CN115463640A - 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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- CN115463640A CN115463640A CN202211195611.7A CN202211195611A CN115463640A CN 115463640 A CN115463640 A CN 115463640A CN 202211195611 A CN202211195611 A CN 202211195611A CN 115463640 A CN115463640 A CN 115463640A
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 53
- 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 24
- 239000003546 flue gas Substances 0.000 title claims abstract description 24
- 229940008718 metallic mercury Drugs 0.000 title claims description 18
- 238000002360 preparation method Methods 0.000 title claims description 14
- 238000003795 desorption Methods 0.000 title claims description 6
- 239000010802 sludge Substances 0.000 claims abstract description 55
- 238000010891 electric arc Methods 0.000 claims abstract description 46
- 150000003839 salts Chemical class 0.000 claims abstract description 44
- 239000002994 raw material Substances 0.000 claims abstract description 43
- 239000000428 dust Substances 0.000 claims abstract description 36
- 238000000197 pyrolysis Methods 0.000 claims abstract description 32
- 238000002156 mixing Methods 0.000 claims abstract description 30
- 238000001035 drying Methods 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000011230 binding agent Substances 0.000 claims abstract description 21
- 238000005189 flocculation Methods 0.000 claims abstract description 18
- 230000016615 flocculation Effects 0.000 claims abstract description 18
- 230000004913 activation Effects 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 238000000227 grinding Methods 0.000 claims abstract description 9
- 238000004898 kneading Methods 0.000 claims abstract description 9
- 239000011261 inert gas Substances 0.000 claims abstract description 8
- 238000003763 carbonization Methods 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 230000003213 activating effect Effects 0.000 claims description 13
- 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
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 229920002472 Starch Polymers 0.000 claims description 4
- 229910052786 argon Inorganic materials 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
- 239000011780 sodium chloride Substances 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
- 239000010426 asphalt Substances 0.000 claims description 3
- 229910052753 mercury Inorganic materials 0.000 abstract description 19
- 150000002505 iron Chemical class 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 239000002910 solid waste Substances 0.000 abstract description 3
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 abstract description 2
- 230000001737 promoting effect Effects 0.000 abstract 1
- 239000002956 ash Substances 0.000 description 27
- 239000007789 gas Substances 0.000 description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 239000012190 activator Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 239000000571 coke Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000002028 Biomass Substances 0.000 description 8
- 239000008187 granular material Substances 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- 230000009286 beneficial effect Effects 0.000 description 7
- 229910001385 heavy metal Inorganic materials 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229910052976 metal sulfide Inorganic materials 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000008394 flocculating agent 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
- 230000001174 ascending effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910000497 Amalgam Inorganic materials 0.000 description 1
- 238000007792 addition 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
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 238000010438 heat treatment Methods 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
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- -1 sulfide modified activated carbon Chemical class 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
- B01J20/20—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 NOT OTHERWISE PROVIDED FOR
- 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 NOT OTHERWISE PROVIDED FOR
- 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 NOT OTHERWISE PROVIDED FOR
- 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
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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
- 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
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- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Treating Waste Gases (AREA)
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 The adsorbent is prepared from the following raw materials: dewatering, drying and grinding the ferric salt flocculated sludge, mixing the dewatered and ground ferric salt flocculated sludge with the electric arc furnace dust removal ash, adding water, uniformly mixing, adding the binder, kneading, uniformly mixing and granulating to obtain a raw material; then it will be bornAnd drying the material, then sending the dried material into a pyrolysis furnace for pyrolysis, after the pyrolysis is finished, introducing water vapor for carbonization and activation, and then cooling the material to room temperature in an inert gas atmosphere. The raw materials adopted by the adsorbent are all solid wastes, so that the adsorbent has the advantages of low cost and simple process; feSO in iron salt flocculation sludge 4 Decomposing at high temperature to produce iron sulfide, benefiting mercury removal, generating oxygen to oxidize Zn in the arc furnace dust into ZnO at high temperature, and promoting H together with ZnO contained in the arc furnace dust 2 And (4) adsorbing 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 flue gas of coke oven gas and blast furnace gas 2 S and metallic mercury adsorbent and preparation method thereof.
