CN115999335A - Flue gas desulfurizing agent and preparation method thereof - Google Patents
Flue gas desulfurizing agent and preparation method thereof Download PDFInfo
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- CN115999335A CN115999335A CN202310299648.2A CN202310299648A CN115999335A CN 115999335 A CN115999335 A CN 115999335A CN 202310299648 A CN202310299648 A CN 202310299648A CN 115999335 A CN115999335 A CN 115999335A
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 46
- 230000003009 desulfurizing effect Effects 0.000 title claims abstract description 36
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000003546 flue gas Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title description 12
- 239000000843 powder Substances 0.000 claims abstract description 34
- 239000002994 raw material Substances 0.000 claims abstract description 34
- 239000002910 solid waste Substances 0.000 claims abstract description 33
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 31
- 230000023556 desulfurization Effects 0.000 claims abstract description 31
- 239000003463 adsorbent Substances 0.000 claims abstract description 29
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 25
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 19
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 19
- -1 amine compounds Chemical class 0.000 claims abstract description 15
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 36
- 239000004568 cement Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 21
- 239000011787 zinc oxide Substances 0.000 claims description 18
- 239000002808 molecular sieve Substances 0.000 claims description 15
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical group [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 15
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 8
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 8
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 8
- XNIOWJUQPMKCIJ-UHFFFAOYSA-N 2-(benzylamino)ethanol Chemical compound OCCNCC1=CC=CC=C1 XNIOWJUQPMKCIJ-UHFFFAOYSA-N 0.000 claims description 7
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 7
- 229910021536 Zeolite Inorganic materials 0.000 claims description 7
- 239000013543 active substance Substances 0.000 claims description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 239000010457 zeolite Substances 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- 229940116318 copper carbonate Drugs 0.000 claims description 2
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims 1
- 230000000996 additive effect Effects 0.000 claims 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 claims 1
- 125000001741 organic sulfur group Chemical group 0.000 abstract description 12
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 3
- 238000010494 dissociation reaction Methods 0.000 abstract description 3
- 230000005593 dissociations Effects 0.000 abstract description 3
- 230000006872 improvement Effects 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 239000011593 sulfur Substances 0.000 description 12
- 229910052717 sulfur Inorganic materials 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 9
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- IDPURXSQCKYKIJ-UHFFFAOYSA-N 1-(4-methoxyphenyl)methanamine Chemical compound COC1=CC=C(CN)C=C1 IDPURXSQCKYKIJ-UHFFFAOYSA-N 0.000 description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 4
- 238000007865 diluting Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 4
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 4
- 229960001763 zinc sulfate Drugs 0.000 description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- 235000019738 Limestone Nutrition 0.000 description 3
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- 229910052675 erionite Inorganic materials 0.000 description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 3
- 239000002440 industrial waste Substances 0.000 description 3
- 239000006028 limestone Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 150000001868 cobalt Chemical class 0.000 description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000009270 solid waste treatment Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- JEWHCPOELGJVCB-UHFFFAOYSA-N aluminum;calcium;oxido-[oxido(oxo)silyl]oxy-oxosilane;potassium;sodium;tridecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.O.[Na].[Al].[K].[Ca].[O-][Si](=O)O[Si]([O-])=O JEWHCPOELGJVCB-UHFFFAOYSA-N 0.000 description 1
- JYIBXUUINYLWLR-UHFFFAOYSA-N aluminum;calcium;potassium;silicon;sodium;trihydrate Chemical compound O.O.O.[Na].[Al].[Si].[K].[Ca] JYIBXUUINYLWLR-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000006664 bond formation reaction Methods 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 229910001603 clinoptilolite Inorganic materials 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910001657 ferrierite group Inorganic materials 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052945 inorganic sulfide Inorganic materials 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910001743 phillipsite Inorganic materials 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000003469 silicate cement Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention discloses a flue gas desulfurizing agent, which comprises the following raw materials in parts by mass: 80-90 parts of solid waste powder, 20-25 parts of metal oxide auxiliary agent, 10-15 parts of adsorbent, 3-5 parts of catalyst and 10-15 parts of carbonate. The invention takes solid waste powder as a main raw material, adds a metal oxide auxiliary agent, improves the surface alkalinity of a desulfurizing agent, promotes sulfide dissociation, promotes the improvement of desulfurization performance, and adopts an adsorbent loaded with amine compounds to improve the removal efficiency of organic sulfur.
