CN115463640B - H in desorption flue gas 2 S and metallic mercury adsorbent and preparation method thereof - Google Patents
H in desorption flue gas 2 S and metallic mercury adsorbent and preparation method thereof Download PDFInfo
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- CN115463640B CN115463640B CN202211195611.7A CN202211195611A CN115463640B CN 115463640 B CN115463640 B CN 115463640B CN 202211195611 A CN202211195611 A CN 202211195611A CN 115463640 B CN115463640 B CN 115463640B
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 48
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 title claims abstract description 35
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000003546 flue gas Substances 0.000 title claims abstract description 23
- 229940008718 metallic mercury Drugs 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000003795 desorption Methods 0.000 title claims description 3
- 239000010802 sludge Substances 0.000 claims abstract description 54
- 150000003839 salts Chemical class 0.000 claims abstract description 51
- 238000010891 electric arc Methods 0.000 claims abstract description 50
- 239000000428 dust Substances 0.000 claims abstract description 48
- 239000002994 raw material Substances 0.000 claims abstract description 39
- 238000005189 flocculation Methods 0.000 claims abstract description 33
- 230000016615 flocculation Effects 0.000 claims abstract description 33
- 238000000197 pyrolysis Methods 0.000 claims abstract description 28
- 238000002156 mixing Methods 0.000 claims abstract description 27
- 238000001035 drying Methods 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000011230 binding agent Substances 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 230000004913 activation Effects 0.000 claims abstract description 9
- 238000004898 kneading Methods 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 22
- 239000012190 activator Substances 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 230000003213 activating effect Effects 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 7
- 229920002472 Starch Polymers 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000010426 asphalt Substances 0.000 claims description 4
- 229920002678 cellulose Polymers 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical group [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- 239000011269 tar Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 229910052753 mercury Inorganic materials 0.000 abstract description 18
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 238000003763 carbonization Methods 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 239000002910 solid waste Substances 0.000 abstract description 3
- 229910000805 Pig iron Inorganic materials 0.000 abstract description 2
- 230000001737 promoting effect Effects 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 19
- 230000000694 effects Effects 0.000 description 11
- 239000002028 Biomass Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000011148 porous material Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 239000000571 coke Substances 0.000 description 8
- 230000009286 beneficial effect Effects 0.000 description 6
- 229910001385 heavy metal Inorganic materials 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052976 metal sulfide Inorganic materials 0.000 description 4
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 3
- 239000002956 ash Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000003949 liquefied natural gas Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 229910000497 Amalgam Inorganic materials 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000004763 sulfides Chemical class 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
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
-
- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/024—Compounds of Zn, Cd, Hg
- B01J20/0244—Compounds of Zn
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/30—Destroying solid waste or transforming solid waste into something useful or harmless involving mechanical treatment
- B09B3/38—Stirring or kneading
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/80—Destroying solid waste or transforming solid waste into something useful or harmless involving an extraction step
-
- 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
- B01D2257/304—Hydrogen sulfide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/60—Heavy metals or heavy metal compounds
- B01D2257/602—Mercury or mercury compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
-
- 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
Abstract
The invention relates to the technical field of flue gas pollution treatment, in particular to a method for removing H in flue gas 2 S and metallic mercury adsorbent and preparation method thereof, the adsorbent is prepared from the following raw materials: the method comprises the steps of dewatering ferric salt flocculated sludge, electric arc furnace dust, a binder and water, drying and grinding the ferric salt flocculated sludge, mixing the ferric salt flocculated sludge with the electric arc furnace dust, adding water, mixing uniformly, adding the binder, kneading, mixing uniformly, and granulating to obtain raw materials; and then drying the raw materials, then sending the dried raw materials into a pyrolysis furnace for pyrolysis, after the pyrolysis is finished, introducing steam for carbonization and activation, and then cooling to room temperature under the inert gas atmosphere. The raw materials adopted by the adsorbent are solid wastes, and the adsorbent has the advantages of low cost and simple process; feSO in ferric salt flocculation sludge 4 Decomposing at high temperature to produce sulfide of pig iron, facilitating mercury removal, generating oxygen to oxidize Zn in the electric arc furnace dust into ZnO at high temperature, and promoting H together with ZnO contained in the electric arc furnace dust 2 Adsorption of S.