Background
With the increasing of energy demand and the increasing of environmental protection requirements, low-calorific-value gas resources such as coke oven gas, blast furnace gas and the like are utilized in the processThe problems of heavy metal mercury pollution and desulfurization caused by the mercury are more and more prominent. The current commonly used wet desulphurization process is to SO 2 Has better removing effect, but can remove H in coke oven gas and blast furnace gas 2 The pollutant removal effect is poor; activated carbon is relatively low in price, but for H 2 The adsorption capacity of S is limited, and the microcrystalline or polycrystalline adsorption material has good effect but higher cost; in addition, mercury pollutants in the coke oven gas or the blast furnace gas can be combined with other metals to generate amalgam, so that the liquefaction device is corroded, and trace mercury enters the Liquefied Natural Gas (LNG) product and is released in the using process of the LNG, so that the surrounding environment is damaged; the commonly used mercury removing agent comprises activated carbon, in particular sulfide modified activated carbon and the like, and the matching of the adsorbent and facilities greatly increases the treatment cost of the coke oven gas or the blast furnace gas.
On the other hand, ferrous sulfate (FeSO) 4 ) As a typical flocculating agent, the iron flocculating agent is widely used in the flocculation dehydration process of urban domestic sewage treatment, the dosage of the iron flocculating agent is higher, generally about 3-5% of the weight of dry sludge, a large amount of iron salt flocculation sludge is generated, and the sludge capacity increase also increases the final sludge treatment amount and the treatment difficulty.
In addition, in the steelmaking process in an electric arc furnace, a large amount of fly ash is generated, which is essentially that during the production of the electric arc furnace, due to heating and accompanying violent stirring at high temperature, some metals are evaporated, some metals are brought out of the furnace by the ascending hot gas flow, and some oxides in the slag may be brought into the dust collecting system by the ascending hot gas flow directly to form the dust removed from the electric arc furnace. The main component of the electric arc furnace dust removing ash is Fe x O y (21-48 percent), zn and ZnO (15-50 percent), caO (1-10 percent), mgO (1-5 percent) and Al 2 O 3 (0.5% -8%) and the like. Because the production amount of the electric arc furnace dedusting ash is large and the application means is limited, a large amount of electric arc furnace dedusting ash cannot be effectively utilized and can only be stacked in a storage yard, and a large amount of land resources are occupied.
Therefore, it is necessary to design a device which can be used forThe iron salt flocculated sludge and the value components in the dust removed by the electric arc furnace are fully utilized, and H in the flue gas of the coke oven gas and the blast furnace gas can be removed simultaneously 2 S and metallic mercury adsorbent and a preparation method thereof, which aim to solve the problems.
Disclosure of Invention
The invention aims to provide a method for removing H in flue gas 2 The S and metallic mercury adsorbent and the 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 to remove H in the flue gas 2 The adsorbent for S and metallic mercury is prepared from the following raw materials: ferric salt flocculation sludge, electric arc furnace dedusting ash, a binder and water.
As an embodiment, the mass ratio of the iron salt flocculated sludge to the electric arc furnace fly ash is 3:1 to 10:1.
in one embodiment, the amount of the binder is 20% to 40% of the mass sum of the iron salt-flocculated sludge and the electric arc furnace dust, and the amount of the water is 15% to 30% of the mass sum of the iron salt-flocculated sludge and the electric arc furnace dust.
In one embodiment, the binder comprises one or more of starch, cellulose, pitch, tar.
As one embodiment, the raw material for preparing the adsorbent further comprises an activator, and the activator comprises H 2 SO 4 、NaCl、KCl、ZnCl 2 One or more of them.
As one embodiment, the amount of the activator is 3 to 15% of the mass sum of the iron salt flocculated sludge and the electric arc furnace dust removal ash.
The invention also provides a method for removing H in flue gas 2 The preparation method of the S and metal mercury adsorbent comprises the following steps:
s1, dehydrating, drying and grinding the ferric salt flocculated sludge for later use;
s2, mixing the ground ferric salt flocculation sludge with the electric arc furnace dedusting ash according to a proportion to obtain a mixture, adding water into the mixture, uniformly mixing, and adding a binder to obtain a kneaded material;
s3, kneading and uniformly mixing the kneaded material, and granulating to obtain a raw material;
s4, drying the raw materials in a natural airing or low-temperature drying mode;
s5, feeding the dried raw material into a pyrolysis furnace for pyrolysis;
and S6, after pyrolysis is finished, introducing water vapor for carbonization and activation, and then cooling to room temperature in an inert gas atmosphere to obtain the adsorbent.
