CN106861671A - 一种废弃铬吸附剂的资源化应用 - Google Patents
一种废弃铬吸附剂的资源化应用 Download PDFInfo
- Publication number
- CN106861671A CN106861671A CN201710129043.3A CN201710129043A CN106861671A CN 106861671 A CN106861671 A CN 106861671A CN 201710129043 A CN201710129043 A CN 201710129043A CN 106861671 A CN106861671 A CN 106861671A
- Authority
- CN
- China
- Prior art keywords
- chromium
- catalyst
- methyl mercaptan
- adsorbent
- discarded
- 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.)
- Granted
Links
- 239000011651 chromium Substances 0.000 title claims abstract description 53
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 52
- 239000003463 adsorbent Substances 0.000 title claims abstract description 29
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000002699 waste material Substances 0.000 claims abstract description 7
- 238000001179 sorption measurement Methods 0.000 claims abstract description 4
- 239000002131 composite material Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 39
- 238000000034 method Methods 0.000 abstract description 10
- 238000000354 decomposition reaction Methods 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 239000006228 supernatant Substances 0.000 description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 11
- 229910052710 silicon Inorganic materials 0.000 description 11
- 239000010703 silicon Substances 0.000 description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 230000004913 activation Effects 0.000 description 7
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 7
- 239000002351 wastewater Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 5
- 238000011049 filling Methods 0.000 description 5
- 239000012467 final product Substances 0.000 description 5
- 239000006260 foam Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000003421 catalytic decomposition reaction Methods 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000002920 hazardous waste Substances 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000002956 ash Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 229910021487 silica fume Inorganic materials 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000002594 sorbent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 201000009030 Carcinoma Diseases 0.000 description 1
