CN104383873B - 利用低品位凹凸棒石黏土制备复合吸附剂的方法 - Google Patents
利用低品位凹凸棒石黏土制备复合吸附剂的方法 Download PDFInfo
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- 229910052625 palygorskite Inorganic materials 0.000 title claims abstract description 60
- 229960000892 attapulgite Drugs 0.000 title claims abstract description 58
- 239000004927 clay Substances 0.000 title claims abstract description 40
- 239000003463 adsorbent Substances 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 24
- 239000002131 composite material Substances 0.000 title description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910000514 dolomite Inorganic materials 0.000 claims abstract description 11
- 239000010459 dolomite Substances 0.000 claims abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- 239000010453 quartz Substances 0.000 claims abstract description 6
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 claims description 7
- 235000019353 potassium silicate Nutrition 0.000 claims description 6
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 claims description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 5
- 229910021532 Calcite Inorganic materials 0.000 claims description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 4
- 159000000007 calcium salts Chemical class 0.000 claims description 4
- 229910052912 lithium silicate Inorganic materials 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- 159000000003 magnesium salts Chemical group 0.000 claims description 4
- 239000011022 opal Substances 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- 150000003751 zinc Chemical class 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 3
- 235000013905 glycine and its sodium salt Nutrition 0.000 claims description 3
- 239000004247 glycine and its sodium salt Substances 0.000 claims description 3
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 claims description 3
- 235000011147 magnesium chloride Nutrition 0.000 claims description 3
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 claims description 3
- 229940029258 sodium glycinate Drugs 0.000 claims description 3
- WUWHFEHKUQVYLF-UHFFFAOYSA-M sodium;2-aminoacetate Chemical compound [Na+].NCC([O-])=O WUWHFEHKUQVYLF-UHFFFAOYSA-M 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 229960001763 zinc sulfate Drugs 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical group [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- 239000004111 Potassium silicate Substances 0.000 claims description 2
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical group [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 2
- 239000001639 calcium acetate Substances 0.000 claims description 2
- 235000011092 calcium acetate Nutrition 0.000 claims description 2