As an embodiment, the pyrolysis conditions in step S5 are: inert atmosphere, temperature 650-750 deg.C, time 30min-120min; the conditions for activation in step S6 are: the temperature is 550-800 deg.C, and the time is 5min-20min.
The invention also provides another method for removing H in the flue gas 2 The preparation method of the S and metal mercury adsorbent comprises the following steps:
s1, dehydrating, drying and grinding the ferric salt flocculated sludge for later use;
s2, mixing the ground ferric salt flocculation sludge and the electric arc furnace dedusting 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 then adding a binder to obtain a kneaded material;
s3, kneading and uniformly mixing the kneaded material, and granulating to obtain a raw material;
s4, drying the raw materials in a natural airing or low-temperature drying mode;
and S5, feeding the dried raw material into a pyrolysis furnace for pyrolysis, and then cooling to room temperature in an inert gas atmosphere to obtain the adsorbent.
As an embodiment, the pyrolysis conditions in step S5 are: inert atmosphere, temperature 650-750 deg.C, time 30min-120min; 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) Book (notebook)The invention couples the ferric salt flocculation sludge with the effective components in the dust removal ash of the electric arc furnace, prepares the biomass adsorbent rich in the components of pore channel structure, metal sulfide and ZnO by pyrolysis and activation, and can simultaneously adsorb H in the coke furnace smoke and the blast furnace smoke 2 S and heavy metal mercury are adsorbed and removed;
(2) The ferric salt flocculates FeSO in the sludge 4 Decomposition at high temperature or ZnCl 2 When the activated carbon is used as an activating agent, the activated carbon is decomposed to produce sulfides of iron, which is beneficial to removing mercury, and the produced oxygen can oxidize Zn in the electric arc furnace dust into ZnO at high temperature and promote H together with the ZnO contained in the electric arc furnace dust 2 S is adsorbed;
(3) The invention can directly adopt ZnCl 2 NaCl and KCl can be used as the activator, which is cheap and easily available, and ZnCl can be formed due to the existence of Zn element in the system 2 The form of the (B) is used as an activating agent, has the function of reaming and is beneficial to the generation of iron sulfide; may also adopt H 2 SO 4 As activator, H 2 SO 4 Can erode biomass, is favorable for reaming, H 2 SO 4 Decomposition at high temperature to produce SO 2 、H 2 O、O 2 Is also advantageous for reaming, and SO 4 2- The existence of (2) is beneficial to the generation of sulfide and the demercuration;
(4) The ferric salt flocculation sludge and the electric arc furnace dust removal ash adopted by the adsorbent are solid wastes, so that the high-value utilization of the solid wastes can be realized, the environmental protection is facilitated, and the adsorbent has the advantages of low cost and simple process.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is an XPS spectrum of Zn 2p in adsorbents prepared in example three of the present invention and a comparative example;
FIG. 2 is an XPS spectrum of Fe 2p in adsorbents prepared in example three of the present invention and a comparative example;
FIG. 3 is an XPS spectrum of S2 p in adsorbents prepared in example three of the present invention and a comparative example.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example one
This embodiment provides H in desorption flue gas 2 The adsorbent for S and metallic mercury is prepared from the following raw materials: ferric salt flocculation sludge, electric arc furnace dedusting ash, a binder and water. Wherein, the binder comprises one or more of starch, cellulose, asphalt and tar.