- CXRFDZFCGOPDTD-UHFFFAOYSA-M Cetrimide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)C CXRFDZFCGOPDTD-UHFFFAOYSA-M 0.000 description 1
- 206010058467 Lung neoplasm malignant Diseases 0.000 description 1
- 206010033799 Paralysis Diseases 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 206010043515 Throat cancer Diseases 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 201000005202 lung cancer Diseases 0.000 description 1
- 208000020816 lung neoplasm Diseases 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 210000004400 mucous membrane Anatomy 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000241 respiratory effect Effects 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 210000003491 skin Anatomy 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
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
- B01J23/16—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
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/26—Chromium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/306—Organic sulfur compounds, e.g. mercaptans
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
- Catalysts (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
本发明公开了一种废弃铬吸附剂的资源化应用，将吸附铬后废弃的铬吸附剂进行干燥、焙烧，用于催化分解甲硫醇。不仅可以大幅度降低甲硫醇分解的温度，而且催化剂的寿命得到了显著提高，达到了“以废治废”的目的，具有良好的应用前景。
Description
技术领域
本发明涉及一种废弃铬吸附剂的资源化应用，属于危险废物资源化技术领域。
背景技术
水溶性六价铬（剧毒物），具有强氧化性，其中六价铬离子对人体的毒害非常大，它对消化道、呼吸道、皮肤和黏膜都有危害，甚至可以引发皮肤癌、咽喉癌、肺癌等疾病。近年来多地发生铬污染事件，如2011年云南南盘江铬污染、云南曲靖铬污染、河南义马铬污染、广西柳州铬污染、2014年广州顺德铬污染等，对含铬废水处理迫在眉睫。
吸附法是目前研究比较多的处理含铬废水的方法，介孔无机有机复合吸附剂用于吸附含铬废水，但对于吸附后的含铬吸附剂处理问题，传统的方法是进行再生（产生高浓度含铬废水、易产生二次污染）和以危险废物进行固化填埋（不仅成本高而且会产生二次污染：含铬吸附剂的空气污染：呈粉末状的含铬吸附剂会引起扬尘，很容易在空气中散发，对生态环境造成极大的污染，成为人类的健康杀手；含铬吸附剂的水污染：堆放、填埋场的含铬吸附剂含有水溶态和酸溶态的铬，会随雨水大量流失，严重污染地表、地下水系，对人类健康、作物生长造成严重威胁，处理成本高，会产生重金属渗滤液污染地下水、地表水、土壤等）。因此，亟需为废弃含铬吸附剂选择一种无污染、低成本处理方法。
甲硫醇作为一种特殊的挥发性有机物（Volatile Organic Compounds，VOCs），在空气中易累积形成有机气溶胶，导致大气光化学烟雾和雾霾等严重的大气污染问题。甲硫醇也具有嗅阈值低和高毒、高腐蚀的性质，会引起人体神经系统麻醉；如果长期工作或生活在浓度很高环境中，会引发呼吸系统问题，严重时导致呼吸瘫痪。同时甲硫醇具有的高酸度会腐蚀反应设备。此外，甲硫醇来源极其广泛，主要来源于石油加工过程、天然气、炼焦炉、制革厂、造纸厂、污染控制设施（废水处理系统、卫生填埋系统）。因此，对甲硫醇处理技术的应用基础研究已是迫在眉睫，针对工业生产过程中的甲硫醇尾气治理以及石油产品中硫醇去除的研究工作具有重要的现实意义。目前国内外尚无利用废弃含铬吸附剂制备催化降解甲硫醇的报道研究。
发明内容
本发明的目的在于提供一种废弃铬吸附剂的资源化应用，将吸附铬后废弃的铬吸附剂进行干燥，再在350~800℃焙烧3~8h后，用于催化分解甲硫醇。