- 229960005147 calcium acetate Drugs 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- PXEDJBXQKAGXNJ-QTNFYWBSSA-L disodium L-glutamate Chemical compound [Na+].[Na+].[O-]C(=O)[C@@H](N)CCC([O-])=O PXEDJBXQKAGXNJ-QTNFYWBSSA-L 0.000 claims description 2
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 2
- 239000011654 magnesium acetate Substances 0.000 claims description 2
- 235000011285 magnesium acetate Nutrition 0.000 claims description 2
- 229940069446 magnesium acetate Drugs 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- 235000014380 magnesium carbonate Nutrition 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- XDKQUSKHRIUJEO-UHFFFAOYSA-N magnesium;ethanolate Chemical compound [Mg+2].CC[O-].CC[O-] XDKQUSKHRIUJEO-UHFFFAOYSA-N 0.000 claims description 2
- 235000013923 monosodium glutamate Nutrition 0.000 claims description 2
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 claims description 2
- 229940073490 sodium glutamate Drugs 0.000 claims description 2
- WGIWBXUNRXCYRA-UHFFFAOYSA-H trizinc;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WGIWBXUNRXCYRA-UHFFFAOYSA-H 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 239000011667 zinc carbonate Substances 0.000 claims description 2
- 235000004416 zinc carbonate Nutrition 0.000 claims description 2
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 2
- 229940043825 zinc carbonate Drugs 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000011746 zinc citrate Substances 0.000 claims description 2
- 235000006076 zinc citrate Nutrition 0.000 claims description 2
- 229940068475 zinc citrate Drugs 0.000 claims description 2
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims description 2
- 229940007718 zinc hydroxide Drugs 0.000 claims description 2
- 229910021511 zinc hydroxide Inorganic materials 0.000 claims description 2
- ZPEJZWGMHAKWNL-UHFFFAOYSA-L zinc;oxalate Chemical compound [Zn+2].[O-]C(=O)C([O-])=O ZPEJZWGMHAKWNL-UHFFFAOYSA-L 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims 1
- 229910052901 montmorillonite Inorganic materials 0.000 claims 1
- 230000032683 aging Effects 0.000 abstract description 7
- 239000002734 clay mineral Substances 0.000 abstract description 7
- 238000001179 sorption measurement Methods 0.000 abstract description 6
- 238000004043 dyeing Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 235000013305 food Nutrition 0.000 abstract description 2
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 2
- 239000012535 impurity Substances 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract description 2
- 238000005067 remediation Methods 0.000 abstract description 2
- 239000000843 powder Substances 0.000 abstract 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 abstract 2
- 229910052751 metal Inorganic materials 0.000 abstract 2
- 239000002184 metal Substances 0.000 abstract 2
- 239000000203 mixture Substances 0.000 abstract 2
- 150000003839 salts Chemical class 0.000 abstract 2
