CN112619595A - Attapulgite-based regenerable flue gas demercuration adsorbent and preparation method thereof - Google Patents
Attapulgite-based regenerable flue gas demercuration adsorbent and preparation method thereof Download PDFInfo
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- attapulgite
- flue gas
- mercury removal
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- 229960000892 attapulgite Drugs 0.000 title claims abstract description 64
- 229910052625 palygorskite Inorganic materials 0.000 title claims abstract description 64
- 239000003463 adsorbent Substances 0.000 title claims abstract description 52
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000003546 flue gas Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 36
- 230000004048 modification Effects 0.000 claims abstract description 7
- 238000012986 modification Methods 0.000 claims abstract description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000005470 impregnation Methods 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 21
- 238000001354 calcination Methods 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 18
- 239000000725 suspension Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000012266 salt solution Substances 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 229960002089 ferrous chloride Drugs 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 4
- -1 iron ions Chemical class 0.000 claims description 4
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 4
- 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 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- HPDFFVBPXCTEDN-UHFFFAOYSA-N copper manganese Chemical compound [Mn].[Cu] HPDFFVBPXCTEDN-UHFFFAOYSA-N 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 150000002505 iron Chemical class 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 229940099607 manganese chloride Drugs 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 150000001879 copper Chemical class 0.000 claims description 2
- 229910001431 copper ion Inorganic materials 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- 229910001447 ferric ion Inorganic materials 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- 229910001437 manganese ion Inorganic materials 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims 1
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 claims 1
- 150000002696 manganese Chemical class 0.000 claims 1
- 229910052748 manganese Inorganic materials 0.000 claims 1
- 239000011572 manganese Substances 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 4
- 239000011707 mineral Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 2
- QGLPVBJFHJIQJZ-UHFFFAOYSA-N [N+](=O)([O-])[O-].[Cu+2].[Mn+2].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] Chemical compound [N+](=O)([O-])[O-].[Cu+2].[Mn+2].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] QGLPVBJFHJIQJZ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003344 environmental pollutant Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 231100000719 pollutant Toxicity 0.000 abstract description 2
- 239000011593 sulfur Substances 0.000 abstract description 2
- 229910052717 sulfur Inorganic materials 0.000 abstract description 2
- 239000002689 soil Substances 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 239000007787 solid Substances 0.000 description 9
- 238000001914 filtration Methods 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- 239000010881 fly ash Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910000896 Manganin Inorganic materials 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- MQLVWQSVRZVNIP-UHFFFAOYSA-L ferrous ammonium sulfate hexahydrate Chemical compound [NH4+].[NH4+].O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O MQLVWQSVRZVNIP-UHFFFAOYSA-L 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229940032296 ferric chloride Drugs 0.000 description 1
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
- XBDUTCVQJHJTQZ-UHFFFAOYSA-L iron(2+) sulfate monohydrate Chemical compound O.[Fe+2].[O-]S([O-])(=O)=O XBDUTCVQJHJTQZ-UHFFFAOYSA-L 0.000 description 1
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 description 1
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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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
- 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
- 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
- B01D53/02—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 by adsorption, e.g. preparative gas chromatography
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/3021—Milling, crushing or grinding
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- B01J20/3071—Washing or leaching
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- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3234—Inorganic material layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2257/00—Components to be removed
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- B01D2257/602—Mercury or mercury compounds
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Abstract
本发明属于燃煤烟气污染物控制技术领域，具体涉及一种基于凹凸棒土的可再生烟气脱汞吸附剂及其制备方法，所述的可再生烟气脱汞吸附剂是以凹凸棒土为原料，利用铁氧化物磁改性和锰铜硝酸盐浸渍改性制备而成。本发明利用凹凸棒土这种廉价矿物质材料来制取烟气脱汞吸附剂，有效利用廉价的天然矿物质，相比其他类型吸附剂成本更加低廉。本发明制备的烟气脱汞吸附剂具有磁性，可在完成汞吸附后进行分离回收，并进行循环再生利用，有效节约实际生产成本。本发明的烟气脱汞吸附剂，制备过程简单且环境友好具有较大的实际应用前景。本发明的烟气脱汞吸附剂具有较高的脱汞性能，脱汞效率高达90％以上，即使在含硫烟气中依然拥有80％以上的脱汞效率。
The invention belongs to the technical field of coal-fired flue gas pollutant control, and in particular relates to a renewable flue gas mercury removal adsorbent based on attapulgite and a preparation method thereof. The renewable flue gas mercury removal adsorbent is an attapulgite rod Soil is used as raw material, and it is prepared by magnetic modification of iron oxide and impregnation modification of manganese-copper nitrate. The invention utilizes attapulgite, a cheap mineral material, to prepare a flue gas mercury removal adsorbent, effectively utilizes cheap natural minerals, and is cheaper than other types of adsorbents. The flue gas mercury removal adsorbent prepared by the invention has magnetic properties, can be separated and recovered after mercury adsorption is completed, and can be recycled and reused, thereby effectively saving the actual production cost. The flue gas mercury removal adsorbent of the present invention has a simple preparation process and is environmentally friendly, and has a great practical application prospect. The flue gas mercury removal adsorbent of the present invention has high mercury removal performance, the mercury removal efficiency is as high as 90% or more, and the mercury removal efficiency is still more than 80% even in the sulfur-containing flue gas.