Description
Technical Field
The invention relates to the technical field of desulfurization, in particular to a flue gas desulfurizing agent and a preparation method and application thereof.
Background
As the demand for cement is increasing, raw materials for cement production are somewhat scarce, and thus, a large number of high sulfur raw materials (e.g., high sulfur limestone) are used in cement production during cement production. Due to the use of low quality sulfur-containing raw materials and the influence of sulfur form in solid waste and cement kiln process characteristics, during the period of grinding stopFlue gas SO from cement kiln tail 2 The phenomenon of exceeding standard occurs when the concentration is discharged, the normal operation of a production line is seriously influenced and restricted, and particularly, the environmental pollution caused by sulfides discharged to the atmosphere when the cement clinker is sintered is more serious. Thus, SO in the flue gas is reduced 2 The discharge concentration is usually achieved by adding a desulfurizing agent during the production process or by changing the production process.
Common desulfurization process technologies used in cement plants include dry reactant injection, hot raw meal injection, spray-dried desulfurization, and wet desulfurization. Among them, the dry reactant injection method has higher desulfurization efficiency, but its cost is higher, mainly the cost of purchasing slaked lime. The investment of the spray drying desulfurization method is lower than that of a wet process, and the desulfurization method can be realized by improving a humidifying tower of a cement plant, and has the advantages that the desulfurization efficiency is higher, the problem of treatment of desulfurization products is solved, but the blockage problems of pipelines, valves, spray heads and fans of a preheater in the lime slurry injection process are serious, and the overhaul and maintenance workload is large; a solids content of the desulfurizing agent slurry exceeding 13% will cause nozzle atomization difficulties, and this series of operational problems presents challenges for its application in the cement industry. The wet desulfurization method has good effect, the desulfurization efficiency can reach 80% -95%, the solid content of slurry can reach 30%, and the problems of blockage and maintenance are less, but the wet desulfurization method is limited by high equipment investment, running cost and technical requirements, and is difficult to popularize and apply. The solid desulfurizing agent with relatively small energy consumption, low cost and excellent desulfurizing effect has certain advantages.
Some solid desulfurizing agents are disclosed in the prior art, for example, patent CN115445411A discloses a solid waste powder desulfurizing agent for a cement kiln and a preparation method thereof, the raw materials of the desulfurizing agent comprise 20-45 parts of solid waste powder, 8-15 parts of auxiliary agents, 10-36 parts of metal oxides, 5-20 parts of functional particles, 20-45 parts of carbonates and the like, and the powder desulfurizing agent disclosed in the patent and most desulfurizing agents in the prior art mainly relate to sulfur dioxide (SO 2 ) Has the removal capacity, but the removal efficiency still needs to be improved, and the removal efficiency is improved for hydrogen sulfide, especially COS and CS 2 The removal effect of the organic sulfides is not obvious, and the total sulfur content in the cement is difficult to reduce, so that the solid is still neededThe bulk flue gas desulfurizing agent is further researched and developed.
Disclosure of Invention
The invention aims to solve the problems and provides a flue gas desulfurizing agent and a preparation method and application thereof.
The aim of the invention is achieved by the following technical scheme:
the flue gas desulfurizing agent comprises the following raw materials in parts by mass: 80-90 parts of solid waste powder, 20-25 parts of metal oxide auxiliary agent, 10-15 parts of adsorbent, 3-5 parts of catalyst and 10-15 parts of carbonate.
As a preferable technical scheme, the flue gas desulfurizing agent comprises the following raw materials in parts by mass: 85-88 parts of solid waste powder, 22-24 parts of metal oxide auxiliary agent, 12-13 parts of adsorbent, 3-5 parts of catalyst and 12-13 parts of carbonate.
