑ xMnxO3催化剂近似球形,粒径为10~50nm,比表面积为5~40cm3g‑1,孔径尺寸分布为1.5‑18nm,是具有高稳定性、高活性、低成本的非贵金属改性钙钛矿型催化剂材料,在应用到催化臭氧过氧化氢协同氧化反应处理间甲酚模型废水、火炸药生化出水具有较好的效果。
Description
技术领域
本发明提供一种铁/锰酸镧催化剂的制备方法及应用,属于废水处理领域。
背景技术
在当前,高毒性、难生物降解工业有机废水的高效、快速和无害化处理是当前废水处理的重点和难点。催化臭氧氧化(Catalytic Wet Ozonation Oxidation,CWOO)技术的出现和不断发展为此类废水的处理提供了一条可行路径,由于它具有氧化能力强、工艺简单、无二次污染的特点。已成为工业废水预处理及深度处理的主流技术,被大量工业园区及企业所采用。目前采用其单一技术,在达标排放方面也存在去除率低的问题,尚需要进一步优化。
由于催化剂是CWOO反应体系的核心,学者们围绕高性能催化剂的开发,从材料选择、制备方法和反应工艺等多个角度开展了大量研究,使得CWOO技术取得了长足进步。目前常用的CWOO催化剂为金属负载型催化剂,活性组分有Fe、Cu、Ni、Mn、Pt、Pd等,载体主要有氧化铝、分子筛、活性炭等。由于国内环保市场价格导向,成熟工业化CWOO催化剂活性组分以过渡金属Fe和Mn为主,该类催化剂以高活性及低成本占据国内主要CWOO催化剂市场。但该类催化剂最大的弊端在于活性组分容易流失,且催化剂失活后无法进行回收再生,只能作为危废进行处理。废水处理时TOC去除率低,若根据目前国内危险废物处理规定,该类危废处理处置费用高达5000元/吨,这意味着3~4年后,使用此种CWOO催化剂处理废水的企业每年将需要承担上亿元的废催化剂处置费用。因此急需开发新型、高效、可快速再生的CWOO催化剂,以减少失活催化剂的后处理费用,同时应对国内日益严格的环保法规。
发明内容
本发明的目的是为了解决现有废水处理时TOC去除率低,无法满足排放要求的问题,提供一种铁/锰酸镧催化剂的制备方法及应用。本发明旨在制备非贵金属改性钙钛矿催化剂,在典型ABO3钙钛矿结构基础上,更换A、B位点稀土金属La和过渡金属Fe、Mn,合成Mn掺杂LaFeO3为基本组成的钙钛矿型催化剂,通过对A位和B位进行非贵金属改性以提高其氧化还原性能。通过调控铁猛含量,找到催化剂最佳活性催化剂,最终制备一种高稳定性、高活性、低成本的非贵金属改性钙钛矿型催化剂。将其应用到催化臭氧过氧化氢协同氧化反应处理间甲酚模型废水,火炸药废水成分二苯胺模型废水、火炸药生化出水具有较好的效果,对于军工火炸药废水的处理具有重大意义。
本发明的目的是通过如下技术方案实现的。
一种铁/锰酸镧催化剂的制备方法,将碱溶液逐滴加入无机盐溶液形成混合溶液,再经过搅拌、水热老化处理,之后冷却、抽滤、洗涤、干燥、焙烧得到铁/猛酸镧催化剂。
具体步骤如下:
步骤一、以聚乙二醇(PEG)为分散剂,与氨水共同溶解于水溶液中形成碱溶液A;氨水体积分数为5~10%,PEG质量分数为0.1~0.4%,PEG分子量为1000~20000;
步骤二、将硝酸铁、硝酸锰中的一种或两种与硝酸镧共同溶解于水溶液中,得到盐溶液B,硝酸铁、硝酸锰、硝酸铁和硝酸猛与硝酸镧的摩尔比均为0~1:1;
步骤三、将步骤一中得到的碱溶液A逐滴加入步骤二中得到的盐溶液B中,同时磁力搅拌,碱溶液A与盐溶液B体积比1:1;
步骤四、将步骤三中得到的溶液于室温下磁力搅拌0.5~2h;得到的混合溶液于80~200℃进行水热处理4~48小时,之后冷却至室温,抽滤水洗,120℃烘干6~24h;
步骤五、将步骤四中得到材料转移至坩埚内,在在马弗炉中空气气氛下以1~3℃/min的升温速率升温至700~900℃煅烧2~4h,记为LaFe1-xMnxO3催化剂;
步骤二中当硝酸铁、硝酸猛与硝酸镧共同溶解于水溶液中时,所述硝酸铁和硝酸猛摩尔比为1-x:x,x=0~1,摩尔比优选不大于0.24;
制得的LaFe1-xMnxO3催化剂近似球形,粒径为10~50nm;
制得的LaFe1-xMnxO3催化剂比表面积为5~40cm3g-1,孔径尺寸分布为1.5-18nm;
所述铁猛酸镧催化剂的应用,其适用于催化臭氧过氧化氢协同氧化反应处理工业废水,尤其适用于火炸药生化废水,反应条件:常温、常压,废水初始pH:3.0~9.0,O3(mg/L):COD(mg/L)=(1~3.18):1,H2O2(mg/L):COD(mg/L)=(0~2.36):1,臭氧流量与废水流量比为(3~10):1。