Description
Technical Field
The invention belongs to the technical field of coal-fired flue gas pollutant control, and particularly relates to a renewable flue gas demercuration adsorbent based on attapulgite and a preparation method thereof.
Background
Mercury is a toxic heavy metal element, has volatility, durability and bioaccumulation, can enter a human body through a food chain, and has fatal influence on the nervous system and growth and development of people. The proportion of artificial emissions is highest among all sources of mercury emissions. In artificial emissions, the proportion of coal emissions is the highest.
Three different forms of mercury can be generated in the combustion process of coal, namely bivalent mercury, elementary mercury and granular mercury, wherein the bivalent mercury is easily dissolved in water and can be efficiently removed in a wet desulphurization system, and the granular mercury can be removed together with fly ash in flue gas in the existing ash removal device of a power plant. Compared with bivalent mercury and granular mercury, elemental mercury is difficult to be effectively removed due to high volatility and low water solubility. Many technologies for controlling mercury pollution emission in flue gas generated in coal combustion process are available, and among them, adsorption of mercury in flue gas by adsorbent is the most studied method. The mechanism of adsorption methods relies primarily on porous junctions on the surface of the adsorbent to adsorb contaminants. At present, the mercury removal adsorbent mainly studied comprises activated carbon, fly ash, calcium-based adsorbent, zeolite material and the like. The most studied is the activated carbon adsorbent which has high mercury removal efficiency but high price; the price of the fly ash and the calcium-based adsorbent is low, but the removal efficiency of the elemental mercury is not very high. In addition, the amount of the adsorbent used in the actual industrial production is large, and after mercury removal is completed, the adsorbent is usually mixed with fly ash and cannot be regenerated, so that the operation cost is high. Therefore, finding a new flue gas demercuration adsorbent that is inexpensive, efficient, and regenerable is one of the keys to current work.
Disclosure of Invention
One of the purposes of the invention is to provide a renewable flue gas demercuration adsorbent based on attapulgite, which can effectively remove zero-valent mercury in coal-fired flue gas, and has high demercuration efficiency and good separation cycle regeneration performance.
The invention also aims to provide a preparation method of the renewable flue gas demercuration adsorbent based on attapulgite, which has the advantages of simple preparation process, low cost and easy adjustment.
The scheme adopted by the invention for realizing one of the purposes is as follows: the renewable flue gas demercuration adsorbent is prepared by taking attapulgite as a raw material and utilizing iron oxide magnetic modification and manganese copper nitrate impregnation modification.
The second scheme adopted by the invention for achieving the purpose is as follows: the preparation method of the attapulgite-based regenerable flue gas demercuration adsorbent comprises the following steps:
(1) preparing a ferric salt solution with a certain concentration, adding pretreated attapulgite with a solid-to-liquid ratio of 1: 35-45, uniformly mixing, adding excessive concentrated ammonia water, stirring at a constant temperature to form stable and uniform black turbid liquid, filtering, washing to be neutral, drying, calcining, and grinding to obtain magnetic attapulgite;
(2) and (2) adding a proper amount of the magnetic attapulgite obtained in the step (1) into a manganin salt solution with a certain concentration, soaking, drying and calcining to obtain the regenerable flue gas demercuration adsorbent.
