CN113304757A - 一种回收重金属污染元素制备整体式催化剂的方法 - Google Patents
一种回收重金属污染元素制备整体式催化剂的方法 Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 7
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- 229910000616 Ferromanganese Inorganic materials 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
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- 229910052725 zinc Inorganic materials 0.000 claims description 6
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 5
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- 239000000203 mixture Substances 0.000 claims description 4
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- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 229910021538 borax Inorganic materials 0.000 claims description 2
- 229960001759 cerium oxalate Drugs 0.000 claims description 2
- ZMZNLKYXLARXFY-UHFFFAOYSA-H cerium(3+);oxalate Chemical compound [Ce+3].[Ce+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O ZMZNLKYXLARXFY-UHFFFAOYSA-H 0.000 claims description 2
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 2
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 claims description 2
- 239000011656 manganese carbonate Substances 0.000 claims description 2
- 229940093474 manganese carbonate Drugs 0.000 claims description 2
- 235000006748 manganese carbonate Nutrition 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 230000007613 environmental effect Effects 0.000 abstract description 3
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
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- 231100000693 bioaccumulation Toxicity 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
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- 229910052748 manganese Inorganic materials 0.000 description 2
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0063—Granulating
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
本发明涉及环境保护技术领域，更具体地说，是涉及一种回收重金属污染元素制备整体式催化剂的方法。步骤为，从污染场地回收含重金属材料，并进行初步破碎的预处理，得到含重金属备料；将质量比为30～70：20～50：5～10：5～10的含重金属备料、粘土、粘结剂和活性炭粉末混合均匀，加入水溶液进行预示润；利用造粒设备将上述浆料造成圆形颗粒，高温烧结后即可得到整体式催化剂。
Description
技术领域：
本发明涉及环境保护技术领域，更具体地说，是涉及一种回收重金属污染元素制备整体式催化剂的方法。
背景技术：
在自然环境中，不同形态的重金属元素具有不可降解性和生物积累性，工业企业排放的含重金属污染水样和各种含重金属矿渣，如果进入环境中，其中的重金属会通过生物积累性及食物链传递，影响生态系统和人体健康。化学沉淀法是处理水体重金属污染的主要方法之一，但是，其产生的重金属污泥常需要作为危险废物处理，增加了企业的运营成本。