具体的为将所述铁猛酸镧催化剂应用到催化臭氧过氧化氢协同氧化反应处理间甲酚模型废水,火炸药废水成分二苯胺模型废水、火炸药生化出水。
有益效果
1、本发明的一种铁/锰酸镧催化剂的制备方法,旨在非贵金属改性钙钛矿催化剂,合成Mn掺杂LaFeO3为基本组成的钙钛矿型催化剂,制得具有高稳定性、高活性、低成本的非贵金属改性钙钛矿型催化剂材料,为催化过氧化氢协同臭氧氧化处理火炸药废水的处理具有重大意义。且工艺流程简单、经济环保。
2、本发明的一种铁/锰酸镧催化剂的制备方法制得的催化剂活性高、寿命长、易再生。
3、将本发明制得的铁/锰酸镧催化剂用于催化臭氧过氧化氢协同氧化反应处理工业废水,特别适合催化臭氧过氧化氢协同氧化反应处理间甲酚模型废水,火炸药废水成分二苯胺模型废水、火炸药生化出水。
附图说明
图1为LaFe1-xMnxO3 CWOO间歇实验间甲酚转化率;
图2为LaFe0.26Mn0.74O3放大10倍后间歇实验间甲酚转化率;
图3为LaFeO3放大50000倍SEM图;
图4为LaFe0.26Mn0.74O3放大50000倍SEM图;
图5为LaFe0.5Mn0.5O3放大50000倍SEM图;
图6为LaFe0.74Mn0.26O3放大50000倍SEM图;
图7为LaMnO3放大50000倍SEM图;
图8为LaFe0.26Mn0.74O3与Mn/Al2O3反应效果对比图;
图9为反应机理推测图。
具体实施方式
下面结合附图与实施例对本发明作进一步说明。
以火炸药生产废水或二苯胺模型底物为研究对象,使用间歇式催化过氧化氢协同臭氧氧化(CWOO)反应装置评价合成的LaFe1-xMnxO3催化剂,如图1所示;对放大10倍后的LaFe0.26Mn0.74O3催化剂进行间歇实验,结果如图2所示,从图中可以看出放大10倍后的催化剂依然对间甲酚有着较好的转化效果,在16分钟左右接近完全转化;TOC去除率为34.09%。以ICP分析出水中La、Fe、Mn金属离子的浓度,评价催化剂活性组分溶出率。
实施例1:
称取9.0101g La(NO3)3·6H2O、8.4491g Fe(NO3)3·9H2O溶于100mL蒸馏水混合均匀;取8mL氨水和0.25g聚乙二醇(PEG)(分子量20000)加入92mL蒸馏水中;将混合均匀的碱液逐滴加入到盐溶液中,滴加完毕后磁力搅拌一个小时;至于100℃老化24小时,真空过滤,用蒸馏水洗涤至中型,过滤后在120℃烘箱内进行干燥14小时,之后用马弗炉在空气气氛下以3℃/min的升温速率升温至800℃煅烧4h,记为LaFeO3。对LaFeO3进行物理吸附表征(见表1)及SEM表征(见图3),并进行催化臭氧氧化实验,反应条件:常温、常压,100ppm间甲酚模型废水,废水初始pH:7.0,O3(mg/L):COD(mg/L)=1.9:1,臭氧流量与废水流量比为3.7:1。
实施例2:
称取9.0538g La(NO3)3·6H2O、7.4085g Mn(NO3)2(50%)溶于100mL蒸馏水混合均匀;取8mL氨水和0.25g聚乙二醇(PEG)(分子量20000)加入92mL蒸馏水中;将混合均匀的碱液逐滴加入到盐溶液中,滴加完毕后磁力搅拌一个小时;至于100℃老化24小时,真空过滤,用蒸馏水洗涤至中型,过滤后在120℃烘箱内进行干燥14小时,之后用马弗炉在空气气氛下以3℃/min的升温速率升温至800℃煅烧4h,记为LaMnO3。对LaMnO3进行物理吸附表征(见表1)及SEM表征(见图4),并进行催化臭氧氧化实验,反应条件:常温、常压,100ppm间甲酚模型废水,废水初始pH:7.0,O3(mg/L):COD(mg/L)=1.9:1,臭氧流量与废水流量比为3.7:1。
实施例3:
称取9.0101g La(NO3)3·6H2O、4.2246g Fe(NO3)3·9H2O、3.6864g Mn(NO3)2(50%)溶于100mL蒸馏水混合均匀;取8mL氨水和0.25g聚乙二醇(PEG)(分子量20000)加入92mL蒸馏水中;将混合均匀的碱液逐滴加入到盐溶液中,滴加完毕后磁力搅拌一个小时;至于100℃老化24小时,真空过滤,用蒸馏水洗涤至中型,过滤后在120℃烘箱内进行干燥14小时,之后用马弗炉在空气气氛下以3℃/min的升温速率升温至800℃煅烧4h,记为LaFe0.5Mn0.5O3。对LaFe0.5Mn0.5O3进行物理吸附表征(见表1)及SEM表征(见图5),并进行催化臭氧氧化实验,反应条件:常温、常压,100ppm间甲酚模型废水,废水初始pH:7.0,O3(mg/L):COD(mg/L)=1.9:1,臭氧流量与废水流量比为3.7:1。