Further, the mass ratio of the ferric salt flocculated sludge to the electric arc furnace dust removing ash is 3:1 to 10:1. when the mass ratio of the ferric salt flocculation sludge to the electric arc furnace dust removal ash is lower than 3:1 hour, the content of the dust removed by the electric arc furnace is relatively high, the proportion of Zn is increased, the generated ZnO is increased, and H is removed 2 The S effect is increased, but the content of ferric salt flocculated sludge is relatively low, the generated biomass is less, the specific surface area is low, the content of active sulfide is low, the demercuration effect is poor, and the generated oxygen generated by decomposition is less, so that the generated ZnO is limited, and H is removed 2 The improvement of S effect is limited; when the mass ratio of the ferric salt flocculated sludge to the electric arc furnace dust removal ash is higher than 10:1, the content of the ferric salt flocculated sludge is relatively high, the adsorbent with slightly high specific surface area and high content of active sulfides can be prepared, the demercuration effect is good, but the content of the electric arc furnace dust is relatively low, the Zn content of the system is limited, the generated ZnO is limited, and H is removed 2 S EffectPoor fruit quality; when the mass ratio of the ferric salt flocculation sludge to the electric arc furnace dedusting ash is 3:1 to 10:1, the adsorbent containing a large number of pore channel structures, rich ZnO and rich metal sulfides can be prepared, and H is removed 2 S and the mercury removal effect are good.
Further, the amount of the binder is 20% -40% of the mass sum of the ferric salt flocculated sludge and the electric arc furnace dust removal ash, and the amount of the water is 15% -30% of the mass sum of the ferric salt flocculated sludge and the electric arc furnace dust removal ash.
The embodiment also provides the method for removing H in the flue gas 2 The preparation method of the S and metal mercury adsorbent comprises the following steps:
s1, dehydrating, drying and grinding the ferric salt flocculated sludge to below 50 meshes for later use;
s2, mixing the ground ferric salt flocculated sludge and the electric arc furnace dust removal ash according to the proportion of 3:1 to 10:1 to obtain a mixture, adding water accounting for 15-30% of the mass of the mixture into the mixture, uniformly mixing, and adding a binder accounting for 20-40% of the mass of the mixture to obtain a kneaded material;
s3, kneading and uniformly mixing the kneaded material, and granulating to obtain a raw material, wherein the granules of the raw material can be spherical, columnar, blocky and the like, and the size of the granules is about d =5-10 mm;
s4, drying the raw materials in a natural airing or low-temperature (below 200 ℃) drying mode;
s5, feeding the dried raw materials into a pyrolysis furnace, wherein the pyrolysis furnace is in an inert atmosphere and pyrolyzes at 650-750 ℃ for 30-120 min;
s6, after pyrolysis is finished, keeping the temperature in the furnace within the range of 550-800 ℃, introducing steam for carbonization and activation, controlling the activation time to be 5-20min, and then cooling to room temperature in an inert gas atmosphere to obtain the adsorbent. Wherein the inert atmosphere is helium, argon, nitrogen, CO 2 One of the atmospheres.
The embodiment fully utilizes the value components in the ferric salt flocculation sludge and the electric arc furnace dust removal ash, and prepares the product containing the large iron through biomass pyrolysis and activationBiomass carbon adsorbent with metering orifice structure and rich ZnO and metal sulfide, and the biomass carbon adsorbent is used as H in blast furnace gas and coke oven gas 2 S and heavy metal mercury purifying material can greatly improve the effect on H 2 S and adsorbing heavy metal mercury.
Example two
This embodiment provides H in desorption flue gas 2 The adsorbent for S and metallic mercury is prepared from the following raw materials: ferric salt flocculated sludge, electric arc furnace dust removal ash, a binder, water and an activating agent. 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 them.
Further, the mass ratio of the ferric salt flocculated sludge to the electric arc furnace dust removal ash is 3:1 to 10:1.
further, the amount of the binder is 20% -40% of the mass sum of the ferric salt flocculated sludge and the electric arc furnace dust removal ash, and the amount of the water is 15% -30% of the mass sum of the ferric salt flocculated sludge and the electric arc furnace dust removal ash; the dosage of the activating agent is 3-15% of the mass sum of the ferric salt flocculated sludge and the electric arc furnace dust removal ash.