As an optimal technical scheme, the solid waste powder consists of alkaline residue and red mud in a weight ratio of 5-6:1.
In a specific embodiment, diluting a co-agent (such as sodium polyacrylate) with water according to a weight ratio of 1:150-200, adding alkaline residue, stirring and washing, and filtering and separating to obtain the cleaned alkaline residue; heating the cleaned alkaline residue at 1000-1200 ℃ for 3-5 min to obtain heat-treated alkaline residue; and heating the red mud at 900-950 ℃ for 10-15 min to obtain the heat-treated red mud. And uniformly mixing the heat-treated alkaline residues and the heat-treated red mud to obtain solid waste powder for preparing the desulfurizing agent.
Before specific use, the alkaline residue is subjected to heat treatment after being cleaned and removed of impurities and activated by an active agent aqueous solution, and calcium sulfate and calcium carbonate in the alkaline residue are reduced into calcium oxide with desulfurization function to be used as main components of a desulfurizing agent; and red mud is compounded, and the red mud has the advantages of small particle size, multiple pores and large specific surface area, and after the red mud is heated and activated, the pores on the surface are further increased, so that the specific surface area is further increased, the desulfurization time is prolonged, and the desulfurization efficiency is improved.
The invention takes mixed solid waste powder composed of industrial waste alkaline residue and red mud as main raw materials for preparing flue gas desulfurizing agent, and the industrial solid is prepared byThe solid waste is reused, so that the method has huge environmental protection advantage and economic value, solves the problem of solid waste treatment, and simultaneously saves the waste of mine resources. Wherein, the alkaline residue is alkaline residue discharged in the process of alkali preparation and alkali treatment in industrial production, the components mainly comprise calcium salts such as calcium carbonate, calcium sulfate, calcium chloride and the like as the residue of main components, the red mud is industrial solid waste discharged after alumina is extracted from bauxite, and the main components are SiO 2 、Al 2 O 3 、CaO、Fe 2 O 3 The two are matched for use, so that the desulfurization effect is excellent.
According to the preferred technical scheme, the metal oxide auxiliary agent is modified nano zinc oxide, the modified nano zinc oxide is Co-doped nano ZnO, the Co doping amount is 2-5% of the molar mass of the nano ZnO, and rod-shaped nano ZnO is prepared by utilizing a zinc salt and cobalt salt mixed solution through a uniform precipitation method.
In the specific embodiment, zinc salt (such as zinc sulfate) and cobalt salt (such as cobalt nitrate) are added into water, a certain NaOH solution is added, the reaction is carried out for 2-8 hours at 40-70 ℃, centrifugal washing is carried out after the reaction is finished, and the precipitate is dried in a vacuum drying oven at 60-80 ℃ to obtain the modified nano zinc oxide. The rod-shaped nano Co doped ZnO is prepared by the method, the prepared nano ZnO with a rod-shaped structure and uniform distribution is uniform in distribution, and the overall density is proper; co as Co 2+ The form doping of the catalyst is used for entering ZnO, so that the specific surface area is increased, the lattice defect concentration of the ZnO surface is improved, the alkalinity of the surface of the desulfurizing agent is further improved, sulfide dissociation is promoted, and the desulfurizing performance is improved.
As a preferable technical scheme, the adsorbent is a molecular sieve adsorbent loaded with amine compounds.
As a preferable technical scheme, the method comprises the steps of soaking the molecular sieve in an aqueous solution (for example, 50-70%) containing amine compounds with a certain concentration on the molecular sieve loaded by a solution precipitation method for 4-8 hours, centrifuging, and fully drying the precipitate to obtain the catalyst.
As a preferred technical scheme, the amine compound is one or a mixture of more of benzylamine, benzyl ethanolamine and derivatives thereof, and as a further preferred mode, the amine compound is selected from 4-methoxybenzyl amine and/or N-benzyl ethanolamine.
As a preferable technical scheme, the molecular sieve is natural zeolite or artificial synthetic zeolite, and the natural zeolite is selected from erionite, clinoptilolite, luminescent zeolite, ferrierite and phillipsite; the synthetic zeolite is selected from 4A, 5A, 13X, ZSM-5 and metal modified X-type, Y-type, na-X-type, na-Y-type molecular sieves and the like.