实施例4:
称取9.0101g La(NO3)3·6H2O、6.2532g Fe(NO3)3·9H2O、1.9169g Mn(NO3)2(50%)溶于100mL蒸馏水混合均匀;取8mL氨水和0.25g聚乙二醇(PEG)(分子量20000)加入92mL蒸馏水中;将混合均匀的碱液逐滴加入到盐溶液中,滴加完毕后磁力搅拌一个小时;至于100℃老化24小时,真空过滤,用蒸馏水洗涤至中型,过滤后在120℃烘箱内进行干燥14小时,之后用马弗炉在空气气氛下以3℃/min的升温速率升温至800℃煅烧4h,记为LaFe0.74Mn0.26O3。对LaFe0.74Mn0.26O3进行物理吸附表征(见表1)及SEM表征(见图6),并进行催化臭氧氧化实验,反应条件:常温、常压,100ppm间甲酚模型废水,废水初始pH:7.0,O3(mg/L):COD(mg/L)=1.9:1,臭氧流量与废水流量比为3.7:1。
实施例5:
称取9.0538g La(NO3)3·6H2O、2.2074g Fe(NO3)3·9H2O、5.4823g Mn(NO3)2(50%)溶于100mL蒸馏水混合均匀;取8mL氨水和0.25g聚乙二醇(PEG)(分子量20000)加入92mL蒸馏水中;将混合均匀的碱液逐滴加入到盐溶液中,滴加完毕后磁力搅拌一个小时;至于100℃老化24小时,真空过滤,用蒸馏水洗涤至中型,过滤后在120℃烘箱内进行干燥14小时,之后用马弗炉在空气气氛下以3℃/min的升温速率升温至800℃煅烧4h,记为LaFe0.26Mn0.74O3。对LaFe0.26Mn0.74O3进行物理吸附表征(见表1)及SEM表征(见图7),并进行催化臭氧氧化实验,反应条件:常温、常压,100ppm间甲酚模型废水,废水初始pH:7.0,O3(mg/L):COD(mg/L)=1.9:1,臭氧流量与废水流量比为3.7:1。并放大10倍量制备LaFe0.26Mn0.74O3同样做以上催化臭氧氧化实验。此外,考察稳定性(见图8)及降解间甲酚反应机理(见图9)。如图8所示,LaFe0.26Mn0.74O3与Mn/Al2O3进行对比,使用相同锰含量制备锰负载氧化铝的Mn/Al2O3催化剂,从图中可以看出,两种催化剂在间甲酚转化率方面均表现出了较好的效果,但是在TOC去除率方面,钙钛矿相比于Mn/Al2O3催化剂具有更好的TOC去除效果。如图9所示,间甲酚经过羟基自由基(·OH)、超氧化物自由基(O2 ·-)、单线态氧自由基(1O2)的攻击可能先生成一批聚合中间产物,之后这些产物开环生成小分子的酸类醇类等,然后进一步矿化生成二氧化碳,也有可能不经过大分子环节,直接生成小分子然后矿化生成二氧化碳。
表1 LaFe1-xMnxO3物理吸附微观结构
Sample | BET surface area(m<sup>2</sup> g<sup>-1</sup>) | Pore volume(cm<sup>3</sup> g<sup>-1</sup>) | Pore width(nm) |
LaMnO<sub>3</sub> | 26.739 | 0.065 | 2.897 |
LaFe<sub>0.26</sub>Mn<sub>0.74</sub>O<sub>3</sub> | 38.052 | 0.092 | 1.564 |
LaFe<sub>0.5</sub>Mn<sub>0.5</sub>O<sub>3</sub> | 33.843 | 0.151 | 17.296 |
LaFe<sub>0.74</sub>Mn<sub>0.26</sub>O<sub>3</sub> | 31.2 | 0.165 | 10.681 |
LaFeO<sub>3</sub> | 7.92 | 0.04 | 17.523 |
从表中可以看出相比于LaFeO3具有7.92的比表面积以及17.523的孔径来说LaFe0.26Mn0.74O3具有最大的比表面积38.052(m2g-1),同时孔径最小1.564(nm)。较大的比表面积以及较小的孔径对于催化反应具有积极的作用。
从图3~图7中可以看出,合成的催化剂具有较多的孔隙,结构较为松散,平均粒径在40nm左右。不同掺杂量在形貌上的影响并不显著。
以上所述的具体描述,对发明的目的、技术方案和有益效果进行了进一步详细说明,所应理解的是,以上所述仅为本发明的具体实施例而已,并不用于限定本发明的保护范围,凡在本发明的精神和原则之内,所做的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (10)