Description
Technical Field
The invention relates to the technical field of flue gas pollution treatment, in particular to a method for removing H in coke oven gas and blast furnace gas flue gas 2 S and metallic mercury adsorbent and its preparation method.
Background
Along with the continuous increase of energy demand and the continuous improvement of environmental protection requirements, the problems of heavy metal mercury pollution and desulfurization caused by low-heat-value gas resources such as coke oven gas, blast furnace gas and the like in the utilization process are more and more prominent. The wet desulfurization process commonly used at present is applicable to SO 2 Has better removal effect, but has good removal effect on H in coke oven gas and blast furnace gas 2 S pollutant removing effect is poor; activated carbon is relatively low in price but is specific to H 2 S has limited adsorption capacity, and the microcrystalline or polycrystalline adsorption material has good effect, but has higher cost; in addition, mercury pollutants in coke oven gas or blast furnace gas can be combined with other metals to generate amalgam, so that a liquefying device is corroded, and trace mercury enters Liquefied Natural Gas (LNG) as a product and is released in the use process of the LNG, so that the surrounding environment is harmed; typical mercury scavengers are activated carbon, in particular sulfide modified activated carbonAnd the like, the matching of the adsorbent and facilities greatly increases the treatment cost of coke oven gas or blast furnace gas.
On the other hand, ferrous sulfate (FeSO) 4 ) As a typical flocculant widely used in flocculation dehydration process links of urban domestic sewage treatment, the dosage of the iron flocculation agent is higher, usually about 3-5% of the weight of dry sludge, a large amount of ferric salt flocculation sludge is generated, and the sludge capacity is increased to increase the treatment capacity and the treatment difficulty of final sludge.
In addition, during the production of electric arc furnaces, a large amount of fly ash is produced, which is essentially that during the production of electric arc furnaces, due to the heating and the intense agitation associated with high temperatures, some metals are evaporated, some metals are carried out of the furnace by the rising hot gas flow, and some oxides in the slag may also be carried directly into the dust collection system by the rising hot gas flow, thus forming electric arc furnace dust. The main component of the electric arc furnace dust is Fe x O y (21% -48%), zn and ZnO (15% -50%), caO (1% -10%), mgO (1% -5%), al 2 O 3 (0.5% -8%) of a metal or metal oxide. Because the electric arc furnace dust is produced in a large amount and the application means are limited, a large amount of electric arc furnace dust cannot be effectively utilized, and the electric arc furnace dust can only be stacked in a storage yard, so that a large amount of land resources are occupied.
Therefore, it is necessary to design a method which can fully utilize the valuable components in ferric salt flocculated sludge and electric arc furnace dust and simultaneously remove H in coke oven gas and blast furnace gas flue gas 2 S and metallic mercury adsorbent and preparation method thereof, to solve the above problems.
Disclosure of Invention
The invention aims to provide a method for removing H in flue gas 2 S and metallic mercury adsorbent and preparation method thereof can at least solve part of defects in the prior art.
In order to achieve the aim, the technical scheme of the invention is that H in the flue gas is removed 2 S and metallic mercury, wherein the adsorbent is prepared from the following raw materials: ferric salt flocculated sludge and electric arc furnace dustBinder, water.
As one of the embodiments, the mass ratio of the ferric salt flocculated sludge to the electric arc furnace dust is 3:1 to 10:1.
as one of the embodiments, the amount of the binder is 20% -40% of the sum of the mass of the ferric salt flocculated sludge and the mass of the electric arc furnace dust, and the amount of the water is 15% -30% of the sum of the mass of the ferric salt flocculated sludge and the mass of the electric arc furnace dust.
As one embodiment, the binder includes one or more of starch, cellulose, asphalt, and tar.
As one embodiment, the preparation raw material of the adsorbent further comprises an activator, wherein the activator comprises H 2 SO 4 、NaCl、KCl、ZnCl 2 One or more of the following.