The molecular sieve has the advantages of regular pore structure, large specific surface area, high local concentration of polar charges and the like, has good physical adsorption capacity, can efficiently adsorb polar molecules due to pi complexation adsorption and sulfur-metal chemical bond formation during desulfurization, and has stronger adsorptivity to inorganic sulfides such as hydrogen sulfide and the like, but weaker adsorptivity to organic sulfur. According to the invention, amine compounds such as benzylamine, benzyl ethanolamine and the like are loaded on the molecular sieve, and the amino group has better organic sulfur reaction activity and stronger interaction among organic sulfur molecules due to the electronic effect of the benzene ring, so that the organic sulfur removal efficiency is improved.
As a preferable technical scheme, the carbonate is at least one of sodium carbonate, calcium carbonate, magnesium carbonate, potassium carbonate, barium carbonate and copper carbonate, and as a preferable scheme, the carbonate is calcium carbonate.
As a preferable technical scheme, the catalyst is TiO 2 -Bi 2 O 3 The composite carrier is prepared by loading active substances by an impregnation method, wherein the active substances are one or more of vanadium pentoxide, oxalic acid and tartaric acid. In TiO 2 -Bi 2 O 3 In the composite carrier, tiO 2 60-80wt% of Bi 2 O 3 From 20 to 40% by weight, e.g. TiO 2 70wt%, bi 2 O 3 Accounting for 30 weight percent. The loaded active substance is TiO 2 -Bi 2 O 3 6-11 wt% of composite carrier. TiO (titanium dioxide) 2 -Bi 2 O 3 The composite carrier is prepared by a sol-gel method, and the preparation method specifically comprises the following steps: tetrabutyl titanate and acetic acidAfter bismuth is hydrolyzed, adding an auxiliary agent, heating in water bath to form gel, aging, drying, calcining and grinding to obtain TiO 2 -Bi 2 O 3 And (3) a composite carrier. In particular, the commercial products of Nanjing Yongsheng New Material Co., ltd can also be selected.
Compared with the prior art, the invention has the following innovation:
according to the invention, through improving the components of the desulfurizer formula, firstly, mixed solid waste powder consisting of industrial waste alkali residues and red mud is used as a main raw material, and through recycling the waste, the problem of solid waste treatment is solved, and the waste of mine resources is saved; secondly, by adding modified nano zinc oxide, the surface alkalinity of the desulfurizing agent is improved, sulfide dissociation is promoted, and the desulfurizing performance is improved; the organic sulfur removal efficiency is again improved by using an amine compound-loaded adsorbent.
Specifically, on one hand, the desulfurizer of the invention has excellent chemical sulfur removal efficiency, metal oxides such as calcium oxide, zinc oxide and the like fully chemically react with sulfur dioxide in flue gas to generate sulfite and then oxidize to generate sulfate, the modified zinc oxide also has excellent removal effect on hydrogen sulfide, and a small amount of catalyst is added to further enhance the efficiency of sulfur dioxide removal; on the other hand, the desulfurizing agent has excellent physical adsorption and sulfur removal efficiency, and the molecular sieve adsorbent can efficiently adsorb polar molecules by forming pi complex adsorption and sulfur-metal chemical bonds, and particularly has better organic sulfur reaction activity and stronger interaction among organic sulfur molecules after amine compounds such as benzylamine, benzyl ethanolamine and the like are loaded, thus improving COS and CS 2 The removal efficiency of organic sulfur such as mercaptan can greatly reduce the total sulfur content, has good chemical stability and decomposition promotion efficiency, has low cost, no corrosiveness, radioactivity and toxicity, and has obvious technical progress.
Detailed Description
Through extensive and intensive research, the inventor adopts mixed solid waste powder consisting of industrial waste alkaline residue and red mud as a main raw material through technical improvement of a desulfurizing agent raw material, and adds a metal oxide auxiliary agent, an adsorbent, a catalyst and carbonate, so that the desulfurizing agent has excellent sulfur dioxide removal performance and organic sulfur removal performance, and the total sulfur content in cement is greatly reduced.