1.一种铁/锰酸镧催化剂的制备方法,其特征在于:将碱溶液逐滴加入无机盐溶液形成混合溶液A;将硝酸铁、硝酸锰中的一种或两种与硝酸镧共同溶解于水溶液中,得到盐溶液B;将溶液A与溶液B混合、搅拌、水热老化处理,之后冷却、抽滤、洗涤、干燥、焙烧得到铁/猛酸镧催化剂。
2.一种铁/锰酸镧催化剂的制备方法,其特征在于:包括如下步骤:
步骤一、以聚乙二醇为分散剂,与氨水共同溶解于水溶液中形成碱溶液A;氨水体积分数为5~10%,聚乙二醇质量分数为0.1~0.4%;
步骤二、将硝酸铁、硝酸锰中的一种或两种与硝酸镧共同溶解于水溶液中,得到盐溶液B,硝酸铁、硝酸锰、硝酸铁和硝酸猛与硝酸镧的摩尔比均为0~1:1;
步骤三、将步骤一中得到的碱溶液A逐滴加入步骤二中得到的盐溶液B中,同时磁力搅拌,碱溶液A与盐溶液B体积比1:1;
步骤四、将步骤三中得到的溶液于室温下磁力搅拌;得到的混合溶液于80~200℃进行水热处理,然后冷却至室温,抽滤水洗、烘干;煅烧后得到LaFe1-xMnxO3催化剂。
3.如权利要求2所述一种铁/锰酸镧催化剂的制备方法,其特征在于:步骤四所述煅烧为在马弗炉中空气气氛下以1~3℃/min的升温速率升温至700~900℃煅烧2~4h。
4.如权利要求2所述一种铁/锰酸镧催化剂的制备方法,其特征在于:步骤一所述聚乙二醇分子量为1000~20000。
5.如权利要求2所述一种铁/锰酸镧催化剂的制备方法,其特征在于:步骤二中当硝酸铁、硝酸猛与硝酸镧共同溶解于水溶液中时,所述硝酸铁和硝酸猛摩尔比为1-x:x,x=0~1,摩尔比优选不大于0.24。
6.如权利要求2所述一种铁/锰酸镧催化剂的制备方法,其特征在于:步骤四所述搅拌时间为0.5~2h;所述水热处理时间为4~48小时;所述烘干为120℃烘干6~24h。
7.如权利要求1或2所述一种铁/锰酸镧催化剂的制备方法,其特征在于:制得的LaFe1- xMnxO3催化剂近似球形,粒径为10~50nm。
8.如权利要求2所述一种铁/锰酸镧催化剂的制备方法,其特征在于:制得的LaFe1- xMnxO3催化剂比表面积为5~40cm3g-1,孔径尺寸分布为1.5-18nm。
9.将权利要求1或2方法制备的铁/锰酸镧催化剂应用于工业废水处理的方法,其特征在于:将所述铁猛酸镧催化剂用于催化臭氧过氧化氢协同氧化反应处理工业废水,具体方法为:常温、常压,废水初始pH:3.0~9.0,O3(mg/L):COD(mg/L)=(1~3.18):1,H2O2(mg/L):COD(mg/L)=(0~2.36):1,臭氧流量与废水流量比为(3~10):1;
10.如权利要求9所述方法,其特征在于:所述工业废水包括:间甲酚模型废水、火炸药废水成分二苯胺模型废水、火炸药生化出水。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202011499511.4A CN112547087A (zh) | 2020-12-16 | 2020-12-16 | 一种铁/猛酸镧催化剂的制备方法及应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202011499511.4A CN112547087A (zh) | 2020-12-16 | 2020-12-16 | 一种铁/猛酸镧催化剂的制备方法及应用 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN112547087A true CN112547087A (zh) | 2021-03-26 |
Family
ID=75063249
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202011499511.4A Pending CN112547087A (zh) | 2020-12-16 | 2020-12-16 | 一种铁/猛酸镧催化剂的制备方法及应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN112547087A (zh) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112588295A (zh) * | 2020-12-23 | 2021-04-02 | 甄崇礼 | 用于有机废水处理的催化剂及其制备方法 |