焙烧后的铬吸附剂可在以下反应条件下对甲硫醇进行催化分解：催化反应温度为250～500℃；催化反应的压力是常压；甲硫醇气体在总的气体中的含量为1～100000ppm；甲硫醇气体的气时空速范围为500～50000h-1。
所述铬吸附剂包括：（1）市售的介孔材料（如：MCM-41介孔分子筛、SBA-15介孔分子筛、介孔二氧化硅等）用氨基、巯基等活性基团改性制备的复合介孔铬吸附材料（制备方法参照文献《Chromium(VI) removal from water by means of adsorption-reduction atthe surface of amino-functionalized MCM-41 sorbents》）；（2）以化学试剂为原料制备的复合介孔铬吸附材料，如以正硅酸乙酯、硅酸钠等为硅源、十六烷基三甲基溴化铵为模板剂制备的复合介孔铬吸附剂（制备方法参照文献《Bifunctionalized Mesoporous Silicasfor Cr(VI) Reduction and Concomitant Cr(III) Immobilization》）；（3）以工农业废弃物或天然矿物为原料制备的复合介孔铬吸附材料。
以工农业废弃物或天然矿物为原料制备的复合介孔铬吸附材料的制备方法：以粉煤灰、微硅粉、稻壳灰、硅藻土等工农业废弃物或天然矿物中的任意一种或几种作为硅源，与氢氧化钠、氢氧化钾等碱按质量比为1:0.5~2混合研磨后，在400~700℃焙烧1~6h，获得活化硅源，然后将活化硅源与水按质量比为1:3~8混合搅拌，过滤获得上清液；以十二烷基三甲基溴化铵、十四烷基三甲基溴化铵、十六烷基三甲基溴化铵、十八烷基三甲基溴化铵等阳离子表面活性剂中的任意一种或几种为模板剂，将模板剂溶于水中，加入步骤获得的上清液为硅铝源，模板剂和上清液的质量比为1:10~30，加酸搅拌调节pH=9~11，过滤，用清水洗涤至无泡沫，干燥，即得复合介孔铬吸附材料。
本发明的有益效果：
1、本发明充分利用吸附铬后废弃的铬吸附剂作为催化分解恶臭气体甲硫醇的催化剂，不仅消除了甲硫醇对环境的污染，同时实现了危险废物（废弃重金属吸附剂）资源化处理，实现了以废治废，具有极大的工业实用性；
2、本发明制得的催化剂与现有分解甲硫醇的催化剂相比，具有如下优点：
（1）活性高，例如，当反应温度为350℃时，550℃下焙烧的催化剂的活性可达到100%，反应温度比已有文献报道的温度低200℃，比市售CeO2催化剂低100℃；
（2）寿命长，例如，当反应温度为500℃时，550℃下焙烧的催化剂在88h时还可达到甲硫醇100%完全转化，而CeO2催化剂在相同条件下在6h后开始失活；
3、实现了甲硫醇在常压、250~500℃的反应条件下高效催化分解成H2S、CH4和少量其他简单无机碳氢化合物，其产物H2S的治理已趋于成熟，可用克劳斯及其改进工艺去除；而另一主要产物CH4，是重要的工业原料；
4、在催化反应后，催化剂中的高毒性六价铬转化为稳定无毒三价铬，更有利于处理，实现了危险废物无害化。
附图说明
图1为实施例1制备的催化剂与市售CeO2催化剂催化甲硫醇分解的活性对比图；
图2为实施例1制备的催化剂与市售CeO2催化剂在反应温度为500℃时催化甲硫醇完全分解的寿命对比图。
具体实施方式
下面结合实施例对本发明作进一步详细说明，但本发明保护范围不局限于所述内容。
实施例1
将十六烷基三甲基溴化铵（模板剂）以质量比1:46溶于水中，加入氨水，氨水与水的质量比为1:10，混合均匀后，加入正硅酸乙酯，正硅酸乙酯与模板剂溶液质量比为1:13，混合均匀后，过滤，用清水洗涤至无泡沫，干燥，即得铬吸附剂；将制得的铬吸附剂用于对含铬废水进行吸附后干燥，再在800℃焙烧3h，即可用作催化分解甲硫醇的催化剂。
将制得的催化剂和市售CeO2催化剂分别装填在反应器内进行甲硫醇催化分解反应，催化剂填装量为0.2g，进料总空速为9000h-1，反应体系压力为常压，对两种催化剂的催化性能进行对比试验。试验结果：（1）本实施例制得的催化剂在反应温度为350℃时甲硫醇的转化率即可达到100%，市售CeO2催化剂在450℃时甲硫醇的转化率才可达到100%（350℃时甲硫醇转化率仅为67%），如图1所示；（2）在反应温度为500℃的条件下，本实施例制得的催化剂催化甲硫醇完全分解的寿命长达88h，而市售CeO2催化剂催化甲硫醇完全分解的寿命仅为6h，如图2所示。
实施例2
将粉煤灰与氢氧化钠按质量比为1:0.5混合研磨后，在400℃焙烧6h，获得活化硅源，然后将活化硅源与水按质量比为1:8混合搅拌，过滤获得上清液；以十六烷基三甲基溴化铵为模板剂，将模板剂溶于水中，加入获得的上清液，模板剂与上清液的质量比为1:30，加盐酸搅拌调节pH=9，过滤，用清水洗涤至无泡沫，干燥，即得铬吸附剂；将制得的铬吸附剂用于对含铬废水进行吸附，然后在80℃干燥12h并在350℃下焙烧8h，即可用作催化分解甲硫醇的催化剂。
将制得的催化剂装填在反应器内，催化剂填装质量为0.2g，进料总空速为9000 h-1，反应体系压力为常压，反应温度500℃的条件下，进行甲硫醇催化分解反应，甲硫醇的转化率为100%，甲硫醇完全转化寿命可长达50h。
实施例3