On this basis, the present invention has been completed.
The technical solutions of the present invention will be clearly and completely described below in connection with specific embodiments, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. The present embodiment is implemented on the premise of the technical scheme of the present invention, and a detailed embodiment and a specific operation process are given, but the protection scope of the present invention is not limited to the following embodiments. All other embodiments, which can be made by those skilled in the art without the inventive effort, are intended to be within the scope of the present invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein. For example, a "range from 80 to 90" is understood to mean each and every possible number that is continuous between about 80 and about 90. Thus, even if a specific data point within the range, or even no data point within the range, is explicitly identified or refers to only a small number of specific points, it is to be understood that any and all data points within the range are considered to have been explicitly identified. As used herein, the term "about" when used to modify a numerical value means a margin of error measured within + -5% of the numerical value.
The technical scheme of the invention is further illustrated by the following specific examples, and the raw materials are all commercial products unless specifically indicated.
The raw materials used in the examples are specifically as follows:
solid waste powder a
The co-agent sodium polyacrylate was prepared according to a ratio of about 1:160, diluting the feed liquid with water, adding alkaline residue, stirring and washing for about 30min, and filtering and separating to obtain the cleaned alkaline residue;
heating the cleaned alkaline residue at about 1000 ℃ for about 4min to obtain heat-treated alkaline residue;
heating the red mud at about 940 ℃ for about 10min to obtain heat-treated red mud;
and uniformly mixing the heat-treated alkaline residues and the heat-treated red mud according to the weight ratio of 5.5:1 to obtain the solid waste powder a.
Solid waste powder b
The co-agent sodium polyacrylate was prepared according to a ratio of about 1:150, diluting the feed liquid with water, adding alkaline residue, stirring and washing for about 30min, and filtering and separating to obtain the cleaned alkaline residue;
heating the cleaned alkaline residue at about 1100 ℃ for about 5min to obtain heat-treated alkaline residue;
heating the red mud at about 900 ℃ for about 15min to obtain heat-treated red mud;
and uniformly mixing the heat treatment alkaline residue and the heat treatment red mud according to the weight ratio of 5:1 to obtain the solid waste powder b.
Solid waste powder material c
The co-agent sodium polyacrylate was prepared according to a ratio of about 1:200, diluting the feed liquid with water, adding alkaline residue, stirring and washing for about 30min, and filtering and separating to obtain the cleaned alkaline residue;
heating the cleaned alkaline residue at about 1200 ℃ for about 3min to obtain heat-treated alkaline residue;
heating the red mud at about 950 ℃ for about 10min to obtain heat-treated red mud;
and uniformly mixing the heat-treated alkaline residues and the heat-treated red mud according to the weight ratio of 6:1 to obtain the solid waste powder c.
Metal oxide auxiliary a
The preparation method is to dope 3.5 mol% of nano ZnO: zinc sulfate and cobalt nitrate are added into water, naOH solution with the mass of 20% of the water is added for reaction for 6 hours at the temperature of about 55 ℃, centrifugal washing is carried out after the reaction is finished, and the precipitate is dried in a vacuum drying oven at the temperature of 70 ℃ for 6 h.
Metal oxide auxiliary b
The specific preparation method is as follows: zinc sulfate and cobalt nitrate are added into water, naOH solution with the mass of about 20% of the water is added for reaction for 2 hours at about 70 ℃, centrifugal washing is carried out after the reaction is finished, and the precipitate is dried in a vacuum drying oven at 60 ℃ for 5 h.
Metal oxide auxiliary c
The specific preparation method is as follows: zinc sulfate and cobalt nitrate are added into water, naOH solution with the mass of about 20% of the water is added for reaction for 8 hours at about 40 ℃, centrifugal washing is carried out after the reaction is finished, and the precipitate is dried in a vacuum drying oven at 80 ℃ for 3 h.