CN113433187A (zh) * | 2021-07-01 | 2021-09-24 | 常州大学 | 一种LaMnO3/壳聚糖非酶过氧化氢电化学传感器及其制备方法 |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004096435A1 (en) * | 2003-04-29 | 2004-11-11 | Johnson Matthey Public Limited Company | Manganese ozone decomposition catalysts and process for its preparation |
CN101584987A (zh) * | 2009-06-24 | 2009-11-25 | 中北大学 | 磁性光催化剂制备及用于吸附和光催化降解染料废水 |
CN101979327A (zh) * | 2010-09-21 | 2011-02-23 | 北京工业大学 | 一种钙钛矿型氧化物LaMnO3空心球的制备方法 |
CN103214058A (zh) * | 2012-01-20 | 2013-07-24 | 中北大学 | 火炸药废水的一种处理方法 |
CN103861610A (zh) * | 2012-12-18 | 2014-06-18 | 中国科学院大连化学物理研究所 | 具有高活性的钙钛矿空心颗粒催化剂及制备和应用 |
CN107376926A (zh) * | 2017-08-18 | 2017-11-24 | 中国科学院过程工程研究所 | 一种钙钛矿型臭氧分解催化剂及其制备方法和应用 |
US20190240646A1 (en) * | 2016-09-09 | 2019-08-08 | Nanjing University | Mesoporous manganese ferrite fenton-like catalyst, preparation method therefor, and application thereof |
CN110280251A (zh) * | 2019-06-20 | 2019-09-27 | 北京北华中清环境工程技术有限公司 | 一种用于深度处理的铁酸镧臭氧催化剂及其制备方法 |
CN110433821A (zh) * | 2019-08-12 | 2019-11-12 | 武汉工程大学 | 一种铁锰双金属复合催化剂的制备方法及其在工业废水净化中的应用 |
-
2020
- 2020-12-16 CN CN202011499511.4A patent/CN112547087A/zh active Pending
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004096435A1 (en) * | 2003-04-29 | 2004-11-11 | Johnson Matthey Public Limited Company | Manganese ozone decomposition catalysts and process for its preparation |
CN101584987A (zh) * | 2009-06-24 | 2009-11-25 | 中北大学 | 磁性光催化剂制备及用于吸附和光催化降解染料废水 |
CN101979327A (zh) * | 2010-09-21 | 2011-02-23 | 北京工业大学 | 一种钙钛矿型氧化物LaMnO3空心球的制备方法 |
CN103214058A (zh) * | 2012-01-20 | 2013-07-24 | 中北大学 | 火炸药废水的一种处理方法 |
CN103861610A (zh) * | 2012-12-18 | 2014-06-18 | 中国科学院大连化学物理研究所 | 具有高活性的钙钛矿空心颗粒催化剂及制备和应用 |
US20190240646A1 (en) * | 2016-09-09 | 2019-08-08 | Nanjing University | Mesoporous manganese ferrite fenton-like catalyst, preparation method therefor, and application thereof |
CN107376926A (zh) * | 2017-08-18 | 2017-11-24 | 中国科学院过程工程研究所 | 一种钙钛矿型臭氧分解催化剂及其制备方法和应用 |