The embodiment also provides the method for removing H in the flue gas 2 The preparation method of the S and metallic mercury adsorbent comprises the following steps:
s1, dehydrating, drying and grinding the ferric salt flocculated sludge to below 50 meshes for later use;
s2, mixing the ground ferric salt flocculated sludge and the electric arc furnace dust removal ash according to the proportion of 3:1 to 10:1 to obtain a mixture, adding an activating agent accounting for 3-15% of the mass of the mixture into water, uniformly mixing, adding into the mixture, uniformly mixing, and adding a binder accounting for 20-40% of the mass of the mixture to obtain a kneaded material; the activator can be added into part of water to be dissolved firstly, then the activator solution and the other part of water are added into the mixture respectively, or the activator can be directly added into all the water to be dissolved, and then the activator solution is directly added into the mixture.
S3, kneading and uniformly mixing the kneaded material, and granulating to obtain a raw material, wherein the granules of the raw material can be spherical, columnar, blocky and the like, and the size of the granules is about d =5-10 mm;
s4, drying the raw materials in a natural airing or low-temperature (below 200 ℃) drying mode;
and S5, feeding the dried raw material into a pyrolysis furnace, wherein the pyrolysis furnace is in an inert atmosphere, pyrolyzing the raw material at 650-750 ℃ for 30-120 min, and cooling the raw material to room temperature in the inert atmosphere after pyrolysis is finished to obtain the adsorbent. Wherein the inert atmosphere is helium, argon, nitrogen, CO 2 One of the atmospheres.
In the embodiment, the value components in the ferric salt flocculation sludge and the electric arc furnace dust removal ash are fully utilized, the biomass carbon adsorbent containing a large number of pore channel structures and rich ZnO and metal sulfides is prepared by 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 purifying material can greatly improve the effect on H 2 S and adsorbing heavy metal mercury.
EXAMPLE III
This embodiment provides a desorption H in flue gas 2 The preparation method of the S and metallic mercury adsorbent comprises the following steps:
s1, dehydrating, drying and grinding iron salt flocculated sludge to be below 50 meshes for later use;
s2, mixing the ground ferric salt flocculated sludge and the electric arc furnace dust removal ash according to the ratio of 4:1 to obtain a mixture, adding a KCl activator accounting for 5 percent of the mass of the mixture into water accounting for 20 percent of the mass of the mixture, uniformly mixing, adding the mixture into the mixture, uniformly mixing, and adding a binder accounting for 30 percent of the mass of the mixture to obtain a kneaded material;
s3, kneading and uniformly mixing the kneaded material, and then granulating to obtain a raw material, wherein the granules of the raw material can be spherical, columnar, blocky and the like, and the size of the granules is about d =7 mm;
s4, drying the raw materials in a low-temperature (100 ℃) drying mode;
and S5, feeding the dried raw material into a pyrolysis furnace, wherein the pyrolysis furnace is in an inert atmosphere, pyrolyzing the raw material for 80min at 700 ℃, and cooling the raw material to room temperature in the inert gas atmosphere after pyrolysis is finished to obtain the adsorbent.
Comparative example
The present comparative example provides a method for preparing an adsorbent, comprising the steps of:
s1, dehydrating, drying and grinding the ferric salt flocculated sludge to below 50 meshes for later use;
s2, adding the ground ferric salt flocculated sludge into water accounting for 20% of the mass of the ferric salt flocculated sludge, uniformly mixing, and then adding a binder accounting for 30% of the mass of the ferric salt flocculated sludge to obtain a kneaded material;
s3, kneading and uniformly mixing the kneaded material, and then granulating to obtain a raw material, wherein the granules of the raw material can be spherical, columnar, blocky and the like, and the size of the granules is about d =7 mm;
s4, drying the raw materials in a low-temperature (100 ℃) drying mode;
and S5, feeding the dried raw material into a pyrolysis furnace, wherein the pyrolysis furnace is in an inert atmosphere, pyrolyzing the raw material for 80min at 700 ℃, and cooling the raw material to room temperature in the inert gas atmosphere after pyrolysis is finished to obtain the adsorbent.
XPS spectrogram analysis is carried out on the adsorbents prepared in the third embodiment and the comparative example, and the results are shown in figures 1-3, so that compared with the comparative example, after the electric arc furnace dedusting ash and the activating agent are added by the preparation method disclosed by the invention, the improvement of ZnO content is facilitated, and H removal is improved 2 S effect, improves the generation of high valence iron oxide, and is beneficial to removing Hg and H 2 S is adsorbed; but also improves the generation of sulfide and is beneficial to mercury removal.