Adsorbent a
The 5A molecular sieve loaded with 4-methoxybenzylamine is prepared by soaking the 5A molecular sieve in an aqueous solution containing 60% of amine compounds for 6 hours, centrifuging, and fully drying the precipitate.
Adsorbent b
The erionite loaded with 4-methoxybenzylamine is prepared by soaking erionite in water solution containing 70% concentration amine compound for 4 hr, centrifuging, and drying the precipitate.
Adsorbent c
The ZSM-5 is loaded with N-benzyl ethanolamine, and is prepared by soaking ZSM-5 in an aqueous solution containing 50% concentration of amine compound for 8 hours, centrifuging, and fully drying the precipitate.
Adsorbent d
The Y-type molecular sieve loaded with N-benzyl ethanolamine is prepared by soaking the Y-type molecular sieve in an aqueous solution containing 55% concentration amine compound for 7 hours, centrifuging, and fully drying the precipitate.
Catalyst a
Is TiO 2 -Bi 2 O 3 The composite carrier is loaded with vanadium pentoxide active substances and TiO by an impregnation method 2 70wt%, bi 2 O 3 30wt% of the catalyst is prepared by a sol-gel method, and the preparation method specifically comprises the following steps: and (3) hydrolyzing tetrabutyl titanate and bismuth acetate, adding vanadium pentoxide into the mixture, heating the mixture in a water bath to form gel, and aging, drying, calcining and grinding the gel to obtain the product.
Carbonate a
Specifically, calcium carbonate powder of 400 mesh or less is used.
The specific preparation method of the desulfurizing agent in the embodiment comprises the following steps: after preparing all the raw materials, uniformly mixing the raw materials in a mixing tank, and grinding the mixture to 200-400 meshes to obtain the product with the appearance of off-white powder. Examples 1-8 the raw material formulation dosage compositions are shown in Table 1.
Example 1
The specific raw materials are as follows: the specific amounts of the solid waste powder a, the metal oxide auxiliary agent a, the adsorbent a, the catalyst a and the carbonate a are shown in table 1.
Example 2
The specific raw materials are as follows: the specific amounts of the solid waste powder a, the metal oxide auxiliary agent b, the adsorbent a, the catalyst a and the carbonate a are shown in table 1.
Example 3
The specific raw materials are as follows: the specific amounts of the solid waste powder b, the metal oxide auxiliary agent b, the adsorbent b, the catalyst a and the carbonate a are shown in table 1.
Example 4
The specific raw materials are as follows: the specific amounts of the solid waste powder b, the metal oxide auxiliary agent c, the adsorbent b, the catalyst a and the carbonate a are shown in table 1.
Example 5
The specific raw materials are as follows: the specific amounts of the solid waste powder c, the metal oxide auxiliary agent c, the adsorbent c, the catalyst a and the carbonate a are shown in table 1.
Example 6
The specific raw materials are as follows: the specific amounts of the solid waste powder c, the metal oxide auxiliary agent c, the adsorbent d, the catalyst a and the carbonate a are shown in table 1.
Example 7
The specific raw materials are as follows: the specific amounts of the solid waste powder c, the metal oxide auxiliary agent a, the adsorbent d, the catalyst a and the carbonate a are shown in table 1.
Example 8
The specific raw materials are as follows: the specific amounts of the solid waste powder a, the metal oxide auxiliary agent a, the adsorbent d, the catalyst a and the carbonate a are shown in table 1.
Table 1 examples 1-8 raw material formulations were used in parts by weight
To investigate the effect of different raw material compositions on the results, the present invention also provides the following comparative examples.
Comparative example 1
With reference to example 1, the raw materials are only solid waste powder a and carbonate a, and no metal oxide auxiliary agent a, adsorbent a and catalyst a are added.
Comparative example 2
With reference to example 1, the starting material was free of adsorbent a.
Comparative example 3
With reference to example 1, the adsorbent in the feed was replaced with a 5A molecular sieve that was not loaded with 4-methoxybenzylamine.
Comparative example 4
With reference to example 1, no metal oxide promoter a was added to the starting material.
Comparative example 5
Referring to example 1, the metal oxide promoter a in the raw material was replaced with a common nano zinc oxide without Co doping.
