CN115814580B - Desulfurizing agent, preparation method and application thereof - Google Patents
Desulfurizing agent, preparation method and application thereof Download PDFInfo
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- CN115814580B CN115814580B CN202211321486.XA CN202211321486A CN115814580B CN 115814580 B CN115814580 B CN 115814580B CN 202211321486 A CN202211321486 A CN 202211321486A CN 115814580 B CN115814580 B CN 115814580B
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- desulfurizing agent
- carbide slag
- hydrogen peroxide
- slurry
- flue gas
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- 230000003009 desulfurizing effect Effects 0.000 title claims abstract description 103
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 148
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 102
- 239000002893 slag Substances 0.000 claims abstract description 102
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 43
- 230000023556 desulfurization Effects 0.000 claims abstract description 43
- 239000000853 adhesive Substances 0.000 claims abstract description 4
- 230000001070 adhesive effect Effects 0.000 claims abstract description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 38
- 239000003546 flue gas Substances 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 35
- 239000002002 slurry Substances 0.000 claims description 32
- 238000002156 mixing Methods 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 24
- 239000004343 Calcium peroxide Substances 0.000 claims description 22
- LHJQIRIGXXHNLA-UHFFFAOYSA-N calcium peroxide Chemical compound [Ca+2].[O-][O-] LHJQIRIGXXHNLA-UHFFFAOYSA-N 0.000 claims description 22
- 235000019402 calcium peroxide Nutrition 0.000 claims description 22
- 239000012752 auxiliary agent Substances 0.000 claims description 20
- 239000011790 ferrous sulphate Substances 0.000 claims description 20
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 20
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 20
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 14
- 239000011230 binding agent Substances 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000005995 Aluminium silicate Substances 0.000 claims description 9
- 235000012211 aluminium silicate Nutrition 0.000 claims description 9
- 239000000440 bentonite Substances 0.000 claims description 9
- 229910000278 bentonite Inorganic materials 0.000 claims description 9
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 9
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 9
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 6
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 6
- 229960000892 attapulgite Drugs 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 229910052625 palygorskite Inorganic materials 0.000 claims description 5
- 239000011265 semifinished product Substances 0.000 claims description 5
- 239000000919 ceramic Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 4
- 238000010248 power generation Methods 0.000 claims description 4
- 238000004537 pulping Methods 0.000 claims description 4
- 239000004568 cement Substances 0.000 claims description 3
- 239000010440 gypsum Substances 0.000 claims description 3
- 229910052602 gypsum Inorganic materials 0.000 claims description 3
- 241000219793 Trifolium Species 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 26
- 239000011148 porous material Substances 0.000 abstract description 5
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 239000000706 filtrate Substances 0.000 description 19
- 238000007254 oxidation reaction Methods 0.000 description 17
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 16
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 12
- 230000003647 oxidation Effects 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 238000000227 grinding Methods 0.000 description 9
- 230000001590 oxidative effect Effects 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 238000000465 moulding Methods 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- -1 iron ions Chemical class 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000009827 uniform distribution Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 229910001447 ferric ion Inorganic materials 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 239000005997 Calcium carbide Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 206010011224 Cough Diseases 0.000 description 1
- 208000000059 Dyspnea Diseases 0.000 description 1
- 206010013975 Dyspnoeas Diseases 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate 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
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- JGIATAMCQXIDNZ-UHFFFAOYSA-N calcium sulfide Chemical compound [Ca]=S JGIATAMCQXIDNZ-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000005980 lung dysfunction Effects 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Landscapes
- Treating Waste Gases (AREA)
Abstract
The invention provides a carbide slag modified desulfurizing agent composition, a desulfurizing agent, a preparation method and application thereof. The carbide slag modified desulfurizer composition comprises the following components in parts by weight: 60-90 parts of carbide slag; 50-300 parts of hydrogen peroxide, wherein the concentration of hydrogen peroxide in the hydrogen peroxide is between 10% and 50%; 10-30 parts of adhesive; 180-720 parts of water. According to the invention, the hydrogen peroxide is used for modifying the carbide slag, the specific surface area and the effective pore volume of the carbide slag are increased after modification, and the desulfurization performance of the desulfurizing agent can be improved.
Description
Technical Field
The invention relates to the fields of chemical industry, energy sources, environmental protection and the like, in particular to a carbide slag modified desulfurizing agent composition, a desulfurizing agent, a preparation method and application thereof.