As one embodiment, the activator is used in an amount of 3% -15% of the sum of the mass of the ferric salt flocculated sludge and the electric arc furnace dust.
The invention also provides a method for removing H in the flue gas 2 The preparation method of the adsorbent for S and metallic mercury comprises the following steps:
s1, dehydrating ferric salt flocculation sludge, drying and grinding for later use;
s2, mixing the ground ferric salt flocculation sludge with electric arc furnace dust ash according to a proportion to obtain a mixture, adding water into the mixture, uniformly mixing, and then adding a binder to obtain a kneaded material;
s3, kneading and uniformly mixing the kneaded materials, and granulating to obtain raw materials;
s4, drying the raw materials in a natural airing or low-temperature drying mode;
s5, sending the dried raw materials into a pyrolysis furnace for pyrolysis;
and S6, after pyrolysis is finished, introducing steam to perform carbonization and activation, and then cooling to room temperature in an inert gas atmosphere to obtain the adsorbent.
As one embodiment, the conditions of pyrolysis in step S5 are: inert atmosphere at 650-750deg.C for 30-120 min; the conditions for activation in step S6 are: the temperature is 550-800 ℃ and the time is 5-20 min.
The invention also provides another method for removing H in the flue gas 2 The preparation method of the adsorbent for S and metallic mercury comprises the following steps:
s1, dehydrating ferric salt flocculation sludge, drying and grinding for later use;
s2, mixing the ground ferric salt flocculation sludge with electric arc furnace dust ash according to a proportion to obtain a mixture, adding an activating agent into water, uniformly mixing, adding the activating agent into the mixture, uniformly mixing, and adding a binder to obtain a kneaded material;
s3, kneading and uniformly mixing the kneaded materials, and granulating to obtain raw materials;
s4, drying the raw materials in a natural airing or low-temperature drying mode;
and S5, sending the dried raw materials into a pyrolysis furnace for pyrolysis, and then cooling to room temperature in an inert gas atmosphere to obtain the adsorbent.
As one embodiment, the conditions of pyrolysis in step S5 are: inert atmosphere at 650-750deg.C for 30-120 min; the inert atmosphere is helium, argon, nitrogen and CO 2 One of the atmospheres.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention couples ferric salt flocculation sludge with effective components in the electric arc furnace dust, prepares the biomass adsorbent rich in pore channel structure, metal sulfide and ZnO components through pyrolysis and activation, and can simultaneously focus H in furnace flue gas and blast furnace flue gas 2 S and heavy metal mercury are adsorbed and removed;
(2) FeSO in the ferric salt flocculation sludge of the invention 4 Decomposing at high temperature or at high temperature ZnCl 2 When the catalyst is used as an activator, the catalyst is decomposed to generate sulfides of pig iron, which is favorable for removing mercury, and generated oxygen can oxidize Zn in the electric arc furnace dust into ZnO at high temperature, and the ZnO contained in the electric arc furnace dust can promote H together with ZnO contained in the electric arc furnace dust 2 S is adsorbed;
(3) The invention canDirectly adopt ZnCl 2 As an activator, naCl and KCl can be used as the activators, so that the catalyst is low in cost and easy to obtain, and ZnCl can be formed due to the existence of Zn in the system 2 The form of (2) is used as an activator, has the function of reaming and is beneficial to the generation of iron sulfide; h can also be used 2 SO 4 As an activator, H 2 SO 4 Can erode biomass, is favorable for reaming and H 2 SO 4 Decomposing at high temperature to produce SO 2 、H 2 O、O 2 Is also favorable for reaming and SO 4 2- The existence of the catalyst is favorable for generating sulfide and removing mercury;
(4) The ferric salt flocculation sludge and the electric arc furnace dust ash adopted by the adsorbent are solid wastes, so that the high-value utilization of the solid wastes can be realized, the environment is protected, and the advantages of low cost and simple process are realized.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an XPS spectrum of Zn 2p in adsorbents prepared in example III and comparative example of the present invention;
FIG. 2 is an XPS spectrum of Fe 2p in the adsorbents prepared in example III and comparative example of the present invention;
FIG. 3 is an XPS spectrum of S2 p in the adsorbents prepared in example III and comparative example of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
This embodiment provides a method for removing H from flue gas 2 S and metallic mercury, wherein the adsorbent is prepared from the following raw materials: ferric salt flocculates sludge, electric arc furnace dust, binder and water. Wherein the binder comprises one or more of starch, cellulose, asphalt and tar.