将市售的MCM-41介孔分子筛，用浸渍法嫁接有机官能团（APTES）。将1g MCM-41与1mLAPTES混合，80℃搅拌6h，用水和乙醇洗涤未嫁接上的APTES，干燥后获得复合材料即为铬吸附剂；将制得的铬吸附剂用于对含铬废水进行吸附后干燥，再在650℃下焙烧4h，即可用作催化分解甲硫醇的催化剂。
将制得的催化剂装填在反应器内，催化剂填装质量为0.2g，进料总空速为9000 h-1，反应体系压力为常压，反应温度500℃的条件下，进行甲硫醇催化分解反应，甲硫醇的转化率为100%，甲硫醇完全转化寿命可长达80h。
实施例4
将稻壳灰和硅藻土的混合物与氢氧化钾按质量比为1:1.2混合研磨后，在550℃焙烧4h，获得活化硅源，然后将活化硅源与水按质量比为1:5混合搅拌，过滤获得上清液；以十二烷基三甲基溴化铵为模板剂，将模板剂溶于水中，加入获得的上清液，模板剂与上清液的质量比为1:25，加硫酸搅拌调节pH=10，过滤，用清水洗涤至无泡沫，干燥，即得铬吸附剂；将制得的铬吸附剂用于对含铬废水进行吸附后干燥，并在550℃下焙烧5h，即可用作催化分解甲硫醇的催化剂。
将制得的催化剂装填在反应器内，催化剂填装质量为0.2g，进料总空速为9000 h-1，反应体系压力为常压，反应温度500℃的条件下，进行甲硫醇催化分解反应，甲硫醇的转化率为100%，甲硫醇完全转化寿命可长达80h。
实施例5
将微硅粉与氢氧化钠和氢氧化钾的混合物按质量比为1:2混合研磨后，在700℃焙烧1h，获得活化硅源，然后将活化硅源与水按质量比为1:3混合搅拌，过滤获得上清液；以十八烷基三甲基溴化铵为模板剂，将模板剂溶于水中，加入获得的上清液，模板剂与上清液的质量比为1:10，加醋酸搅拌调节pH=11，过滤，用清水洗涤至无泡沫，干燥，即得铬吸附剂；将制得的铬吸附剂用于对含铬废水进行吸附后干燥，并在450℃下焙烧7h，即可用作催化分解甲硫醇的催化剂。
将制得的催化剂装填在反应器内，催化剂填装质量为0.2g，进料总空速为9000 h-1，反应体系压力为常压，反应温度500℃的条件下，进行甲硫醇催化分解反应，甲硫醇的转化率为100%，甲硫醇完全转化寿命可长达68h。
Claims (3)
1.一种废弃铬吸附剂的资源化应用，将吸附铬后废弃的铬吸附剂干燥、焙烧后，用于催化分解甲硫醇。
2.根据权利要求1所述的资源化应用，其特征在于，所述铬吸附剂包括：（1）市售的介孔材料用活性基团改性制备的复合介孔铬吸附材料；（2）以化学试剂为原料制备的复合介孔铬吸附材料；（3）以工农业废弃物或天然矿物为原料制备的复合介孔铬吸附材料。
3.根据权利要求1所述的资源化应用，其特征在于，焙烧步骤为在350~800℃焙烧3~8h。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710129043.3A CN106861671B (zh) | 2017-03-06 | 2017-03-06 | 一种废弃铬吸附剂的资源化应用 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710129043.3A CN106861671B (zh) | 2017-03-06 | 2017-03-06 | 一种废弃铬吸附剂的资源化应用 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106861671A true CN106861671A (zh) | 2017-06-20 |
| CN106861671B CN106861671B (zh) | 2020-07-10 |
Family
ID=59169638
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710129043.3A Active CN106861671B (zh) | 2017-03-06 | 2017-03-06 | 一种废弃铬吸附剂的资源化应用 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106861671B (zh) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112316896A (zh) * | 2020-10-12 | 2021-02-05 | 昆明理工大学 | 一种废弃铜吸附剂资源化利用的方法 |
| CN115007130A (zh) * | 2021-11-30 | 2022-09-06 | 昆明理工大学 | 一种氧化锌/硅酸锌/生物炭复合材料的制备方法及应用 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1108150A (zh) * | 1993-11-22 | 1995-09-13 | 株式会社金星社 | 空气净化剂和空气净化装置 |
| WO2000056692A1 (en) * | 1999-03-24 | 2000-09-28 | Lehigh University | Production of formaldehyde from ch4 and h2s |
-
2017
- 2017-03-06 CN CN201710129043.3A patent/CN106861671B/zh active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1108150A (zh) * | 1993-11-22 | 1995-09-13 | 株式会社金星社 | 空气净化剂和空气净化装置 |