- 231100000678 Mycotoxin Toxicity 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 239000002636 mycotoxin Substances 0.000 abstract 1
- 238000007639 printing Methods 0.000 abstract 1
- 230000002285 radioactive effect Effects 0.000 abstract 1
- 229910052761 rare earth metal Inorganic materials 0.000 abstract 1
- 150000002910 rare earth metals Chemical class 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 238000004065 wastewater treatment Methods 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 14
- 239000013078 crystal Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 238000000498 ball milling Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000010298 pulverizing process Methods 0.000 description 5
- 239000012265 solid product Substances 0.000 description 5
- 239000006004 Quartz sand Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 235000011116 calcium hydroxide Nutrition 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 235000012254 magnesium hydroxide Nutrition 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000926 separation method Methods 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
- 230000009466 transformation Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229960001296 zinc oxide Drugs 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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
-
- 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
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- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dispersion Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
本发明公开了利用低品位凹凸棒石黏土制备吸附剂的方法,它是将含石英和白云石的凹凸棒石黏土矿粉与占其质量20%‑600%的可溶性硅酸盐和10%‑500%的金属盐或含金属盐的溶液均匀混合后进行研磨,再按固液比1:100‑1:10分散在水中,加入适量助剂,陈化1‑4h;然后转入水热反应釜中,温度120~300℃反应5~60h,分离、洗涤、干燥、粉碎处理,得到吸附剂。本发明将低品位凹凸棒石黏土矿粉中的石英杂质、白云石转变为具有强吸附活性的无定形硅酸盐,比表面积大,孔径分布均一,用于染料、重金属、有机分子、放射性元素、稀土、霉菌毒素的吸附和脱除,在生物、食品、石油化工、环境修复、印染废水处理等领域具有广阔的应用前景。
Description
技术领域
本发明涉及一种利用低品位凹凸棒石黏土制备复合吸附剂的方法,属于天然非金属矿深加工、综合利用和纳米吸附剂合成技术领域。
背景技术
凹凸棒石黏土(也称为坡缕石或坡缕缟石)是一种以凹凸棒石为主要成分的含水富镁铝硅酸盐黏土矿物,具有纳米棒状晶体形貌和丰富的纳米孔道。其单晶体直径为20-70nm,长度0.5-5 μm,具有较大的比表面积,是一种价格低廉的天然吸附剂。
我国凹凸棒石黏土资源丰富,但总体而言产品附加值较低,资源利用率不高,严重制约了产业的发展。主要原因是:(1)多数凹凸棒石黏土矿纯度不高,常伴有石英砂、白云石、方解石、蛋白石等杂矿,这些杂矿不具备吸附性能,不能用于开发高端吸附剂产品;(2)现有技术不能对低品位凹凸棒石黏土中杂矿进行高效综合利用,因此多数低品位矿被作为尾矿处理,造成了资源的严重浪费。为了实现低品位凹凸棒石黏土的应用,常对凹凸棒石黏土矿进行复杂提纯处理,或以除去石英砂或蛋白石;或通过酸化处理除去白云石和方解石,以提高纯度和使用性能。专利CN102874826A公开了一种凹凸棒石黏土的提纯方法,具体是将凹凸棒石黏土分散在水中制浆、加入活化剂活化、加入酸除杂、陈化、重力沉降、多次离心分离,最后得到提纯凹凸棒石黏土。专利CN 103738975A公开了一种凹凸棒石黏土的提纯方法,采用制浆-加活化剂-陈化-沉降-分离等步骤来提高凹凸棒石黏土的纯度。提纯处理在一定程度上可以降低杂矿含量,提高凹凸棒石的纯度,改善使用性能。然而,提纯的工艺复杂、成本高、耗水耗能,活化剂还会引起环境污染。尽管采用各种物理方法(中国专利CN104014299A)或化学改性方法(中国专利CN 102527325A;CN102553519A;CN 103611494A;CN102247807A;103723785A)在一定程度上提高凹凸棒石的吸附性能,但现有技术方法并不能实现对凹凸棒石黏土矿中所有组分的无废弃、高效综合利用。
水热法可以在反应过程中形成新的晶体或改变晶体的形态和结构,目前已在高岭土、埃洛石、蛇纹石等矿物的合成中获得应用。我们曾利用水热法使短径凹凸棒石长径化(专利CN 103086392 A),在此基础上我们又开展了凹凸棒石中伴生矿的晶体形态转变研究,该研究将为低品位凹凸棒石黏土矿或尾矿综合利用开拓新方法。