Further, the mass ratio of the ferric salt flocculation sludge to the electric arc furnace dust is 3:1 to 10:1. when the mass ratio of ferric salt flocculated sludge to electric arc furnace dust is lower than 3:1, the content of the electric arc furnace dust is relatively high, the proportion of Zn is increased, znO is generated more, and H is removed 2 S effect is increased, but ferric salt flocculated sludge content is relatively low, biomass is less, specific surface area is low, active sulfide content is low, mercury removal effect is poor, meanwhile, oxygen generated by decomposition is less, znO is limited, and H is removed 2 S effect improvement is limited; when the mass ratio of ferric salt flocculated sludge and electric arc furnace dust is higher than 10:1, the content of ferric salt flocculation sludge is relatively high, an adsorbent with a slightly high specific surface area and high content of active sulfide can be prepared, the mercury removal effect is good, but the content of electric arc furnace dust is relatively low, the Zn content of a system is limited, the generated ZnO is limited, and H is removed 2 S effect is poor; when the mass ratio of ferric salt flocculated sludge to electric arc furnace dust is 3:1 to 10:1, can prepare the adsorbent which contains a large number of pore structures, contains abundant ZnO and contains abundant metal sulfides, and removes H 2 S and mercury removal effects are good.
Further, the amount of the binder is 20% -40% of the sum of the mass of the ferric salt flocculated sludge and the mass of the electric arc furnace dust, and the amount of the water is 15% -30% of the sum of the mass of the ferric salt flocculated sludge and the mass of the electric arc furnace dust.
The embodiment also provides the method for removing H in the flue gas 2 The preparation method of the adsorbent for S and metallic mercury comprises the following steps:
s1, dehydrating ferric salt flocculation sludge, drying and grinding to below 50 meshes for later use;
s2, mixing the ground ferric salt flocculation sludge with electric arc furnace dust according to the following ratio of 3:1 to 10:1, obtaining a mixture, adding 15-30% of water by mass of the mixture into the mixture, uniformly mixing, and adding 20-40% of binder by mass of the mixture to obtain a kneaded material;
s3, kneading and mixing the kneaded materials uniformly, and granulating to obtain raw materials, wherein the raw materials can be spherical, columnar, blocky and the like, and the size of the raw materials is d=about 5-10 mm;
s4, drying the raw materials by adopting a natural airing or low-temperature (below 200 ℃) drying mode;
s5, sending the dried raw materials into a pyrolysis furnace which is inert atmosphere, and pyrolyzing at 650-750 ℃ for 30-120 min;
s6, after pyrolysis is completed, maintaining the temperature in the furnace at 550-800 ℃, introducing steam for carbonization and activation, controlling the activation time at 5-20min, and cooling to room temperature under the inert gas atmosphere to obtain the adsorbent. Wherein the inert atmosphere is helium, argon, nitrogen and CO 2 One of the atmospheres.
In the embodiment, the valuable components in ferric salt flocculation sludge and electric arc furnace dust are fully utilized, a biomass carbon adsorbent which contains a large number of pore structures and contains rich ZnO and metal sulfides is prepared through biomass pyrolysis and activation, and the biomass carbon adsorbent is used as H in blast furnace gas and coke oven gas 2 S and heavy metal mercury purification material can greatly improve H pair 2 S and adsorbing heavy metal mercury.
Example two
This embodiment provides a method for removing H from flue gas 2 S and metallic mercury, wherein the adsorbent is prepared from the following raw materials: ferric salt flocculated sludge, electric arc furnace dust, binder, water and activator. Wherein the binder comprises one or more of starch, cellulose, asphalt and tar; the activator comprises H 2 SO 4 、NaCl、KCl、ZnCl 2 One or more of the following.