Preferably, in the step (1), the iron salt solution is a mixed salt solution containing iron ions and ferrous ions; the salt containing iron ions is at least one of ferric sulfate, ferric chloride and ferric nitrate; the salt containing ferrous ions is at least one of ferrous sulfate, ferrous chloride and ferrous ammonium sulfate; the mass ratio of the attapulgite to the ferrous ions to the ferric ions is 1: 0.109-0.133: 0.218-0.266.
Preferably, in the step (1), the stirring temperature is 65-75 ℃; the drying temperature is 95-105 ℃.
Preferably, in the step (1), the calcining temperature is 230-270 ℃, and the calcining time is 3-4 h.
Preferably, in the step (1), the attapulgite clay pretreatment step is to add attapulgite clay into water, stir and disperse the attapulgite clay into suspension, and then filter, dry and grind the suspension to obtain the pretreated attapulgite clay.
Preferably, in the step (2), in the manganin salt solution, the manganin salt is at least one of manganese nitrate, manganese chloride and manganese acetate, and the copper salt is at least one of copper nitrate, copper chloride and copper acetate.
Preferably, the mass ratio of the magnetic attapulgite to the manganese ions to the copper ions is 1: 0.08-0.20: 0.013-0.077.
Preferably, in the step (2), the dipping method is ultrasonic dipping, and the drying temperature is 95-105 ℃.
Preferably, in the step (2), the calcining temperature is 400-450 ℃; the calcination time is 3.5-4.5 h.
The material used by the invention is attapulgite which is a layer chain-shaped magnesium-rich silicate clay mineral, is needle-shaped or fibrous, and has larger specific surface area and stronger adsorption performance. The flue gas demercuration adsorbent is prepared from attapulgite serving as a raw material by pretreatment, magnetic modification and active substance loading. The preparation method of the regenerable flue gas demercuration adsorbent is simple and low in cost, can realize separation and recovery and cyclic regeneration and utilization by a simple method besides high demercuration performance, and has high application value and market prospect.
The invention has the following advantages and beneficial effects:
(1) the invention utilizes the attapulgite which is a cheap mineral material to prepare the flue gas demercuration adsorbent, effectively utilizes the cheap natural mineral, and has lower cost compared with other types of adsorbents.
(2) The flue gas demercuration adsorbent prepared by the invention has magnetism, can be separated and recovered after mercury adsorption is finished, and can be recycled, so that the actual production cost is effectively saved.
(3) The flue gas demercuration adsorbent prepared by the invention is simple in preparation process, environment-friendly and wide in practical application prospect.
(4) The flue gas demercuration adsorbent prepared by the invention has higher demercuration performance, the demercuration efficiency is up to more than 90%, and the demercuration efficiency is still more than 80% even in sulfur-containing flue gas.
Drawings
FIG. 1 is a schematic process flow diagram of the present invention for preparing a renewable flue gas demercuration adsorbent based on attapulgite;
fig. 2 is SEM images of raw attapulgite (a) and a renewable flue gas demercuration adsorbent based on attapulgite prepared in the present invention (b), respectively.
Detailed Description
The following examples are provided to further illustrate the present invention for better understanding, but the present invention is not limited to the following examples.
Example 1
According to the process flow shown in figure 1, 20g of attapulgite is added into 600ml of deionized water, the mixture is stirred for 45min at normal temperature, the suspension is filtered, the obtained solid is dried in an oven at 100 ℃ for 10h, and then the solid is ground to 80 meshes for later use.
Putting 5g of attapulgite pretreated in the step into 200ml of deionized water, adding 2.14g of ferrous chloride tetrahydrate and 5.83g of ferric chloride hexahydrate, stirring at normal temperature for 30min, adding 30ml of concentrated ammonia water to make the suspension alkaline, heating to 75 ℃, stirring at constant temperature to form stable and uniform black suspension, filtering, washing to be neutral, then placing in a 100 ℃ oven for drying for 12h, and finally placing the obtained solid in a 250 ℃ oven for calcining for 4h to obtain the magnetic attapulgite.
Dispersing 1g of magnetic attapulgite in 10ml of deionized water, adding 0.26g of 50% manganese nitrate solution and 0.076g of copper nitrate, stirring uniformly, ultrasonically soaking for 1.5h, then drying in an oven at 100 ℃ for 12h, then transferring into a muffle furnace, and calcining at 400 ℃ for 4h to obtain the reproducible flue gas demercuration adsorbent. A Scanning Electron Microscope (SEM) of the original attapulgite and a renewable flue gas demercuration adsorbent prepared according to the present invention is shown in fig. 2.