CN110280251A (zh) * | 2019-06-20 | 2019-09-27 | 北京北华中清环境工程技术有限公司 | 一种用于深度处理的铁酸镧臭氧催化剂及其制备方法 |
CN110433821A (zh) * | 2019-08-12 | 2019-11-12 | 武汉工程大学 | 一种铁锰双金属复合催化剂的制备方法及其在工业废水净化中的应用 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112588295A (zh) * | 2020-12-23 | 2021-04-02 | 甄崇礼 | 用于有机废水处理的催化剂及其制备方法 |
CN113433187A (zh) * | 2021-07-01 | 2021-09-24 | 常州大学 | 一种LaMnO3/壳聚糖非酶过氧化氢电化学传感器及其制备方法 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US20190240646A1 (en) | Mesoporous manganese ferrite fenton-like catalyst, preparation method therefor, and application thereof | |
CN106807376B (zh) | 一种磁性纳米复合催化剂及其制备方法与应用 | |
CN109894115A (zh) | 一种用于类芬顿处理的改性活性炭催化剂的制备方法 | |
CN102580746A (zh) | 活性炭负载钴氧化物催化剂及在降解有机污染物上的应用 | |
CN111821982B (zh) | 一种氧化石墨烯-氧化铈-氧化铁复合材料、合成方法及其在催化降解性中的应用 | |
CN111889125B (zh) | 一种富缺陷的单原子材料及其制备方法与应用 | |
CN112547087A (zh) | 一种铁/猛酸镧催化剂的制备方法及应用 | |
CN112169797A (zh) | 一种应用于湿式氧化的Cu-Fe双金属络合型磁性壳聚糖炭气凝胶催化剂的制备方法 | |
CN111905751B (zh) | 一种利用高温淬火改性LaCoO3-δ材料催化降解水体中苯酚的方法 | |
CN108083347B (zh) | 钴离子诱导花状钴锰氧化物的制备及其产品和应用 | |
CN112206779B (zh) | MIL-100(Fe/Co)衍生磁性复合材料催化降解水中氯霉素的方法及应用 | |
CN106552644B (zh) | 难生化废水用臭氧催化剂及其制备方法 | |
CN108314214B (zh) | 一种非均相臭氧催化降解印染废水的工艺 | |
CN112121798B (zh) | MIL-101(Fe/Co)衍生磁性铁酸钴催化降解水中氯霉素的方法及应用 | |
CN111545211B (zh) | 一种氧化石墨烯-氧化镧-氢氧化钴复合材料、合成方法及其应用 | |
CN111569890B (zh) | 一种氧化石墨烯-氧化铽-氧化铁复合材料、合成方法及其在催化降解中的应用 | |
CN109876816A (zh) | 一种微波辅助催化湿式氧化纳米催化剂及其应用 | |
CN111704229B (zh) | 降解腈纶废水用纳米低维催化剂的制备方法及降解方法 | |
CN113731402A (zh) | 一种催化剂及其制备方法和应用 | |
CN108275767B (zh) | 一种臭氧催化降解印染废水的处理工艺 | |
CN112479345A (zh) | 用富氧空位氧化镁和氢氧化镁去除水中有机污染物的方法 | |
CN111821984B (zh) | 一种氧化石墨烯-氧化铈-四氧化三钴复合材料、合成方法及其应用 | |
CN117225464B (zh) | 一种用于有机污染物处理的沸石催化剂及其制备方法 | |
CN115385713B (zh) | 一种磁性钴铁合金/硅藻土复合陶粒及其制备方法与应用 | |
CN112774683B (zh) | 一种碳基包覆Ac-Fe/Co催化剂及微乳液制备方法和应用 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20210326 |
|
WD01 | Invention patent application deemed withdrawn after publication |