Further, the mass ratio of the ferric salt flocculation sludge to the electric arc furnace dust is 3:1 to 10:1.
further, the using amount of the binder is 20-40% of the sum of the mass of the ferric salt flocculation sludge and the mass of the electric arc furnace dust, and the using amount of the water is 15-30% of the sum of the mass of the ferric salt flocculation sludge and the mass of the electric arc furnace dust; the dosage of the activating agent is 3% -15% of the sum of the mass of the ferric salt flocculated sludge and the mass of the electric arc furnace dust.
The embodiment also provides the method for removing H in the flue gas 2 The preparation method of the adsorbent for S and metallic mercury comprises the following steps:
s1, dehydrating ferric salt flocculation sludge, drying and grinding to below 50 meshes for later use;
s2, mixing the ground ferric salt flocculation sludge with electric arc furnace dust according to the following ratio of 3:1 to 10:1, obtaining a mixture, adding 3-15% of an activating agent by mass of the mixture into water, uniformly mixing, adding the activating agent into the mixture, uniformly mixing, and adding a binder by mass of the mixture, wherein the binder is 20-40% of the mass of the mixture, so as to obtain a kneaded material; the activator can be added into part of water to dissolve, then the activator solution and the other part of activator solution are respectively added into the mixture, or the activator can be directly added into all water to dissolve, and then the activator solution is directly added into the mixture.
S3, kneading and mixing the kneaded materials uniformly, and granulating to obtain raw materials, wherein the raw materials can be spherical, columnar, blocky and the like, and the size of the raw materials is d=about 5-10 mm;
s4, drying the raw materials by adopting a natural airing or low-temperature (below 200 ℃) drying mode;
s5, sending the dried raw materials into a pyrolysis furnace, wherein the pyrolysis furnace is in an inert atmosphere, pyrolyzing at 650-750 ℃ for 30-120 min, and cooling to room temperature in the inert atmosphere after pyrolysis is finished to obtain the adsorbent. Wherein the inert atmosphere is helium, argon, nitrogen and CO 2 One of the atmospheres.
This embodimentFully utilizing valuable components in ferric salt flocculation sludge and electric arc furnace dust, preparing biomass carbon adsorbent which contains a large number of pore structures and contains rich ZnO and metal sulfides through biomass pyrolysis and activation, and adopting the biomass carbon adsorbent as H in blast furnace gas and coke oven gas 2 S and heavy metal mercury purification material can greatly improve H pair 2 S and adsorbing heavy metal mercury.
Example III
The embodiment provides a method for removing H in flue gas 2 The preparation method of the adsorbent for S and metallic mercury comprises the following steps:
s1, dehydrating ferric salt flocculation sludge, drying and grinding to below 50 meshes for later use;
s2, mixing the ground ferric salt flocculation sludge with electric arc furnace dust according to the following ratio of 4:1, mixing to obtain a mixture, adding a KCl activator accounting for 5% of the mass of the mixture into water accounting for 20% of the mass of the mixture, uniformly mixing the mixture, adding a binder accounting for 30% of the mass of the mixture, and obtaining a kneaded material;
s3, kneading and mixing the kneaded materials uniformly, and granulating to obtain raw materials, wherein the raw materials can be spherical, columnar, blocky and the like, and the size of the raw materials is d=7mm;
s4, drying the raw material by adopting a low-temperature (100 ℃) drying mode;
s5, sending the dried raw materials into a pyrolysis furnace, wherein the pyrolysis furnace is inert atmosphere, pyrolyzing at 700 ℃ for 80min, and cooling to room temperature under the inert atmosphere after pyrolysis is finished to obtain the adsorbent.
