CN108993578A - 一种清除甲醛复合材料的制备方法 - Google Patents
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 239000002808 molecular sieve Substances 0.000 claims abstract description 13
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 239000000376 reactant Substances 0.000 claims abstract description 12
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 7
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims abstract description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 7
- 229910000162 sodium phosphate Inorganic materials 0.000 claims abstract description 7
- 239000001488 sodium phosphate Substances 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- SQKWGPOIVHMUNF-UHFFFAOYSA-K cerium(3+);trichloride;hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Ce+3] SQKWGPOIVHMUNF-UHFFFAOYSA-K 0.000 claims abstract description 6
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 5
- KKSAZXGYGLKVSV-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO KKSAZXGYGLKVSV-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 230000036571 hydration Effects 0.000 claims abstract description 4
- 238000006703 hydration reaction Methods 0.000 claims abstract description 4
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 11
- 229910006213 ZrOCl2 Inorganic materials 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 6
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 4
- JXLWTLZBAJWNSG-UHFFFAOYSA-N CCCC[Ti] Chemical compound CCCC[Ti] JXLWTLZBAJWNSG-UHFFFAOYSA-N 0.000 claims description 3
- QUVMSYUGOKEMPX-UHFFFAOYSA-N 2-methylpropan-1-olate;titanium(4+) Chemical compound [Ti+4].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] QUVMSYUGOKEMPX-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract description 5
- 229910000421 cerium(III) oxide Inorganic materials 0.000 abstract description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract description 4
- 230000001699 photocatalysis Effects 0.000 abstract description 4
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract description 3
- NZSLBYVEIXCMBT-UHFFFAOYSA-N chloro hypochlorite;zirconium Chemical class [Zr].ClOCl NZSLBYVEIXCMBT-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011941 photocatalyst Substances 0.000 abstract description 2
- 239000003463 adsorbent Substances 0.000 abstract 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000008118 PEG 6000 Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical class O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 210000004072 lung Anatomy 0.000 description 1
- 206010025482 malaise Diseases 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 210000004400 mucous membrane Anatomy 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 1
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Abstract
本发明公开了一种清除甲醛复合材料的制备方法,其技术要点是:首先,在一定量浓盐酸HCl中,加入分子筛ZSM‑5和聚乙二醇,搅拌条件下,滴加丁醇钛,加入八水合氧氯化锆、六水合三氯化铁及六水合氯化铈,搅拌一段时间后,得到反应物A;其次,向反应物A中,加入磷酸钠,搅拌一段时间后,转移至水热反应釜中,控温反应,得到混合物B;然后,混合物B经过滤、水洗、干燥,制得清除甲醛复合材料。该清除甲醛复合材料以分子筛ZSM‑5为吸附剂,TiO2‑ZrO2、TiO2‑Fe2O3、TiO2‑Ce2O3、Zr(HPO4)2•H2O为复合光催化剂,可有效吸附并通过光催化清除甲醛气体。
Description
技术领域
本发明涉及环保技术领域,特别是一种清除甲醛复合材料的制备方法。
背景技术