From the comparison of the SEM photographs of the raw attapulgite in fig. 2 with the adsorbent prepared according to the present invention, it was observed that the raw attapulgite had a rod-like structure, and in the adsorbent prepared according to the present invention, crystals having uniform sizes were formed on the surface of the rod-like structure, indicating that both the magnetic substance and the manganese-copper active component were successfully loaded on the surface of the attapulgite.
Example 2
Adding 20g of attapulgite into 600ml of deionized water, stirring at normal temperature for 45min, carrying out suction filtration on the suspension, drying the obtained solid in an oven at 100 ℃ for 10h, and then grinding to 80 meshes for later use.
Putting 5g of attapulgite pretreated in the step into 200ml of deionized water, adding 1.64g of ferrous sulfate monohydrate and 7.84g of ferric nitrate nonahydrate, stirring at normal temperature for 30min, adding 30ml of concentrated ammonia water to make the suspension alkaline, heating to 75 ℃, stirring at constant temperature to form stable and uniform black suspension, filtering, washing to be neutral, then placing in a 100 ℃ oven for drying for 12h, and finally calcining the obtained solid at 250 ℃ for 4h to obtain the magnetic attapulgite.
Dispersing 1g of magnetic attapulgite in 10ml of deionized water, adding 0.39g of 50% manganese nitrate solution and 0.082g of anhydrous copper chloride, stirring uniformly, ultrasonically soaking for 1.5h, drying in a 100 ℃ oven for 12h, transferring into a muffle furnace, and calcining at 400 ℃ for 4h to obtain the reproducible flue gas demercuration adsorbent.
Example 3
Adding 20g of attapulgite into 600ml of deionized water, stirring at normal temperature for 45min, carrying out suction filtration on the suspension, drying the obtained solid in an oven at 100 ℃ for 10h, and then grinding to 80 meshes for later use.
Putting 5g of attapulgite pretreated in the step into 200ml of deionized water, simultaneously adding 4.65g of ammonium ferrous sulfate hexahydrate and 4.73g of ferric sulfate, stirring at normal temperature for 30min, adding 30ml of concentrated ammonia water to make the suspension alkaline, heating to 75 ℃, stirring at constant temperature to form stable and uniform black suspension, filtering, washing to be neutral, then placing in a 100 ℃ oven for drying for 12h, and finally placing the obtained solid at 250 ℃ for calcining for 4h to obtain the magnetic attapulgite.
Dispersing 1g of magnetic attapulgite in 10ml of deionized water, adding 0.183g of anhydrous manganese chloride and 0.19g of copper nitrate, stirring uniformly, ultrasonically soaking for 1.5h, drying in a 100 ℃ oven for 12h, transferring into a muffle furnace, and calcining at 450 ℃ for 4h to obtain the reproducible flue gas demercuration adsorbent.
Example 4
Adding 20g of attapulgite into 600ml of deionized water, stirring at normal temperature for 45min, carrying out suction filtration on the suspension, drying the obtained solid in an oven at 100 ℃ for 10h, and then grinding to 80 meshes for later use.
Putting 5g of attapulgite pretreated in the step into 200ml of deionized water, simultaneously adding 2.14g of ferrous chloride tetrahydrate and 4.32g of ferric sulfate, stirring at normal temperature for 30min, adding 30ml of concentrated ammonia water to make the suspension alkaline, heating to 75 ℃, stirring at constant temperature to form stable and uniform black suspension, filtering, washing to be neutral, then placing in a 100 ℃ oven for drying for 12h, and finally calcining the obtained solid at 250 ℃ for 4h to obtain the magnetic attapulgite.
Dispersing 1g of magnetic attapulgite in 10ml of deionized water, adding 0.356g of manganese acetate tetrahydrate and 0.243g of copper acetate monohydrate, stirring uniformly, ultrasonically soaking for 1.5h, then drying in an oven at 100 ℃ for 12h, then transferring into a muffle furnace, and calcining at 450 ℃ for 4h to obtain the reproducible flue gas demercuration adsorbent.
While the foregoing is directed to the preferred embodiment of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
Claims (10)
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