Comparative example
The comparative example provides a method for preparing an adsorbent, comprising the following steps:
s1, dehydrating ferric salt flocculation sludge, drying and grinding to below 50 meshes for later use;
s2, adding the grinded ferric salt flocculation sludge into water with the mass of 20% of that of the ferric salt flocculation sludge, uniformly mixing, and then adding a binder with the mass of 30% of that of the ferric salt flocculation sludge to obtain a kneading material;
s3, kneading and mixing the kneaded materials uniformly, and granulating to obtain raw materials, wherein the raw materials can be spherical, columnar, blocky and the like, and the size of the raw materials is d=7mm;
s4, drying the raw material by adopting a low-temperature (100 ℃) drying mode;
s5, sending the dried raw materials into a pyrolysis furnace, wherein the pyrolysis furnace is inert atmosphere, pyrolyzing at 700 ℃ for 80min, and cooling to room temperature under the inert atmosphere after pyrolysis is finished to obtain the adsorbent.
The XPS spectrogram analysis is carried out on the adsorbents prepared in the third embodiment and the comparative embodiment, and the results are shown in figures 1-3, so that compared with the comparative embodiment, the preparation method disclosed by the invention is beneficial to improving the ZnO content and H removal after adding the electric arc furnace dust and the activator 2 S effect, improves the generation of high-valence iron oxide, and is beneficial to Hg and H removal 2 S is adsorbed; the generation of sulfide is also improved, which is beneficial to mercury removal.
The specific surface area, pore volume and pore diameter parameters of the adsorbents prepared in the third and comparative examples are tested, and the results are shown in Table 1, and it can be seen that compared with the comparative examples, the specific surface area and total pore volume of the prepared adsorbent can be remarkably improved by adopting the preparation method of the invention, which is beneficial to Hg and H 2 Adsorption of S.
TABLE 1 specific surface area, pore volume and pore size parameters of different additions to adsorbents
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (6)
1. H in desorption flue gas 2 S and metallic mercury' S adsorbent, its characterized in that: the adsorbent is prepared from the following raw materials by pyrolysis and activation:ferric salt flocculation sludge, electric arc furnace dust, binder, water and activator; the activator comprises H 2 SO 4 、NaCl、KCl、ZnCl 2 One or more of the following; the mass ratio of the ferric salt flocculated sludge to the electric arc furnace dust is 3: 1-10: 1.
2. the method for removing H in flue gas according to claim 1 2 S and metallic mercury' S adsorbent, its characterized in that: the consumption of the binder is 20% -40% of the sum of the mass of the ferric salt flocculation sludge and the mass of the electric arc furnace dust, and the consumption of the water is 15% -30% of the sum of the mass of the ferric salt flocculation sludge and the mass of the electric arc furnace dust.
3. The method for removing H in flue gas according to claim 1 2 S and metallic mercury' S adsorbent, its characterized in that: the binder comprises one or more of starch, cellulose, asphalt and tar.
4. The method for removing H in flue gas according to claim 1 2 S and metallic mercury' S adsorbent, its characterized in that: the dosage of the activating agent is 3% -15% of the sum of the mass of the ferric salt flocculated sludge and the mass of the electric arc furnace dust.
5. The method for removing H in flue gas according to any one of claims 1 to 4 2 The preparation method of the adsorbent for S and metallic mercury is characterized by comprising the following steps:
s1, dehydrating ferric salt flocculation sludge, drying and grinding for later use;
s2, mixing the ground ferric salt flocculation sludge with electric arc furnace dust ash according to a proportion to obtain a mixture, adding an activating agent into water, uniformly mixing, adding the activating agent into the mixture, uniformly mixing, and adding a binder to obtain a kneaded material;
s3, kneading and uniformly mixing the kneaded materials, and granulating to obtain raw materials;
s4, drying the raw materials in a natural airing or low-temperature drying mode;
and S5, sending the dried raw materials into a pyrolysis furnace for pyrolysis, and then cooling to room temperature in an inert gas atmosphere to obtain the adsorbent.
6. The method of manufacturing according to claim 5, wherein: the conditions for pyrolysis in step S5 are: inert atmosphere at 650-750deg.C for 30-120 min; the inert atmosphere is helium, argon, nitrogen and CO 2 One of the atmospheres.
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