Background
SO 2 Is one of main pollutants of atmospheric pollutants, mainly derived from the utilization of coal, but the coal cannot be completely replaced in a short time, SO that SO is controlled at present 2 The emission adopts methods such as coal desulfurization, in-furnace desulfurization and the like, but the flue gas desulfurization method is a method which is fast in progress and obvious in effect at present, has low investment and simple operation and running, and is also the most widely applied desulfurization method at present.
Flue gas desulfurization is also divided into two types: one is wet flue gas desulfurization and the other is called dry flue gas desulfurization. The dry flue gas desulfurization is characterized in that: the desulfurization efficiency is higher and stable, the operation elasticity is good, the operation and control are easy, the desulfurization process is simple, and the management is easy; the dry flue gas desulfurization and dust removal can be completed at the same time, equipment pipelines are not easy to corrode, no wastewater is discharged, and the troubles of equipment corrosion and wastewater treatment are reduced; the flue gas temperature drop in the purification process is small, and the waste heat is easy to recover and the high-altitude emission is easy. In the dry flue gas desulfurization technology, a dry desulfurizing agent is the most important research and development direction.
The carbide slag contains carbide slag and percolate with certain water content, and also contains sulfide, phosphide and other toxic and harmful matters, and has strong alkalinity. The main components of the carbide slag are calcium hydroxide (the mass fraction is 90.1%), silicon oxide (the mass fraction is 3.5%), aluminum oxide (the mass fraction is 2.5%) and a small amount of impurities such as calcium carbonate, ferric oxide, magnesium oxide, titanium dioxide, carbon slag, calcium sulfide and the like. The carbide slag appears grey with a sharp smell. At present, researches on preparing desulfurizing agents by using carbide slag have been reported, and the desulfurizing agents are applied to wet desulfurization and dry desulfurization.
In the process of realizing the invention, the applicant finds that the traditional desulfurization product using carbide slag as the main raw material has lower desulfurization efficiency, can not realize the long-term aim of treating waste by waste, and can not meet the requirement of actual production.
Disclosure of Invention
First, the technical problem to be solved
In view of this, the present invention is intended to partially solve the problem of low desulfurization efficiency.
(II) technical scheme
In order to achieve the above object, according to a first aspect of the present invention, there is provided a desulfurizing agent composition. The carbide slag modified desulfurizer composition comprises the following components in parts by weight: 60-90 parts of carbide slag; 50-300 parts of hydrogen peroxide, wherein the concentration of hydrogen peroxide in the hydrogen peroxide is between 10% and 50%; 10-30 parts of adhesive; 180-720 parts of water.
In some embodiments of the invention, further comprising: 5-20 parts of an auxiliary agent; wherein the auxiliary agent comprises one or more of the following materials: ferric sulfate, ferrous sulfate, ferric acetate, ferric chloride, and ferric nitrate.
In some embodiments of the invention, the binder comprises one or more of the following materials: cement, gypsum, kaolin, attapulgite, bentonite and diatomite.
In order to achieve the above object, according to a second aspect of the present invention, there is also provided a desulfurizing agent production method using the above desulfurizing agent composition. The preparation method of the desulfurizing agent comprises the following steps:
step A, mixing carbide slag with water for pulping to obtain carbide slag slurry;
step B, mixing and reacting carbide slag slurry with hydrogen peroxide to obtain calcium peroxide slurry;
step C, adding a binder into the calcium peroxide slurry to obtain a desulfurizing agent wet material;
step D, forming the wet desulfurizing agent into a semi-finished desulfurizing agent product;
and E, drying the semi-finished product of the desulfurizing agent to obtain a finished product of the desulfurizing agent.
In some embodiments of the invention, step B comprises: mixing carbide slag slurry and hydrogen peroxide by adopting a parallel flow process in a low-temperature environment of-20-0 ℃, and controlling the mixing ratio of the carbide slag slurry and the hydrogen peroxide by the flow rate.
In some embodiments of the invention, the desulfurizing agent composition further comprises: 5-20 parts of an auxiliary agent; wherein the auxiliary agent comprises one or more of the following materials: ferric sulfate, ferrous sulfate, ferric acetate, ferric chloride, and ferric nitrate.
In some embodiments of the invention, step C comprises: and adding an auxiliary agent and a binder into the calcium peroxide slurry to obtain the desulfurizer wet material.