The specific surface area, the pore volume and the pore diameter parameters of the adsorbents prepared in the third example and the comparative example are detected, and the results are shown in table 1, so that the preparation method can obviously improve the specific surface area and the total pore volume of the prepared adsorbent compared with the comparative example, and is beneficial to Hg and H 2 And (4) adsorbing S.
TABLE 1 specific surface area, pore volume, pore size parameters for different additions to the adsorbent
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the scope of the present invention, which is intended to cover any modifications, equivalents, improvements, etc. within the spirit and scope of the present invention.
Claims (10)
1. H in desorption flue gas 2 S and metallic mercury adsorbent, which is characterized in that: the adsorbent is prepared from the following raw materials: ferric salt flocculated sludge, electric arc furnace dust removal ash, a binder and water.
2. The method for removing H in flue gas as claimed in claim 1 2 S and metallic mercury adsorbent, which is characterized in that: the mass ratio of the ferric salt flocculation sludge to the electric arc furnace dust removal ash is 3:1 to 10:1.
3. the method for removing H in flue gas as claimed in claim 1 2 S and metallic mercury adsorbent, which is characterized in that: the dosage of the binder is 20% -40% of the mass sum of the ferric salt flocculation sludge and the electric arc furnace dust removal ash, and the dosage of the water is 15% -30% of the mass sum of the ferric salt flocculation sludge and the electric arc furnace dust removal ash.
4. The method for removing H in the flue gas as claimed in any one of claim 1 2 The adsorbent for S and metallic mercury is characterized in that: the binder comprises one or more of starch, cellulose, asphalt and tar.
5. The method for removing H in flue gas as claimed in claims 1-4 2 S and metallic mercury adsorbent, which is characterized in that: the raw material for preparing the adsorbent also comprises an activating agent, and the activating agent comprises H 2 SO 4 、NaCl、KCl、ZnCl 2 One or more of them.
6. The method for removing H in flue gas as claimed in claim 5 2 S and metallic mercury adsorbent, which is characterized in that: the dosage of the activating agent is 3-15% of the mass sum of the ferric salt flocculated sludge and the electric arc furnace dust removal ash.
7. The method for removing H in flue gas according to any one of claims 1 to 4 2 The preparation method of the S and metallic mercury adsorbent is characterized by comprising the following steps:
s1, dehydrating, drying and grinding the ferric salt flocculated sludge for later use;
s2, mixing the ground ferric salt flocculation sludge with the electric arc furnace dedusting ash according to a proportion to obtain a mixture, adding water into the mixture, uniformly mixing, and adding a binder to obtain a kneaded material;
s3, kneading and uniformly mixing the kneaded material, and granulating to obtain a raw material;
s4, drying the raw materials in a natural airing or low-temperature drying mode;
s5, feeding the dried raw materials into a pyrolysis furnace for pyrolysis;
and S6, after pyrolysis is finished, introducing water vapor for carbonization and activation, and then cooling to room temperature in an inert gas atmosphere to obtain the adsorbent.
8. The method of claim 7, wherein: the pyrolysis conditions in step S5 are: inert atmosphere, temperature 650-750 deg.C, time 30min-120min; the conditions for activation in step S6 are: the temperature is 550-800 deg.C, and the time is 5min-20min.
9. The method for removing H in flue gas according to any one of claims 5 to 6 2 The preparation method of the S and metallic mercury adsorbent is characterized by comprising the following steps:
s1, dehydrating, drying and grinding the ferric salt flocculated sludge for later use;
s2, mixing the ground ferric salt flocculation sludge and the electric arc furnace dedusting 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 then adding a binder to obtain a kneaded material;
s3, kneading and uniformly mixing the kneaded material, and granulating to obtain a raw material;
s4, drying the raw materials in a natural airing or low-temperature drying mode;
and S5, feeding the dried raw material into a pyrolysis furnace for pyrolysis, and then cooling to room temperature in an inert gas atmosphere to obtain the adsorbent.
10. The method of claim 9, wherein: the pyrolysis conditions in step S5 are: inert atmosphere, temperature 650-750 deg.C, time 30min-120min; the inert atmosphere is helium, argon, nitrogen and CO 2 One of the atmospheres.
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