发明内容
本发明的目的是:提供一种利用低品位凹凸棒石黏土矿或尾矿通过一步反应制备复合吸附剂的方法,解决利用低品位矿或尾矿制备高效吸附剂的技术瓶颈,进一步拓展凹凸棒石的应用领域。
本发明的技术解决方案是:它是将富含石英和白云石的低品位凹凸棒石黏土矿粉与占其质量10%-600%的可溶性硅酸盐和10%-500%的金属盐或含金属离子的溶液均匀混合后进行研磨,按固液比1:100-1:10分散在水中,加入助剂,陈化1-2h;然后转入水热反应釜中,温度120~300℃反应5~60h,分离、洗涤、干燥、粉碎,得到吸附剂产品。
其中,所述可溶性硅酸盐为偏硅酸钾、硅酸钾钠、正(偏)硅酸锂、原硅酸、偏硅酸钾、偏硅酸;
其中,所述金属盐为镁盐、锌盐和钙盐;镁盐为市售商品,包括氯化镁、乙酸镁、碳酸镁、氢氧化镁、硝酸镁、乙醇镁,或用盐湖提钾副产物水氯镁石溶液(浓度10-90%)进行调配;所述锌盐为乙酸锌、氯化锌、硫酸锌、硝酸锌、氧化锌、氢氧化锌、碳酸锌、柠檬酸锌、草酸锌;所述钙盐为氯化钙、硝酸钙、氢氧化钙、乙酸钙。
其中,反应过程中加入的助剂为尿素、硫脲、二甲基甲酰胺、氯乙酸钠、氢氧化铷、甘氨酸钠、谷氨酸钠中的一种,加入量为凹凸棒石黏土质量的0.01-0.5%。
与现有方法相比,本发明具有以下优点:
1、本发明利用低温水热法,通过对反应参数的精确控制,一步反应就实现了低品位凹凸棒黏土矿中非活性的石英砂、蛋白石、白云石、方解石(同时含一种或几种)转变为吸附活性的多孔硅酸盐,得到比表面积大、孔径分布窄、吸附能力强、绿色环保的复合高效吸附剂。
2、该制备方法工艺简单,过程易于控制,产品具有普适性,质量稳定。
3、本发明所述工艺,不仅有助于实现低品位凹凸棒石黏土矿或尾矿的高值化利用,而且还为生物、食品、石油化工、环境修复、印染废水处理等多个领域提供了高效吸附剂。
附图说明
图1为凹凸棒石和复合吸附剂的XRD图。
图2为凹凸棒石和复合吸附剂的TEM图。
图3为凹凸棒石和复合吸附剂的SEM图。
图4为复合吸附剂的吸附性能曲线。
具体实施方式
下面结合实施例对本发明的技术解决方案做进一步说明,这些实施例不能理解为是对技术方案的限制。
实施例 1 :将100 g凹凸棒石黏土矿粉与10 g硅酸钾和10 g氯化镁混合后球磨处理,然后分散到1000 mL水中,加入0.01 g 氯乙酸钠,陈化2h,转入1.5 L高压反应釜中,温度300 ℃反应5 h,自然降温后将固体产物分离出来,用水洗涤,110℃下烘干,粉碎后得到白色复合吸附剂。
实施例 2 :将10 g凹凸棒石黏土矿粉与60 g硅酸钠钾和50 g硫酸锌混合后球磨处理,然后分散到1000 mL水中,加入0.05 g 尿素,陈化1h,转入1.5 L高压反应釜中,温度120 ℃反应60h,自然降温后将固体产物分离出来,用水洗涤,110℃下烘干,粉碎后得到白色复合吸附剂。
实施例 3 :将50 g凹凸棒石黏土矿粉与20 g原硅酸和15 g氢氧化钙混合后球磨处理,然后分散到1000 mL水中,加入0.25 g二甲基甲酰胺,陈化2h,转入1.5 L高压反应釜中,温度180 ℃反应60h,自然降温后将固体产物分离出来,用水洗涤,110℃下烘干,粉碎后得到米白色复合吸附剂。
实施例 4 :将20 g凹凸棒石黏土矿粉与12 g偏硅酸和15 g氢氧化镁混合后球磨处理,然后分散到1000 mL水中,加入0.01 g氢氧化铷,陈化2h,转入1.5 L高压反应釜中,温度200 ℃反应24h,自然降温后将固体产物分离出来,用水洗涤,110℃下烘干,粉碎后得到米白色复合吸附剂。
实施例 5 :将50 g凹凸棒石黏土矿粉与20 g硅酸锂和含5 g水氯镁石的浓盐溶液混合后球磨处理,然后分散到1000 mL水中,加入0.25 g 甘氨酸钠,陈化1h,转入1.5 L高压反应釜中,温度120 ℃反应60h,自然降温后将固体产物分离出来,用水洗涤,110℃下烘干,粉碎后得到白色复合吸附剂。
本发明实施例 1-5 的产品的结构表征:通过透射电子显微镜(TEM)、扫描电子显微镜(SEM)、X-射线粉末衍射(XRD)证实了吸附剂的结构和形态。从附图1可以看出,原凹凸棒石黏土在2θ = 8.38°和2θ =13.85°处分别出现了110和200晶面的特征衍射峰,在2θ =26.68°处出现了较强的石英特征峰,在2θ =30.09°处出现了白云石的特征峰,说明原凹凸棒石黏土中含有石英和白云石杂矿。经过本发明所述方法处理后,凹凸棒石的特征衍射峰明显减弱,石英和白云石特征峰消失,说明水热环境下几种物质共同反应生成了低结晶度的吸附剂;从附图2和3可以看出,凹凸棒石为纳米棒状结构,经本发明所述方法处理后,棒状晶体比例减少,片状晶体比例增加,形成了复合吸附剂。经本发明所述方法处理后,其比表面积从原凹凸棒石黏土的183 m2/g增加到478 m2/g;从附图4可以看出,复合吸附剂对染料的饱和吸附容量为579.9 mg/g,达到了原凹凸棒石黏土(155.4
mg/g)吸附量的3.73倍;对重金属铜离子的饱和吸附容量为250.26 mg/g,达到了原凹凸棒石黏土吸附量(105.43 mg/g)的2.37倍。
Claims (4)
1.利用低品位凹凸棒石黏土制备吸附剂的方法,其特征在于:它是将富含石英和白云石的低品位凹凸棒石黏土矿粉与占其质量10%-600%的可溶性硅酸盐和10%-500%的金属盐或含金属离子的溶液均匀混合后进行研磨,其中含金属离子的溶液中的溶质占凹凸棒石黏土矿粉质量的10%-500%,再按固液比1:100-1:10分散在水中,加入助剂,陈化1-2h;然后转入水热反应釜中,温度120~300℃反应5~60h,分离、洗涤、干燥、粉碎,得到吸附剂产品;反应过程中加入的助剂为尿素、硫脲、二甲基甲酰胺、氯乙酸钠、氢氧化铷、甘氨酸钠、谷氨酸钠中的一种,加入量为凹凸棒石黏土质量的0.01-0.5%。
2.根据权利要求1所述的利用低品位凹凸棒石黏土制备吸附剂的方法,其特征在于:低品位凹凸棒石黏土矿粉为凹凸棒石含量低于20%的原矿或尾矿,主要杂矿为石英、蛋白石、蒙脱石、白云石、方解石中的一种或几种。
3.根据权利要求1所述的利用低品位凹凸棒石黏土制备吸附剂的方法,其特征在于:所述可溶性硅酸盐为偏硅酸钾、硅酸钾钠、正硅酸锂、原硅酸、偏硅酸锂、偏硅酸。
4.根据权利要求1所述的利用低品位凹凸棒石黏土制备吸附剂的方法,其特征在于:所述金属盐为镁盐、锌盐或钙盐;其中,镁盐为市售商品,包括:氯化镁、乙酸镁、碳酸镁、硝酸镁、乙醇镁,或用盐湖提钾副产物水氯镁石溶液进行调配,水氯镁石溶液的浓度是10-90%;所述锌盐为乙酸锌、氯化锌、硫酸锌、硝酸锌、氢氧化锌、碳酸锌、柠檬酸锌、草酸锌;所述钙盐为氯化钙、硝酸钙、乙酸钙。
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