Comparative example 6
With reference to example 1, red mud is not added to the solid waste powder a in the raw material.
Desulfurization effect Performance test
The desulfurizing agents obtained in examples 1 to 8 and comparative examples 1 to 6 were placed in a fixed bed evaluation apparatus under a test flue gas condition of 1m 3 The usage amount of the desulfurizing agent is 25kg/min, and the raw material gas with the following composition is adopted: SO (SO) 2 208 mg/Nm 3 Total organic sulfur 201mg/Nm 3 (wherein COS 49%, methyl mercaptan 24%, ethyl mercaptan 27%), H 2 S is 126 mg/Nm 3 The specific contents of the treated sulfur-containing flue gas are shown in Table 2.
TABLE 2 sulfur-containing flue gas content after desulfurization (mg/Nm) 3 )
As is clear from Table 2, the desulfurizing agent of the present invention has excellent desulfurizing effect and can greatly reduce SO 2 H 2 S content, and has excellent removal effect on organic sulfur. The effects in the comparative examples are all worse than those in the examples.
Specific application Effect verification
The desulfurizing agent of example 1 of the present invention was specifically applied to a cement plant. The cement plant is a 4000t/d novel dry-method cement clinker production line, mainly produces 425R and 325R silicate cement, and produces 160 ten thousand tons of clinker and 200 ten thousand tons of cement each year. The limestone used in the cement plant is high-sulfur limestone, the sulfur content is 0.1-0.2%, and SO is contained in the flue gas of the cement kiln 2 The discharge concentration exceeds the standard (80 mg/Nm in stopping grinding) 3 As much as 20mg/Nm at the time of grinding 3 Multiple) after the desulfurizing agent of example 1, SO was contained in the flue gas of the cement kiln 2 The discharge concentration was reduced to 25mg/Nm 3 Completely meets the emission standard.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (10)
1. The flue gas desulfurizing agent is characterized by comprising the following raw materials in parts by mass: 80-90 parts of solid waste powder, 20-25 parts of metal oxide auxiliary agent, 10-15 parts of adsorbent, 3-5 parts of catalyst and 10-15 parts of carbonate, wherein the adsorbent is loaded with amine compounds.
2. The flue gas desulfurization agent according to claim 1, wherein the solid waste powder comprises alkaline residue and red mud in a weight ratio of 5-6:1.
3. The flue gas desulfurization agent of claim 1, wherein the metal oxide additive is modified nano zinc oxide.
4. The flue gas desulfurization agent according to claim 3, wherein the modified nano zinc oxide is Co-doped nano ZnO, and the Co doping amount is 2-5% of the molar mass of the nano ZnO.
5. A flue gas desulfurization agent according to claim 1, wherein the adsorbent is a molecular sieve adsorbent loaded with an amine compound.
6. A flue gas desulfurization agent according to claim 5, wherein the amine compound is one or more of benzylamine, benzylethanolamine and derivatives thereof; the molecular sieve is natural zeolite or artificial zeolite.
7. The flue gas desulfurization agent according to claim 1, wherein the carbonate is at least one of sodium carbonate, calcium carbonate, magnesium carbonate, potassium carbonate, barium carbonate, and copper carbonate.
8. A flue gas desulfurization agent according to claim 1, wherein the catalyst is TiO 2 -Bi 2 O 3 The composite carrier is prepared by loading active substances by an impregnation method, wherein the active substances are one or more of vanadium pentoxide, oxalic acid and tartaric acid.
9. The method for preparing a flue gas desulfurization agent according to claim 1, comprising the steps of:
(1) The following raw materials are prepared according to the formula: 80-90 parts of solid waste powder, 20-25 parts of metal oxide auxiliary agent, 10-15 parts of adsorbent, 3-5 parts of catalyst and 10-15 parts of carbonate;
(2) And uniformly mixing the raw materials, and grinding the mixture to powder of 200-400 meshes to obtain the composite material.
10. Use of a flue gas desulfurization agent according to claim 1, as a solid desulfurization agent for the desulfurization of cement.
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