催化剂因能降低反应的活化能，在环境保护领域得到广泛应用。如电厂烟气脱硝、汽车尾气三元催化剂、挥发性有机物催化燃烧降解等废气治理领域均有大量应用；在废水治理领域，水中的臭氧催化氧化，因催化剂的加入，能够加速产生强氧化性的羟基自由基，从而促进水中有机物的降解速率，是一种具有前景的高级氧化技术。
常见的臭氧催化剂活性组分主要为过渡金属氧化物及稀土金属氧化物，如铁、镍、铜、锰、锌、铈、钛等。这些元素大部分恰好是工业企业重金属污染水样和矿渣的主要成分。因此，可以通过技术手段，将环境污染中的重金属成分回收利用，用以制备工业催化剂。既解决了重金属污染问题、还生产了催化剂产生经济效益。
发明内容：
本发明正是针对上述问题，提供了一种回收重金属污染元素制备整体式催化剂的方法。
为了实现上述目的，本发明采用如下技术方案，步骤为，
1、从污染场地回收含重金属材料，并进行初步破碎的预处理，得到含重金属备料；
2、将质量比为30～70：20～50：5～10：5～10的含重金属备料、粘土、粘结剂和活性炭粉末混合均匀，加入占固体总质量5％～20％的水进行预湿润；
3、利用造粒设备将上述浆料造成圆形颗粒，在800℃～1200℃的高温条件下焙烧1h～4h，即可得到整体式催化剂。
所述从污染场地回收的含重金属物质，可以是利用沉淀法回收的污染水样中的镍、铜、锌、锰、铁、锆及钯组分，也可以是回收利用的矿渣，或者两者的混合物；矿渣为锰铁矿渣或钒钛矿渣。
步骤2得到的浆料颗粒粒径均球磨至0.1mm～0.5mm以下。
步骤2中的粘结剂为面粉、硼酸钠、聚丙烯酰胺中的一种以上。
步骤2的水中还可以添加草酸铈、碳酸铈、醋酸铈、乙酸锰、碳酸锰、硝酸锰、硫酸镍、草酸镍或醋酸锌，配成的盐溶液质量浓度为0.5％-5％。
制得的催化剂颗粒直径为4～12mm。
本发明的有益效果：
锰铁矿渣、钒钛矿渣和重金属水样沉淀物中含有一定比例的Mn、Fe、Cu、Zn、Ni等重金属成分，本发明利用这些废料中的重金属成分作为臭氧催化剂活性组分的来源，通过焙烧将重金属元素的沉淀物，如氢氧化物、碳酸沉淀物氧化成催化活性优越的金属氧化物；在制备过程中，可以添加Mn、Fe等的金属盐溶液来调节活性组的含量，提高活性组分在催化剂的分散度，优化催化剂的活性；活性炭在焙烧的过程中将被氧化成二氧化碳，使制备而成的颗粒物催化剂具有发达的空隙结构。解决了重金属污染问题的基础上，生产了性能优异的催化剂，产生经济效益。
具体实施方式：
下面结合实施例，具体说明该类催化剂的制备方法，但本发明并不限于这些实施例。
实施例1
1)从锰铁矿渣中回收含锰铁原料，将其初步粉碎后备用；
2)将铁锰矿渣、粘土、面粉和活性炭按重量比60：25：5：10的比例混合均匀，加入占固体总质量8％的水进行预湿润；
3)用造粒机将上述的混合料制备成粒径为5mm的颗粒物；
5)在空气气氛下，150℃烘干，900-1200℃下焙烧2h，冷却后得到粒径为5mm的颗粒状臭氧催化剂。
Claims (6)
1.一种回收重金属污染元素制备整体式催化剂的方法，其特征在于，步骤为，
(1)从污染场地回收含重金属材料，并进行初步破碎的预处理，得到含重金属备料；
(2)将质量比为30～70：20～50：5～10：5～10的含重金属备料、粘土、粘结剂和活性炭粉末混合均匀，加入占固体总质量5％～20％的水进行预湿润；
(3)利用造粒设备将上述混合料造成圆形颗粒，在800℃～1200℃的高温条件下焙烧1h～4h，即可得到整体式催化剂。
2.根据权利要求1所述的回收重金属污染元素制备整体式催化剂的方法，其特征在于，从污染场地回收的含重金属物质，可以是利用沉淀法回收的污染水样中的镍、铜、锌、锰、铁、锆及钯组分，也可以是回收利用的矿渣，或者两者的混合物；矿渣为锰铁矿渣或钒钛矿渣。
3.根据权利要求1所述的回收重金属污染元素制备整体式催化剂的方法，其特征在于，步骤2中的含重金属备料、粘土、粘结剂和活性炭的粒径均小于0.1mm～0.5mm。
4.根据权利要求1所述的回收重金属污染元素制备整体式催化剂的方法，其特征在于，步骤2中的粘结剂为面粉、硼酸钠、聚丙烯酰胺中的一种以上。
5.根据权利要求1所述的回收重金属污染元素制备整体式催化剂的方法，其特征在于，步骤2)的水中还可以添加草酸铈、碳酸铈、醋酸铈、乙酸锰、碳酸锰、硝酸锰、硫酸镍、草酸镍或醋酸锌，配成的盐溶液质量浓度为0.5％-5％。
6.根据权利要求1所述的回收重金属污染元素制备整体式催化剂的方法，其特征在于，制得的催化剂颗粒直径为4～12mm。
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105381804A (zh) * | 2015-10-30 | 2016-03-09 | 北京碧水源膜科技有限公司 | 臭氧催化剂及其制备方法 |
| US20160144343A1 (en) * | 2013-06-28 | 2016-05-26 | South China University Of Technology | Ceramsite catalyst containing metal oxide particles and preparation method and application thereof |
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