In some embodiments of the invention, in step a, the weight ratio of carbide slag to water is between 1:3 and 1:8; in the step B, the weight ratio of the carbide slag to the hydrogen peroxide is between 1:0.5 and 1:3; in the step C, the weight ratio of the carbide slag, the auxiliary agent and the binder is as follows: 5:1:4 to 8:1:1.
In some embodiments of the invention, step E comprises: drying the semi-finished product of the desulfurizing agent at 50-200 ℃ for 1-8 hours to obtain the finished product of the desulfurizing agent.
In order to achieve the above object, according to a third aspect of the present invention, there is also provided a desulfurizing agent produced by the above desulfurizing agent production method. Wherein the desulfurizer is cylindrical, clover-shaped or plum blossom-shaped.
In order to achieve the above object, according to a fourth aspect of the present invention, there is also provided a desulfurizing agent composition as above, use of a desulfurizing agent in low temperature flue gas desulfurization. Wherein the low-temperature flue gas is low-temperature heating furnace flue gas, ceramic flue gas and garbage power generation tail gas.
(III) beneficial effects
As can be seen from the technical scheme, the invention has at least one of the following advantages:
(1) Hydrogen peroxide is a strong oxidizing liquid, and can oxidize carbide slag to generate calcium peroxide. Calcium peroxide has strong oxidizing property and is compatible with SO 2 Reacting to obtain 2CaO 2 +2SO 2 ＝2CaSO 3 +O 2 ，CaO 2 +SO 2 ＝CaSO 4 The method comprises the steps of carrying out a first treatment on the surface of the And the specific surface area and the effective pore volume of the carbide slag are increased after modification, so that the desulfurization performance of the desulfurizing agent can be improved.
In addition, the calcium peroxide has the characteristic of slowly releasing oxygen in a wet and hot flue gas environment, and the calcium peroxide is 2CaO 2 +2H 2 O＝2Ca(OH) 2 +O 2 The pore volume of the desulfurizing agent is increased, the defect is obvious, more active components can be exposed, and the desulfurizing performance is improved. More important is that under severe flue gas conditions, for example: under the environment of low nitrogen oxide and no nitrogen oxide, the existence of strong oxidant calcium peroxide improves SO 2 To SO 3 The conversion efficiency is improved, and the desulfurization efficiency is enhanced.
(2) Compared with other oxidation modes, for example, oxygen and ozone are added into water to oxidize the carbide slag, the oxidation reaction efficiency is extremely low due to extremely low solubility of the oxygen or the ozone in the water, and the oxidation effect on the carbide slag is limited. In the invention, the hydrogen peroxide is obtained by dissolving hydrogen peroxide in water, and the concentration can be adjusted. The parallel flow process is adopted, so that the oxidation of carbide slag is more thorough, and the effect is better.
(3) The consumption of the carbide slag slurry and the hydrogen peroxide is calculated in advance, different flow rates are controlled respectively, and liquid-liquid phase contact is carried out through a parallel flow process, so that the mixing reaction of the carbide slag slurry and the hydrogen peroxide is realized, the consumption of the hydrogen peroxide is minimized, the optimal effect of oxidation is achieved, the raw material cost is saved, and the energy consumption is reduced.
(4) The introduction of the soluble ferric salt auxiliary agent is beneficial to the uniform distribution of the iron ions, and meanwhile, the iron ions have catalytic oxidation effect, so that the desulfurization efficiency can be improved.
(5) The desulfurizer of the invention introduces industrial byproduct carbide slag, has the advantages of cheap and easily obtained raw materials, simple preparation process, high desulfurization efficiency, and the used waste agent can be recycled, thus not causing harm to the environment, and being energy-saving and environment-friendly.
Drawings
FIG. 1 is a flow chart of a method for preparing a desulfurizing agent according to an embodiment of the present invention.
Detailed Description
The invention utilizes hydrogen peroxide to modify carbide slag to generate SO in the flue gas by calcium peroxide 2 And the desulfurization efficiency of the desulfurizing agent can be effectively improved by removing.
The present invention will be further described in detail below with reference to specific embodiments and with reference to the accompanying drawings, in order to make the objects, technical solutions and advantages of the present invention more apparent.
According to a first aspect of the present invention, there is provided a desulfurizing agent composition. The desulfurizer composition comprises the following components in parts by weight: 60-90 parts of carbide slag; hydrogen peroxide, 50-300 parts; 10-30 parts of adhesive; 5-20 parts of an auxiliary agent; a suitable amount of water.
Wherein the auxiliary agent comprises one or more of the following materials: ferric sulfate, ferrous sulfate, ferric acetate, ferric chloride, and ferric nitrate. It can be seen that iron ions are introduced into the auxiliary agent. The introduction of the soluble ferric salt auxiliary agent is beneficial to the uniform distribution of the iron ions, and meanwhile, the iron ions have catalytic oxidation effect, so that the desulfurization efficiency can be improved.
Wherein the binder comprises one or more of the following materials: cement, gypsum, kaolin, attapulgite, bentonite and diatomite. Of course, the above is merely an example, and other binder materials commonly used in the art may be used in the desulfurizing agent composition of the present invention, and will not be described herein.
Wherein, the water is used for mixing carbide slag to prepare carbide slag slurry, the dosage of which can be adjusted according to the need, and the dosage is not strictly limited here. The reference amount of water is 180-720 parts by weight.
According to a second aspect of the present invention, there is also provided a process for preparing a desulfurizing agent using the above desulfurizing agent composition. FIG. 1 is a flow chart of a method for preparing a desulfurizing agent according to an embodiment of the present invention. As shown in fig. 1, the desulfurizing agent preparation method of this embodiment includes:
step A, mixing carbide slag with water for pulping to obtain carbide slag slurry;
specifically, the carbide slag and water are mixed according to the weight ratio of 1:3-1:8 for pulping.
Step B, mixing and reacting carbide slag slurry with hydrogen peroxide to obtain calcium peroxide slurry;
specifically, hydrogen peroxide with the concentration of 30% is adopted, the carbide slag slurry and the hydrogen peroxide are mixed by adopting a parallel flow process in a low-temperature environment of-20-0 ℃, and the mixing ratio of the carbide slag slurry and the hydrogen peroxide is controlled by the flow rate. The calcium carbide slag and the hydrogen peroxide are fully stirred according to the weight ratio of 1:0.5-1:3, and uniform calcium peroxide slurry is obtained.
The hydrogen peroxide is easy to volatilize and decompose at normal temperature to reduce the oxidability, so that the step B is carried out in a low-temperature environment of-20-0 ℃, the volatilization and decomposition of the hydrogen peroxide can be reduced, and the reaction of the effective components of the hydrogen peroxide and the carbide slag can be kept. In addition, although 30% hydrogen peroxide is taken as an example for illustration, those skilled in the art will appreciate that the present invention can be implemented with hydrogen peroxide having a concentration of 10% to 50%.
Step C, adding an auxiliary agent and a binder into the calcium peroxide slurry to obtain a desulfurizing agent wet material;
in this example, the auxiliary agent is added to the calcium peroxide slurry first, followed by the binder. Weight ratio of carbide slag/auxiliary agent/binder: 5:1:4 to 8:1:1. During the addition of the auxiliary agent and the binder, attention should be paid to the enhanced stirring to make the reaction complete. And C, reserving the wet desulfurizing agent filtrate obtained in the step for strip extrusion for standby.
Step D, forming the wet desulfurizing agent into a semi-finished desulfurizing agent product;
in the step, the mixture is extruded and molded on a molding machine to obtain cylindrical or clover-shaped materials. It will be appreciated by those skilled in the art that in addition to the above shapes, the wet desulfurizing agent may be kneaded into other desired shapes by molding equipment commonly used in the art, and will not be described in detail herein.
And E, drying the semi-finished product of the desulfurizing agent to obtain a finished product of the desulfurizing agent.
In this step, the semi-finished product of the desulfurizing agent is dried at 50-200 ℃ for 1-8 hours, preferably at 100-150 ℃ for 2-5 hours, and finally the required finished product of the desulfurizing agent is obtained.
According to a third aspect of the present invention, there is also provided a desulfurizing agent produced by the above desulfurizing agent production method.
According to a fourth aspect of the present invention there is also provided a desulfurizing agent composition as described above, the use of a desulfurizing agent in low temperature flue gas desulfurization. Wherein the low-temperature flue gas is low-temperature heating furnace flue gas, ceramic flue gas and garbage power generation tail gas.
Regarding the above four aspects of the present invention, the following five points need to be explained:
1. action of hydrogen peroxide modified carbide slag
The hydrogen peroxide is a strong oxidizing liquid, and the volatilization and decomposition of the hydrogen peroxide can be reduced in a low-temperature environment; oxidizing carbide slag to generate calcium peroxide. Calcium peroxide has strong oxidizing property and is compatible with SO 2 Reacting to obtain 2CaO 2 +2SO 2 ＝2CaSO 3 +O 2 ，CaO 2 +SO 2 ＝CaSO 4 The method comprises the steps of carrying out a first treatment on the surface of the And the specific surface area and the effective pore volume of the carbide slag are increased after modification, so that the desulfurization performance of the desulfurizing agent can be improved.
Under the wet and hot flue gas environment, the calcium peroxide has the characteristic of slowly releasing oxygen, and 2CaO 2 +2H 2 O＝2Ca(OH) 2 +O 2 The pore volume of the desulfurizing agent is increased, the defect is obvious, more active components can be exposed, and the desulfurizing performance is improved. More important is that under severe flue gas conditions, for example: under the environment of low nitrogen oxide and no nitrogen oxide, the existence of strong oxidant calcium peroxide improves SO 2 To SO 3 The conversion efficiency is improved, and the desulfurization efficiency is enhanced.
2. Advantages over other oxidation modes
Reference 1 (CN 101642674B) provides a wet flue gas desulfurization process for pretreatment of carbide slag slurry, the desulfurizing agent is modified carbide slag slurry: the concrete steps are that manganese sulfate is added into carbide slag slurry, and then air is introduced for oxidation, thus obtaining evenly distributed Mn with oxidation activity 4+ Is prepared from carbide slag slurry;
reference 2 (CN 101816891B) provides an ozone wet flue gas desulfurization process for pretreating carbide slag, which uses carbide slag as a desulfurizing agent to perform wet desulfurization on flue gas, introduces a mixed gas of ozone and oxygen in the process of carbide slag slagging, performs oxidation reaction, oxidizes reducing substances in the carbide slag, and uses the carbide slag after the oxidation reaction as a desulfurizing agent for wet desulfurization of flue gas.
For the solutions proposed in references 1 and 2, oxygen or ozone is added to water to oxidize the carbide slag, and the oxidation reaction efficiency is extremely low and the oxidation effect on the carbide slag is limited because the solubility of oxygen or ozone in water is extremely low and the stability is extremely poor. And oxygen or ozone is continuously introduced for a long time, so that the process is not easy to control, the cost is high, and the popularization in industry is difficult. Meanwhile, for the scheme proposed in reference 2, ozone which is not dissolved in the carbide slag melting process overflows from the reaction vessel, causing environmental pollution, and when the concentration reaches a certain level, cough, dyspnea and pulmonary dysfunction can be caused, life is seriously endangered, and how to treat the ozone is a very troublesome problem.
In the invention, the stable calcium peroxide product can be generated by utilizing the carbide slag modified by hydrogen peroxide only by a proper amount of hydrogen peroxide, so that higher desulfurization efficiency is achieved; has stronger oxidizing property than manganese ions and stable oxidizing efficiency than ozone, and meanwhile, the decomposition product of hydrogen peroxide is H 2 O and O 2 The method is environment-friendly and has stronger adaptability. In addition, the hydrogen peroxide is obtained by dissolving hydrogen peroxide in water, the concentration can be adjusted, the reaction is sufficient, and the control is convenient.
3. Parallel flow process
In the invention, in order to improve the utilization efficiency of hydrogen peroxide, a parallel flow process is adopted to enable carbide slag slurry to react with hydrogen peroxide. Specifically, the consumption of the carbide slag slurry and the hydrogen peroxide are calculated in advance, different flow rates are controlled respectively, and liquid-liquid phase contact is carried out through a parallel flow process, so that the mixing reaction of the carbide slag slurry and the hydrogen peroxide is realized, the consumption of the hydrogen peroxide is minimized, the optimal effect of oxidization is achieved, the raw material cost is saved, and the energy consumption is reduced.
4. Soluble ferric salt auxiliary agent
In the invention, the soluble ferric salt auxiliary agent is introduced, so that the uniform distribution of the ferric ions is facilitated, and meanwhile, the ferric ions have catalytic oxidation effect, so that the desulfurization efficiency can be improved.
5. Efficiency, cost and product reuse
1. Low cost
The invention introduces the industrial by-product carbide slag, and has the advantages of low-cost and easily obtained raw materials and low implementation cost.
2. No toxicity, harm and pollution
The introduced hydrogen peroxide not only generates the effective components of the desulfurizing agent, but also generates no toxic and harmful products. In addition, unreacted hydrogen peroxide can be reused, and even if a small amount volatilizes into the air, the light can be quickly decomposed into water and oxygen, so that the human body is not damaged.
3. High efficiency and wide adaptability
The desulfurizing agent provided by the invention has the advantages of low cost, simple preparation process and high desulfurizing efficiency of more than 95%, and can be used for desulfurizing flue gas with high water content at medium and low temperatures in a dry method and a semi-dry method, such as flue gas of a low-temperature heating furnace, ceramic flue gas, waste power generation tail gas and other working conditions.
The present invention is described below in conjunction with specific comparative examples and examples, which will be directed to various aspects of the invention, including desulfurizing agent compositions, desulfurizing agents, desulfurizing agent preparation methods, applications, and the like.
Comparative example 1
The desulfurizing agent composition comprises: 90g of carbide slag, 10g of kaolin and 40g of water
The preparation method of the desulfurizing agent comprises the following steps: and (3) uniformly mixing carbide slag and kaolin, adding water, kneading and extruding strips, and drying to obtain a sample of comparative example 1.
Comparative example 2
The desulfurizing agent composition comprises: 80g of carbide slag, 10g of ferric sulfate, 10g of diatomite and 40g of water
The preparation method of the desulfurizing agent comprises the following steps: and (3) uniformly mixing carbide slag, ferric sulfate and diatomite, adding water, kneading and extruding strips, and drying to obtain a sample of comparative example 2.
Comparative example 3
The desulfurizing agent composition comprises: 80g of carbide slag, 10g of ferrous sulfate, 10g of kaolin and 300g of water are introduced into the reactor for 1h of ozone (about 1 g).
The preparation method of the desulfurizing agent comprises the following steps: preparing carbide slag and water into a proportion of 1:4, introducing ozone, and filtering to obtain wet cakes and filtrate; drying the wet cake, grinding, uniformly mixing with ferrous sulfate and kaolin, adding a proper amount of filtrate, extruding strips for molding, and drying to obtain a sample of comparative example 3.
Comparative example 4
The desulfurizing agent composition comprises: 80g of carbide slag, 2h of ozone (about 2 g), 10g of ferrous sulfate, 10g of kieselguhr and 300g of water are introduced.
The preparation method of the desulfurizing agent comprises the following steps: preparing carbide slag and water into a proportion of 1:4, introducing ozone, and filtering to obtain wet cakes and filtrate; drying the wet cake, grinding, uniformly mixing with ferrous sulfate and diatomite, adding a proper amount of filtrate, extruding strips for molding, and drying to obtain a sample of comparative example 4.
Example 1
The desulfurizing agent composition comprises: 80g of carbide slag, 50g of 30% (hydrogen peroxide concentration) hydrogen peroxide, 10g of ferrous sulfate, 10g of bentonite and 300g of water.
The preparation method of the desulfurizing agent comprises the following steps: preparing carbide slag and water into a ratio of 1:4, adding hydrogen peroxide into the carbide slag at the temperature of minus 10 ℃ by adopting a parallel flow process, and filtering to obtain wet cakes and filtrate; drying the wet cake, grinding, uniformly mixing with ferrous sulfate and bentonite, adding a proper amount of filtrate, extruding to form strips, and drying at 150 ℃ for 3 hours to obtain a sample of the example 1.
Example 2
The desulfurizing agent composition comprises: 80g of carbide slag, 75g of 30% hydrogen peroxide, 10g of ferrous sulfate, 10g of attapulgite and 300g of water.
The preparation method of the desulfurizing agent comprises the following steps: preparing carbide slag and water into a ratio of 1:4, adding hydrogen peroxide into the carbide slag at the temperature of minus 10 ℃ by adopting a parallel flow process, and filtering to obtain wet cakes and filtrate; drying the wet cake, grinding, uniformly mixing with ferrous sulfate and attapulgite, adding a proper amount of filtrate, extruding to form strips, and drying at 150 ℃ for 3 hours to obtain a sample of the example 2.
Example 3
The desulfurizing agent composition comprises: 80g of carbide slag, 100g of 30% hydrogen peroxide, 10g of ferrous sulfate, 10g of bentonite and 300g of water.
The preparation method of the desulfurizing agent comprises the following steps: preparing carbide slag and water into a ratio of 1:4, adding hydrogen peroxide into the carbide slag at the temperature of minus 10 ℃ by adopting a parallel flow process, and filtering to obtain wet cakes and filtrate; drying the wet cake, grinding, uniformly mixing with ferrous sulfate and bentonite, adding a proper amount of filtrate, extruding strips for molding, and drying to obtain the sample of the example 3.
Example 4
The desulfurizing agent composition comprises: 80g of carbide slag, 100g of 30% hydrogen peroxide, 10g of ferrous sulfate, 10g of diatomite and 300g of water.
The preparation method of the desulfurizing agent comprises the following steps: mixing carbide slag and water into a ratio of 1:4, stirring with a proper amount of hydrogen peroxide, and filtering to obtain wet cakes and filtrate; drying the wet cake, grinding, uniformly mixing with ferrous sulfate and diatomite, adding a proper amount of filtrate, extruding strips for molding, and drying to obtain the sample of the example 4.
Example 5
The desulfurizing agent composition comprises: 80g of carbide slag, 50g of 30% hydrogen peroxide, 10g of ferric chloride, 10g of bentonite and 300g of water.
The preparation method of the desulfurizing agent comprises the following steps: preparing carbide slag and water into a ratio of 1:4, adding hydrogen peroxide into the carbide slag at the temperature of minus 10 ℃ by adopting a parallel flow process, and filtering to obtain wet cakes and filtrate; drying the wet cake, grinding, uniformly mixing with ferric chloride and bentonite, adding a proper amount of filtrate, extruding to form strips, and drying at 150 ℃ for 3 hours to obtain a sample of the example 5.
Example 6
The desulfurizing agent composition comprises: 80g of carbide slag, 50g of hydrogen peroxide with the concentration of hydrogen peroxide, 10g of ferrous sulfate, 10g of kaolin and 300g of water.
The preparation method of the desulfurizing agent comprises the following steps: preparing carbide slag and water into a ratio of 1:4, adding hydrogen peroxide into the carbide slag at the temperature of minus 10 ℃ by adopting a parallel flow process, and filtering to obtain wet cakes and filtrate; drying the wet cake, grinding, mixing with ferrous sulfate and kaolin uniformly, adding appropriate amount of filtrate, extruding to form strips, and drying at 150deg.C for 3 hr to obtain sample of example 6.
Example 7
The desulfurizing agent composition comprises: 80g of carbide slag, 50g of 30% (hydrogen peroxide concentration) hydrogen peroxide, 10g of ferrous sulfate, 10g of diatomite and 300g of water.
The preparation method of the desulfurizing agent comprises the following steps: preparing carbide slag and water into a ratio of 1:4, adding hydrogen peroxide into the carbide slag at the temperature of 0 ℃ by adopting a parallel flow process, and filtering to obtain wet cakes and filtrate; drying the wet cake, grinding, mixing with ferrous sulfate and diatomite, adding appropriate amount of filtrate, extruding, and drying at 150deg.C for 3 hr to obtain sample of example 7.
The performance of each comparative example, example of the present invention is tested as follows. Performance index of flue gas desulfurizing agent: specific surface area, desulfurization efficiency. The detection method of each index is specifically as follows:
(1) The specific surface area detection method refers to: GB/T19587-2017
(2) The calculation method of the sulfur capacity is as follows:
desulfurizing agent sulfur capacity=m 1 ×n/m×100％
m: the mass of the desulfurizing agent, g;
m 1 : the mass of the desulfurizing agent after passing through sulfur-containing flue gas, g;
n: SO after sulfur-containing flue gas is passed through desulfurizing agent 2 Content,%.
SO in flue gas 2 The concentration is monitored on line by a flue gas analyzer, and SO is input 2 The concentration was 2000ppm and the outlet 100ppm (i.e., desulfurization efficiency 95%) was the end point of the end of the experiment.
The test results are shown in Table 1.
TABLE 1 Performance test data for flue gas desulfurization agents
Remarks:
1. the air quantity of the laboratory ozone generator is fixed, the common unit is g/h or mg/h, and the maximum solubility in 100ml of water is 49.4ml at 20 ℃;
2. pure hydrogen peroxide is light blue viscous liquid, can be mixed with water in any proportion, and is commonly called hydrogen peroxide. In the series of experiments, due to the limitation of the conditions, only hydrogen peroxide with the concentration of 10 percent and 30 percent is adopted for experiments, but the technical personnel in the field can realize the invention by adopting the hydrogen peroxide with the concentration of 10 percent to 50 percent.
According to the invention, the effect of modifying the carbide slag by hydrogen peroxide is obviously better than that of the desulfurization agent by adopting oxidation modes such as ozone and the like, so that the desulfurization effect of the desulfurization agent can be effectively improved.
Thus, embodiments of the present invention have been described in detail with reference to the accompanying drawings. The present invention should be clearly recognized by those skilled in the art in light of the above description.
In conclusion, the invention utilizes hydrogen peroxide to modify carbide slag, improves oxidation efficiency, and greatly improves desulfurization efficiency through generated calcium peroxide, thereby providing the desulfurizing agent with high desulfurization efficiency, low cost, simple process and environmental protection, and having better popularization and application prospects.
It should be noted that, for some implementations, if they are not critical to the present invention and are well known to those of ordinary skill in the art, they are not described in detail in the drawings or the specification, and may be understood with reference to the related art.
Further, the embodiments described above are provided solely for the purpose of enabling the present invention to meet the legal requirements and may be implemented in many different forms and should not be construed as limited to the embodiments set forth herein. Furthermore, the above definitions of the elements and methods are not limited to the specific structures, shapes or modes mentioned in the embodiments, and may be simply modified or replaced by those of ordinary skill in the art. In addition, the above embodiments may be mixed with each other or other embodiments based on design and reliability, i.e. the technical features of the different embodiments may be freely combined to form more embodiments.
Unless clearly indicated to the contrary, the numerical parameters in the specification and claims of the present invention may be approximations that may vary depending upon the context in which the present invention is utilized. In particular, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood as being modified in all instances by the term "about", and are intended to include variations of + -10%, in some embodiments + -5%, in some embodiments + -1%, in some embodiments + -0.5% by a particular amount.
While the foregoing is directed to embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
Claims (6)
1. A method for preparing a desulfurizing agent, comprising:
step A, mixing carbide slag with water for pulping to obtain carbide slag slurry;
step B, mixing and reacting the carbide slag slurry with hydrogen peroxide to obtain calcium peroxide slurry, wherein the carbide slag slurry and the hydrogen peroxide are mixed by adopting a parallel flow process in a low-temperature environment of-20-0 ℃, and the mixing ratio of the carbide slag slurry to the hydrogen peroxide is controlled by the flow rate, and the weight ratio of the carbide slag to the hydrogen peroxide is 1:0.5-1:3;
step C, adding a binder into the calcium peroxide slurry to obtain a desulfurizing agent wet material;
step D, forming the wet desulfurizing agent into a semi-finished desulfurizing agent product;
step E, drying the semi-finished product of the desulfurizing agent at 50-200 ℃ for 1-8 hours to obtain a finished product of the desulfurizing agent;
wherein, according to the weight portion, 60 to 90 portions of carbide slag; 50-300 parts of hydrogen peroxide, wherein the concentration of hydrogen peroxide in the hydrogen peroxide is between 10% and 50%; 10-30 parts of adhesive; 180-720 parts of water.
2. The method for producing a desulfurizing agent according to claim 1, wherein,
in the preparation method, the step C includes: adding an auxiliary agent and a binder into the calcium peroxide slurry to obtain a desulfurizing agent wet material, wherein the auxiliary agent is 5-20 parts by weight;
wherein the auxiliary agent comprises one or more of the following materials: ferric sulfate, ferrous sulfate, ferric acetate, ferric chloride, and ferric nitrate.
3. The method for producing a desulfurizing agent according to claim 2, wherein,
in the step A, the weight ratio of the carbide slag to the water is between 1:3 and 1:8.
4. The method of manufacturing according to claim 1, wherein the binder comprises one or more of the following materials: cement, gypsum, kaolin, attapulgite, bentonite and diatomite.
5. A desulfurizing agent prepared by the process according to any one of claims 1 to 4, wherein the desulfurizing agent is in the form of a cylinder, clover or plum blossom.
6. Use of the desulfurizing agent of claim 5 in low temperature flue gas desulfurization;
wherein the low-temperature flue gas is low-temperature heating furnace flue gas, ceramic flue gas and garbage power generation tail gas.
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