甲醛的危害已经引起了人们足够的重视, 该气体对人体皮肤、黏膜具有刺激性、容易引起眼睛、嗓子、肺部等多种不适症状,例如:有些媒体报道了甲醛危害引起白血病。
目前市场上的除甲醛产品,包括固态和液态两种,除甲醛的原理,主要依托物理吸附和化学吸附,配合光催化制剂、生物酶等除甲醛材料来实现。分子筛是一种具有很大比表面积的材料,对于气体的吸附具有良好作用,二氧化钛是一种常用的光催化剂,由于其禁带宽度较大,单一的二氧化钛效果不是十分良好,许多研究者通过将两者复合,例如:CN106423250A报道了一种活化沸石分子筛负载二氧化钛光催化材料的制备方法。
因此,开发绿色、环保、高效的清除甲醛复合材料已经成为环保技术领域的一种迫切需求。
发明内容
本发明的目的在于:提供一种清除甲醛复合材料的制备方法,结合化学技术及物理技术,快速批量制备复合分子筛ZSM-5、二氧化钛、二氧化锆、三氧化铁、氧化铈及磷酸锆的清除甲醛复合材料。
本发明的技术方案:首先,在一定量浓盐酸HCl中,加入分子筛ZSM-5和聚乙二醇,搅拌条件下,滴加丁醇钛,加入八水合氧氯化锆、六水合三氯化铁及六水合氯化铈,搅拌一段时间后,得到反应物A;其次,向反应物A中,加入磷酸钠,搅拌一段时间后,转移至水热反应釜中,控温反应,得到混合物B;然后,混合物B经过滤、水洗、干燥,制得清除甲醛复合材料。
所述的技术方案中,首先,在强酸性条件下,分子筛、聚乙二醇分散在盐酸体系中,丁醇钛Ti(OC4H9)4、八水合氧氯化锆ZrOCl2•8H2O、六水合三氯化铁FeCl3•6H2O及六水合氯化铈CeCl3•6H2O,经水解形成“-O-Ti-O-Zr-O-”、“-O-Ti-O-Fe-O-”、“-O-Ti-O-Ce-O-”复合链式结构,这些复合物均匀分散在分子筛ZSM-5中;其次,在酸性体系中,加入磷酸钠Na3PO4,HPO4 2-与多余ZrOCl2反应,通过水热反应形成含ZSM-5、TiO2-ZrO2、TiO2-Fe2O3、TiO2-Ce2O3、Zr(HPO4)2•H2O的复合物B;最后,复合物B经过滤、水洗、干燥,制得分子筛ZSM-5负载TiO2-ZrO2、TiO2-Fe2O3、TiO2-Ce2O3及Zr(HPO4)2•H2O的清除甲醛复合材料。
本发明与现有技术相比,具有显著优点:该清除甲醛复合材料以分子筛ZSM-5为吸附剂,TiO2-ZrO2、TiO2-Fe2O3、TiO2-Ce2O3、Zr(HPO4)2•H2O为复合光催化剂,可有效吸附并通过光催化去除甲醛气体。
具体实施方式
下面结合具体实施例说明本发明的技术解决方案,这些实施例不能理解为对技术方案的限制。
实施例1:依以下具体步骤制备一种清除甲醛复合材料。
步骤1、在1000mL质量浓度为37%的浓盐酸HCl中,加入354g分子筛ZSM-5和11.8g聚乙二醇PEG-2000,搅拌条件下,滴加203.3g正丁醇钛Ti(OC4H9)4,加入308g八水合氧氯化锆ZrOCl2•8H2O、24.2g六水合三氯化铁FeCl3•6H2O及21.2g六水合氯化铈CeCl3•6H2O,搅拌6h后,得到反应物A;
步骤2、向反应物A中,加入125.5g磷酸钠Na3PO4,搅拌4h后,转移至水热反应釜中,控温220oC,反应6h,得到混合物B;
步骤3、混合物B经过滤、水洗、120oC干燥12h,制得清除甲醛复合材料。
实施例2:依以下具体步骤制备一种清除甲醛复合材料。
步骤1、在1000mL质量浓度为37%的浓盐酸HCl中,加入354g分子筛ZSM-5和35.4g聚乙二醇PEG-8000,搅拌条件下,滴加203.3g异丁醇钛Ti(OC4H9)4,加入308g八水合氧氯化锆ZrOCl2•8H2O、40.4g六水合三氯化铁FeCl3•6H2O及63.5g六水合氯化铈CeCl3•6H2O,搅拌8h后,得到反应物A;
步骤2、向反应物A中,加入172.6g磷酸钠Na3PO4,搅拌6h后,转移至水热反应釜中,控温280oC,反应10h,得到混合物B;
步骤3、混合物B经过滤、水洗、160oC干燥8h,制得清除甲醛复合材料。
实施例3:依以下具体步骤制备一种清除甲醛复合材料。
步骤1、在1000mL质量浓度为37%的浓盐酸HCl中,加入354g分子筛ZSM-5和25g聚乙二醇PEG-6000,搅拌条件下,滴加203.3g正丁醇钛Ti(OC4H9)4,加入308g八水合氧氯化锆ZrOCl2•8H2O、32g六水合三氯化铁FeCl3•6H2O及42g六水合氯化铈CeCl3•6H2O,搅拌7h后,得到反应物A;
步骤2、向反应物A中,加入150g磷酸钠Na3PO4,搅拌5h后,转移至水热反应釜中,控温260oC,反应8h,得到混合物B;
步骤3、混合物B经过滤、水洗、140oC干燥10h,制得清除甲醛复合材料。
Claims (3)
1.一种清除甲醛复合材料的制备方法,其特征是:
(1)、在一定量质量浓度为37%的浓盐酸HCl中,加入分子筛ZSM-5和聚乙二醇PEG,搅拌条件下,滴加丁醇钛Ti(OC4H9)4,加入八水合氧氯化锆ZrOCl2•8H2O、六水合三氯化铁FeCl3•6H2O及六水合氯化铈CeCl3•6H2O,搅拌6h-8h后,得到反应物A,其中,ZSM-5和聚乙二醇占浓盐酸的质量比例分别为30%和1%-3%,Ti(OC4H9)4和ZrOCl2•8H2O占浓盐酸的摩尔比例为5%和8%,FeCl3•6H2O和CeCl3•6H2O占Ti(OC4H9)4的摩尔比例分别为15%-25%和10%-30%;
(2)、向反应物A中,加入磷酸钠Na3PO4,搅拌4h-6h后,转移至水热反应釜中,控温220oC-280oC,反应6h-10h,得到混合物B,其中,Na3PO4与ZrOCl2•8H2O的摩尔比例为0.8-1.1;
(3)、混合物B经过滤、水洗、120oC-160oC干燥8h-12h,制得清除甲醛复合材料。
2.根据权利要求1所述的一种清除甲醛复合材料的制备方法,其特征在于:所述的反应物A中,丁醇钛可选用正丁醇钛或异丁醇钛。
3.根据权利要求1所述的一种清除甲醛复合材料的制备方法,其特征在于:所述的反应物A中,PEG分子量可选用2000-8000。
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CN110882699A (zh) * | 2019-12-06 | 2020-03-17 | 四川源景绿能科技有限公司 | 基于三重异质结结构的光触媒及其制备方法 |
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CN101612578A (zh) * | 2008-06-24 | 2009-12-30 | 中国人民解放军63971部队 | 一种室温消除甲醛的纳米金催化剂及其制备方法 |
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CN102658087A (zh) * | 2012-05-11 | 2012-09-12 | 王志勇 | 甲醛清除剂的制备方法 |
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CN110882699A (zh) * | 2019-12-06 | 2020-03-17 | 四川源景绿能科技有限公司 | 基于三重异质结结构的光触媒及其制备方法 |
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