| WO2000056692A1 (en) * | 1999-03-24 | 2000-09-28 | Lehigh University | Production of formaldehyde from ch4 and h2s |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112316896A (zh) * | 2020-10-12 | 2021-02-05 | 昆明理工大学 | 一种废弃铜吸附剂资源化利用的方法 |
| CN112316896B (zh) * | 2020-10-12 | 2022-10-14 | 昆明理工大学 | 一种废弃铜吸附剂资源化利用的方法 |
| CN115007130A (zh) * | 2021-11-30 | 2022-09-06 | 昆明理工大学 | 一种氧化锌/硅酸锌/生物炭复合材料的制备方法及应用 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106861671B (zh) | 2020-07-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhu et al. | Goethite modified biochar as a multifunctional amendment for cationic Cd (II), anionic As (III), roxarsone, and phosphorus in soil and water | |
| CN103831089B (zh) | 聚乙烯亚胺-凹凸棒土吸附剂的制备及吸附六价铬的方法 | |
| CN108585101B (zh) | 一种重金属污水处理用无机材料杂化的多孔生物质微球的回收方法 | |
| CN106179216A (zh) | 一种磁性活化水热生物炭的制备方法与应用 | |
| Cunha et al. | Applications of magnetic hybrid adsorbent derived from waste biomass for the removal of metal ions and reduction of 4-nitrophenol | |
| CN112705566B (zh) | 一种机械化学修复六氯苯污染土壤的方法 | |
| CN112169755A (zh) | 一种应用于水中四环素去除的水热合成的氯化锌活化的磁性污泥生物炭的制备方法 | |
| CN110982535A (zh) | 一种生物质炭土壤重金属修复剂及其应用方法 | |
| CN110237808A (zh) | 一种y分子筛的硅烷化改性方法 | |
| CN107473467A (zh) | 一种吸附去除工业废水中六价铬离子的方法 | |
| CN106861671A (zh) | 一种废弃铬吸附剂的资源化应用 | |
| CN106000310A (zh) | 一种用于脱除no的埃洛石/炭复合吸附剂的制备方法 | |
| CN110368806A (zh) | 一种具有释放负氧离子去除甲醛功能的空气净化颗粒 | |
| CN107876005A (zh) | 一种脱除氯化污染物的吸附剂及其制备方法和应用 | |
| CN108434956A (zh) | 生活垃圾焚烧烟气超净处理工艺及系统 | |
| CN111715194A (zh) | 一种改性银杏叶生物炭的制备方法及应用 | |
| Yohannes et al. | Emerging Applications of Metal− Organic Frameworks for Environmental Remediation | |
| CN107349905A (zh) | 一种氟氮共掺杂的磁性碳材料去除工业废水中六价铬离子的方法 | |
| CN111977873B (zh) | 一种光活海泡石Si-OH用于水溶性有机污染物吸附与光降解的方法 | |
| CN103566877A (zh) | 一种吸收电磁波改性活性炭及其制备方法 | |
| CN112661968A (zh) | 一种制备mof吸附材料的方法 | |
| CN104725021A (zh) | 常温催化氧化型空气净化装饰材料及其制备方法 | |
| CN104888726A (zh) | 一种除尘杀菌效果优良的活性炭吸附剂 | |
| CN108714418A (zh) | 一种光触媒覆膜载体材料及其制备方法、应用 | |
| Adeiga et al. | Rooibos tea waste binary oxide composite: An adsorbent for the removal of nickel ions and an efficient photocatalyst for the degradation of ciprofloxacin |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |