CN105664892A - 利用褐煤与黄磷水淬渣制备砷吸附材料的方法 - Google Patents
利用褐煤与黄磷水淬渣制备砷吸附材料的方法 Download PDFInfo
- Publication number
- CN105664892A CN105664892A CN201610036237.4A CN201610036237A CN105664892A CN 105664892 A CN105664892 A CN 105664892A CN 201610036237 A CN201610036237 A CN 201610036237A CN 105664892 A CN105664892 A CN 105664892A
- Authority
- CN
- China
- Prior art keywords
- arsenic
- yellow phosphorus
- brown coal
- water quenching
- quenching slag
- 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
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 90
- 239000000463 material Substances 0.000 title claims abstract description 47
- 239000002893 slag Substances 0.000 title claims abstract description 42
- 239000003077 lignite Substances 0.000 title claims abstract description 41
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000012153 distilled water Substances 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 238000012216 screening Methods 0.000 claims abstract description 4
- 238000010791 quenching Methods 0.000 claims description 34
- 230000000171 quenching effect Effects 0.000 claims description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000003463 adsorbent Substances 0.000 claims description 17
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- 239000002689 soil Substances 0.000 abstract description 13
- 238000002360 preparation method Methods 0.000 abstract description 10
- 238000005406 washing Methods 0.000 abstract description 5
- 238000006386 neutralization reaction Methods 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract 2
- 238000001354 calcination Methods 0.000 abstract 1
- 238000000227 grinding Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 238000002715 modification method Methods 0.000 abstract 1
- 239000002245 particle Substances 0.000 abstract 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 11
- 239000011574 phosphorus Substances 0.000 description 10
- 229910052698 phosphorus Inorganic materials 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000002131 composite material Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 239000008399 tap water Substances 0.000 description 5
- 235000020679 tap water Nutrition 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- 229910000616 Ferromanganese Inorganic materials 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000003905 agrochemical Substances 0.000 description 4
- 238000001311 chemical methods and process Methods 0.000 description 4
- 230000036541 health Effects 0.000 description 4
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 244000144972 livestock Species 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002367 phosphate rock Substances 0.000 description 2
- 238000007781 pre-processing Methods 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 239000002699 waste material Chemical group 0.000 description 2
- DJHGAFSJWGLOIV-UHFFFAOYSA-N Arsenic acid Chemical compound O[As](O)(O)=O DJHGAFSJWGLOIV-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- 208000024172 Cardiovascular disease Diseases 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 206010010071 Coma Diseases 0.000 description 1
- 206010010904 Convulsion Diseases 0.000 description 1
- 206010019233 Headaches Diseases 0.000 description 1
- 206010019668 Hepatic fibrosis Diseases 0.000 description 1
- 206010020649 Hyperkeratosis Diseases 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 206010028372 Muscular weakness Diseases 0.000 description 1
- 206010029240 Neuritis Diseases 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 208000002193 Pain Diseases 0.000 description 1
- 208000003782 Raynaud disease Diseases 0.000 description 1
- 208000012322 Raynaud phenomenon Diseases 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 206010041349 Somnolence Diseases 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229940000488 arsenic acid Drugs 0.000 description 1
- 150000001495 arsenic compounds Chemical class 0.000 description 1
- VUEDNLCYHKSELL-UHFFFAOYSA-N arsonium Chemical compound [AsH4+] VUEDNLCYHKSELL-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 230000003683 cardiac damage Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 210000003169 central nervous system Anatomy 0.000 description 1
- 208000026106 cerebrovascular disease Diseases 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000004087 circulation Effects 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 210000000795 conjunctiva Anatomy 0.000 description 1
- 230000036461 convulsion Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- DVUATXGAAOINPS-UHFFFAOYSA-N dimethoxyarsinic acid Chemical compound CO[As](O)(=O)OC DVUATXGAAOINPS-UHFFFAOYSA-N 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
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000002526 effect on cardiovascular system Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 210000001035 gastrointestinal tract Anatomy 0.000 description 1
- 231100000869 headache Toxicity 0.000 description 1
- 231100000206 health hazard Toxicity 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 210000004072 lung Anatomy 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- FRLCRPUWDUKNGO-UHFFFAOYSA-N methoxyarsonic acid Chemical compound CO[As](O)(O)=O FRLCRPUWDUKNGO-UHFFFAOYSA-N 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000004089 microcirculation Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000036473 myasthenia Effects 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 210000000578 peripheral nerve Anatomy 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 230000019612 pigmentation Effects 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 210000003491 skin Anatomy 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- -1 through rainwater Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 230000002485 urinary effect Effects 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- 239000002912 waste gas Chemical group 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000010457 zeolite Substances 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
- B01J2220/4887—Residues, wastes, e.g. garbage, municipal or industrial sludges, compost, animal manure; fly-ashes
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/103—Arsenic compounds
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
本发明公开了一种利用褐煤与黄磷水淬渣制备砷吸附材料的方法,该方法该方法将褐煤或黄磷水淬渣在95℃~125℃条件下烘干3h~4.5h,然后用球磨机破碎,筛分至80—100目,将筛分后混合物与改性剂进行混合,搅拌均匀,焙烧后取出用蒸馏水洗至中性、过滤,滤渣烘干即得砷吸附材料;本方法制备的材料对砷有很高的吸附速率,而且改性方法简单易于制备,对土壤中砷的去除率可达80%~90%。
Description
技术领域
本发明属于吸附材料领域,具体涉及一种利用褐煤与黄磷水淬渣制备砷吸附材料的方法。
背景技术
砷是环境中广泛存在的一种元素,在不同的环境介质条件下以多种氧化态形式存在,环境中暴露的砷主要以As(III)或As(V)的形态存在。自20世纪50年代以来,我国砷矿的开采日益扩大,砷化物广泛应用于工业,农业、畜牧业、医药卫生及食品加工业等行业。在工业生产中,As2O3广泛应用于白银冶炼、颜料、玻璃制造等方面;在农业生产中,砷化物主要应用于杀虫剂,除草剂、防腐剂中;砷化物在畜牧业中主要用于保护鸟类剁毛、兽皮,促进幼畜生长的添加剂;在医药卫生方面,As2O3存在于牙科中用于杀死神经药物中;砷化物也被广泛地应用在色素及食品添加剂中。砷污染来源于化工过程等人类活动。砷和含砷金属的开采、冶炼,用砷或砷化合物作原料的玻璃、颜料、原药的生产以及煤的燃烧等过程,都可产生含砷的废水、废气和废渣,对环境造成污染。大气含砷污染除岩石风化、火山爆发等自然原因外,主要来自工业生产及含砷农药的使用、煤的燃烧。采矿、冶炼的废渣,冶金、化工、农药、染料和制革等的工业废水和地热发电厂的废水中均含砷,被砷污染的河水,会降低生化需氧量。含砷废水、含砷农药及含砷烟尘都会引起土壤砷污染,砷在土壤中累积并由此进入农作物组织中,土壤-农作物中砷的形态主要有无机砷和有机砷,无机砷主要包括亚砷酸(盐)和砷酸(盐),有机砷主要包括单甲基砷酸(盐)和二甲基砷酸(盐)。砷和砷化物一般可通过水、大气和食物等途径进入人体,造成危害。
通常,含砷农药的施用,矿山、工厂含砷废水的排放以及燃煤、冶炼排出的含砷飘尘的降落都可造成土壤中砷的污染,砷主要集中在土壤的表层约10厘米左右,经雨水、地表水等可淋洗至较深土层。相关文献表明:多数植物对土壤中的砷具有不同程度的富集作用。富集在植物体内的砷,会严重地干扰作物对其它养分的吸收,破坏植物的正常生理代谢,进而影响光合作用、糖的转化、淀粉和蛋白质等的合成。砷能抑制水分由根部向地上部分的输送,从而造成叶片凋萎以至枯死等。残留在土壤中的砷很难消失,并且在土壤中积累的砷,很容易通过农作物转移到人体及其它生物体中。在人体内砷通过食物链不断积累,会给人体造成多种疾病,危害人体的生命和健康。砷对健康的危害是多方面的,摄人体内后可经血液迅速分布至全身,皮肤、神经、心、肺等均可受累。砷对皮肤的损害主要包括色素沉着、角化过度和细胞癌变等;长期砷暴露可观察到中枢神经系统抑制症状,包括头痛、嗜睡、烦躁、记忆力下降、惊厥甚至昏迷和外周神经炎伴随的肌无力、疼痛等。砷对循环系统、消化系统和泌尿系统的危害,主要表现为与心肌损害有关的心电图异常和局部微循环障碍导致的雷诺氏综合征、球结膜循环异常、心脑血管疾病等,进入人体的砷主要经尿液排出,对肾脏产生一定的影响,形态和功能均可能出现异常;砷对消化系统影响以肝脏较为多见,有研究发现长期摄入高砷水可导致小鼠非硬化性的肝脏纤维化。饮用水中的砷比土壤中的砷更直接、更快速地危害着人类的健康,我国的台湾、新疆、内蒙等多地均出现过饮用水砷中毒事件。
由于砷对环境的巨大危害,除砷技术和除砷材料受到人们越来越多的关注。常用的除砷处理方法有:(1)化学方法(如铁盐沉淀法、硫化物沉淀法等);(2)物化法(如离子交换、吸附、萃取等);(3)微生物法等。其中物化法中的吸附法,由于其高效、易操作等优点,而被广泛应用。因此,各种去除砷的吸附材料被研究开发出来。例如,张巧丽等人(氧化铁/活性炭复合吸附材料去除水中砷的研究)以实验室制备的氧化铁、经硝酸和草酸铁改性的活性炭12×40(AC1)为原料,制成的氧化铁/活性炭复合吸附材料以及张昱等人(利用稀土基无机合成材料去除饮用水中砷的研究)利用稀土基无机合成材料制备的除砷吸附剂对水中砷的去除效果都比较显著。壳聚糖、纤维素、微生物等生物吸附材料因其生产成本低、环境友好等特点,在饮用水、地下水和工业废水处理中也被广泛应用。但是由于上述方法存在诸多的问题,例如需要较大的化学试剂量、大型的设备、处理后的废物易造成二次污染等。近年来的许多研究致力于寻找一种适当的与生态环境具有良好协调性或直接具有防治污染和修复环境功能的一类矿物材料来去除砷污染。王琼等人(粉煤灰及其改性材料对废水中砷离子的吸附研究)采用NaOH溶液对粉煤灰进行改性处理,并加入铁盐和铝盐制备的吸附材料,在去除硫酸工业废水中砷的试验中,取得了较好效果。李曼尼等人(磷改性斜发沸石去除饮水中砷的机理研究)用焙烧法和微波法固固相同晶取代反应制备了磷改性斜发沸石沸石去除饮用水中的砷,实验发现,微波法磷改性斜发沸石的除As(Ⅲ)效果优于焙烧法。
目前,关于吸附砷的改性材料制备方法的专利报道还不是很多,现有的与吸附重金属的改性材料制备方法密切相关的专利有:《一种纳米铁锰复合氧化物的除砷材料及其制备方法》(201210237752.0),孔淑琼等人公开的一种纳米铁锰复合氧化物的除砷材料是纳米铁锰复合氧化物,所含铁、锰和氧的原子比为4:3:(8~10),其中锰为+4价,铁为+3价,材料的BET比表面积为225~282m2/g,平均粒径为10~20nm。该方法制备得到的纳米铁锰复合氧化物具有较大的比表面积和良好的吸附性能,对水体中砷的去除速度快、效果好,不仅能吸附砷,还能将毒性大的三价砷氧化为毒性较小的五价砷,在除砷的同时具有解毒作用,既可以用于静态吸附方式,也可装入填充柱用动态吸附方式除砷。
传统的褐煤改性大多用于褐煤的提质研究,黄磷水淬渣改性作为吸附材料更为少见,本发明采用褐煤与黄磷水淬渣作为改性原料制备新型吸附砷的材料是吸附材料领域的一个重大创新。
发明内容
本发明提供了一种利用褐煤与黄磷水淬渣制备砷吸附材料的方法,本制备方法操作简单,所需时间短,克服了现有技术制备方法复杂、成本高、条件苛刻的缺点;该方法将褐煤或黄磷水淬渣在95℃~125℃条件下烘干3h~4.5h,然后用球磨机破碎,筛分至80~100目,将筛分后混合物与改性剂进行混合,搅拌均匀,焙烧后取出用蒸馏水洗至中性、过滤,滤渣烘干即得砷吸附材料。
本发明所用褐煤储量大,利用率低且价格低廉。黄磷水淬渣是电炉法制备黄磷时产生的工业固体废物,经过改性后用来作为吸附砷的新型吸附材料达到了二次资源利用。本发明解决了传统的重金属处理技术存在的工艺相对复杂、耗能高等问题,可产生较高的经济效益。
所述改性剂为磷酸或氢氧化钠;褐煤或黄磷水淬渣与磷酸质量体积比为1:1~1:3;褐煤或黄磷水淬渣与氢氧化钠的质量比为1:2~1:4。
所述焙烧温度为150℃~350℃,焙烧时间为0.5h~2.5h。
本发明采用的原料为云南褐煤或黄磷水淬渣。我国已探明的储量达1300多亿吨,西南地区褐煤储量160多亿吨,约占全国褐煤储量的12.5%,其中大部分分布在云南境内,约占全国褐煤储量的11.88%,由于褐煤水分高(一般为40~65%)、热值低(一般为5.45MJ/Kg~14.65MJ/Kg)、活性强、长距离输送经济性差等原因,褐煤的应用受到一定的限制,利用率较低。云南省探明的磷矿资源总量占全国的22%,约为29.4亿t,平均地质品位22.40%(P2O5),磷资源总量位居全国首位,其中可采储量为3.90亿t(P2O5黄磷为27.49%~30.00%)。电炉法制取黄磷时,利用焦炭和硅石作为还原剂和成渣剂,使磷矿石中的钙和二氧化硅化合,形成熔融炉渣,每隔4h从电炉中下部排出,熔融炉渣经水淬冷却,称为水淬渣。每生产1t黄磷产出炉渣8~10t,其中水淬渣7~9t,磷铁0.8~1t,云南省2010年生产黄磷约40多万t,产生黄磷炉渣320~400多万t,其中水淬渣290~360多万t,磷铁32~40多万t。因此,生产黄磷时将产生大量的水淬渣但利用附加值较低,一般用于生产农用硅钙肥、制备路基材料等。经过改性后的褐煤与黄磷水淬渣BET比表面积最多可增大700~900倍,对土壤中砷的去除率可达80%~90%,对于多数地区土壤中砷含量过高的情况,能起到很好的治理效果,与改性前相比利用价值大大提高,获得更大的经济效益。
本发明采用的褐煤主要元素含量为:C60%~76.5%;H4.5%~6.6%;O15%~23%;N1%~2.5%,采用的黄磷水淬渣主要成分含量为:SiO235%~45%;CaO46%~51%;P2O51%~4%。
本发明完成上述制备方法的设备包括预处理设备、制备设备;其中,预处理设备包括:干燥箱Ⅰ-1、球磨机Ⅰ-2、筛子Ⅰ-3;制备设备包括:反应搅拌装置Ⅱ-1、马弗炉Ⅱ-2、水洗装置Ⅱ-3、过滤装置Ⅱ-4、干燥箱Ⅱ-5、中和池Ⅱ-6。
工艺操作及设备使用如下:
将原材料在干燥箱Ⅰ-1中于95℃~125℃条件下烘干3h~4.5h,然后用球磨机Ⅰ-2破碎,筛子Ⅰ-3筛分至80~100目;称取一定质量预处理后的原材料与一定比例的改性剂,在反应搅拌装置Ⅱ-1中以100r/min进行混合,搅拌均匀,放入马弗炉Ⅱ-2中在一定温度下焙烧一段时间,取出用水洗装置Ⅱ-3水洗至中性,经过滤装置Ⅱ-4进行过滤,滤渣在干燥箱Ⅱ-5中烘干;滤液经中和池Ⅱ-6处理后回用至水洗装置Ⅱ-3。
本发明具有以下特点:(1)原料来源广泛,价格低廉。我国已探明的褐煤储量达1300多亿吨,西南地区褐煤储量160多亿吨,约占全国褐煤储量的12.5%,其中大部分分布在云南境内。目前,我国的黄磷生产企业主要集中于云南、贵州、四川等省,其中云南省的生产能力最大。每生产1t黄磷,大约产生8~10t磷渣。以我国目前的黄磷生产能力,每年的磷渣排放量都在500万t以上,且逐年递增。2002年,仅云南省的磷渣排放量就达300~382万t,全国的磷渣排放量则在550~690万t。(2)工艺简单、设备要求低。本发明操作流程简单,未使用大型设备,温度在150~350℃范围内,且不需要高压处理,安全性高。(3)制备方法操作条件简单,反应时间短,连续操作十几个小时即可完成。(4)经磷酸改性的褐煤或黄磷水淬渣BET比表面积最多可增大100~400倍左右,经氢氧化钠改性的褐煤或黄磷水淬渣BET比表面积最多可增大700~1000倍,对土壤中砷的去除率可达80%~90%。
附图说明
图1为本发明方法的流程示意图;
图2为本发明方法的设备流程示意图;
图中:Ⅰ-1为干燥箱;Ⅰ-2为球磨机;Ⅰ-3为筛子;Ⅱ-1为反应搅拌装置;Ⅱ-2为马弗炉;Ⅱ-3为水洗装置;Ⅱ-4为过滤装置;Ⅱ-5为干燥箱;Ⅱ-6为中和池。
具体实施方式
下面通过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:如图1、2所示,本利用褐煤与黄磷水淬渣制备砷吸附材料的方法,具体步骤如下:
(1)将褐煤在干燥箱Ⅰ-1中100℃条件烘干4h,然后用球磨机Ⅰ-2破碎,用筛子Ⅰ-3筛分至100目;
(2)称取2g褐煤与2mL磷酸在反应搅拌装置Ⅱ-1中以100r/min进行混合,搅拌均匀,放入马弗炉Ⅱ-2中在250℃下焙烧2h,取出用水洗装置Ⅱ-3水洗至中性,经过滤装置Ⅱ-4进行过滤,滤渣在干燥箱Ⅱ-5中烘干,即得砷吸附材料;该吸附材料对壤中砷的去除率可达90%。
实施例2:本利用褐煤与黄磷水淬渣制备砷吸附材料的方法,具体步骤如下:
(1)将褐煤在95℃条件下烘干4.5h,然后用球磨机破碎,用筛子筛分至80目;
(2)称取2g褐煤与4g氢氧化钠在反应搅拌装置以100r/min进行混合,搅拌均匀,放入马弗炉在150℃下焙烧2.5h,取出用蒸馏水水洗至中性,过滤,滤渣在干燥箱中烘干,即得砷吸附材料;该吸附材料对壤中砷的去除率可达84%。
实施例3:本利用褐煤与黄磷水淬渣制备砷吸附材料的方法,具体步骤如下:
(1)将黄磷水淬渣在125℃条件下烘干3h,然后用球磨机破碎,用筛子筛分至100目;
(2)称取2g黄磷水淬渣与4mL磷酸在反应搅拌装置以100r/min进行混合,搅拌均匀,放入马弗炉在200℃下焙烧1h,取出用蒸馏水水洗至中性,过滤,滤渣在干燥箱中烘干,即得砷吸附材料;该吸附材料对壤中砷的去除率可达80%。
实施例4:本利用褐煤与黄磷水淬渣制备砷吸附材料的方法,具体步骤如下:
(1)将黄磷水淬渣在110℃条件下烘干3.5h,然后用球磨机破碎,用筛子筛分至90目;
(2)称取2g黄磷水淬渣与8g氢氧化钠在反应搅拌装置以100r/min进行混合,搅拌均匀,放入马弗炉在250℃下焙烧2h,取出用蒸馏水水洗至中性,过滤,滤渣在干燥箱中烘干,即得砷吸附材料;该吸附材料对壤中砷的去除率可达82%。
Claims (4)
1.一种利用褐煤与黄磷水淬渣制备砷吸附材料的方法,其特征在于:将褐煤或黄磷水淬渣在95℃~125℃条件下烘干3h~4.5h,然后用球磨机破碎,筛分至80~100目,将筛分后混合物与改性剂进行混合,搅拌均匀,焙烧后取出用蒸馏水洗至中性、过滤,滤渣烘干即得砷吸附材料。
2.根据权利要求1所述利用褐煤与黄磷水淬渣制备砷吸附材料的方法,其特征在于:改性剂为磷酸或氢氧化钠。
3.根据权利要求1所述利用褐煤与黄磷水淬渣制备砷吸附材料的方法,其特征在于:褐煤或黄磷水淬渣与磷酸质量体积比为1:1~1:3;褐煤或黄磷水淬渣与氢氧化钠的质量比为1:2~1:4。
4.根据权利要求1所述利用褐煤与黄磷水淬渣制备砷吸附材料的方法,其特征在于:焙烧温度为150℃~350℃,焙烧时间为0.5h~2.5h。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610036237.4A CN105664892A (zh) | 2016-01-20 | 2016-01-20 | 利用褐煤与黄磷水淬渣制备砷吸附材料的方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610036237.4A CN105664892A (zh) | 2016-01-20 | 2016-01-20 | 利用褐煤与黄磷水淬渣制备砷吸附材料的方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN105664892A true CN105664892A (zh) | 2016-06-15 |
Family
ID=56301803
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610036237.4A Pending CN105664892A (zh) | 2016-01-20 | 2016-01-20 | 利用褐煤与黄磷水淬渣制备砷吸附材料的方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN105664892A (zh) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113060791A (zh) * | 2021-04-01 | 2021-07-02 | 昆明理工大学 | 一种改性煤渣吸附剂处理高砷污酸的方法 |
CN113371783A (zh) * | 2021-06-11 | 2021-09-10 | 东北大学 | 一种水淬渣-粉煤灰基4a沸石处理氮磷废水的方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1994000382A1 (en) * | 1992-06-19 | 1994-01-06 | Calgon Carbon Corporation | Activated carbon by treatment of lignites with potassium and/or sodium hydroxide or salts and adsorption therewith |
CN1562739A (zh) * | 2004-03-19 | 2005-01-12 | 昆明理工大学 | 一种用褐煤渣生产活性炭的方法 |
CN101850979A (zh) * | 2010-04-29 | 2010-10-06 | 昆明理工大学 | 黄磷炉渣的综合利用方法 |
CN102600800A (zh) * | 2012-04-06 | 2012-07-25 | 昆明理工大学 | 一种半焦吸附剂的制备方法 |
CN105214625A (zh) * | 2015-11-02 | 2016-01-06 | 山东思源水业工程有限公司 | 一种活化褐煤及应用该活化褐煤的焦化废水的处理工艺 |
-
2016
- 2016-01-20 CN CN201610036237.4A patent/CN105664892A/zh active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1994000382A1 (en) * | 1992-06-19 | 1994-01-06 | Calgon Carbon Corporation | Activated carbon by treatment of lignites with potassium and/or sodium hydroxide or salts and adsorption therewith |
CN1562739A (zh) * | 2004-03-19 | 2005-01-12 | 昆明理工大学 | 一种用褐煤渣生产活性炭的方法 |
CN101850979A (zh) * | 2010-04-29 | 2010-10-06 | 昆明理工大学 | 黄磷炉渣的综合利用方法 |
CN102600800A (zh) * | 2012-04-06 | 2012-07-25 | 昆明理工大学 | 一种半焦吸附剂的制备方法 |
CN105214625A (zh) * | 2015-11-02 | 2016-01-06 | 山东思源水业工程有限公司 | 一种活化褐煤及应用该活化褐煤的焦化废水的处理工艺 |
Non-Patent Citations (3)
Title |
---|
K.K. MAR等: "Comparison of Arsenic Adsorption on Lignite, Bentonite, Shale,and Iron Sand from Indonesia", 《PROCEDIA EARTH AND PLANETARY SCIENCE》 * |
王琼等: "粉煤灰及其改性材料对废水中砷离子的吸附研究", 《矿治》 * |
贺斌等: "褐煤活性焦处理含铜、铅、砷工业废水的研究", 《矿治》 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113060791A (zh) * | 2021-04-01 | 2021-07-02 | 昆明理工大学 | 一种改性煤渣吸附剂处理高砷污酸的方法 |
CN113371783A (zh) * | 2021-06-11 | 2021-09-10 | 东北大学 | 一种水淬渣-粉煤灰基4a沸石处理氮磷废水的方法 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN105713619B (zh) | 一种铁硅硫多元素复合生物炭土壤重金属调理剂的制备方法 | |
CN108772418B (zh) | 一种稻田土壤镉砷同步钝化剂及其制备方法与应用 | |
Song et al. | Changes of nutrients and potentially toxic elements during hydrothermal carbonization of pig manure | |
CN105295938B (zh) | 一种降低土壤中镉生物有效性的重金属钝化剂 | |
CN110014032B (zh) | 一种农田土壤重金属污染的修复方法 | |
KR100996498B1 (ko) | 식물 생육 활성제, 및 이를 이용한 식물의 재배 방법 | |
CN109082277B (zh) | 一种镉砷复合污染修复剂及其制备方法与应用 | |
CN103301803A (zh) | 一种用于氨氮废水处理的凹凸棒石改性黏土的制备方法 | |
CN105838379B (zh) | 一种尾矿重金属污染土壤的生态修复药剂 | |
CN105950165A (zh) | 一种铬污染土壤修复改良剂及其修复方法 | |
KR101239540B1 (ko) | 식물성장 촉진용 미네랄수의 제조방법 및 그의 사용방법 | |
CN105801307A (zh) | 一种纳米腐殖质精粉的生产方法 | |
Lu et al. | Remediation of cadmium-polluted weakly alkaline dryland soils using iron and manganese oxides for immobilized wheat uptake | |
CN106365899A (zh) | 一种工业废渣制备硅肥的方法 | |
CN103204748A (zh) | 一种提高磷素利用率的有机无机复混肥料及其制备方法 | |
CN110144221A (zh) | 一种改良剂及其制备方法和应用 | |
CN107325820B (zh) | 一种适于景观生态系统的土壤修复剂 | |
CN104803772A (zh) | 一种中药渣生物质炭基钙镁磷肥及其制备方法 | |
CN104119194B (zh) | 碳酸钙渣压缩营养土的生产方法 | |
CN105664892A (zh) | 利用褐煤与黄磷水淬渣制备砷吸附材料的方法 | |
CN102513067A (zh) | 一种废水中重金属离子吸附剂及吸附工艺 | |
CN103663582A (zh) | 一种营养缓释型饮用水净水剂及制备方法 | |
CN101368103A (zh) | 一种防控设施蔬菜硝酸盐污染的土壤调理剂及其制备方法 | |
CN109749744A (zh) | 土壤改良专用矿物质水的制备方法 | |
CN106673909A (zh) | 一种环保型肥料 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160615 |