CN113413758A - Desulfurization additive and preparation method thereof - Google Patents
Desulfurization additive and preparation method thereof Download PDFInfo
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- CN113413758A CN113413758A CN202110889585.7A CN202110889585A CN113413758A CN 113413758 A CN113413758 A CN 113413758A CN 202110889585 A CN202110889585 A CN 202110889585A CN 113413758 A CN113413758 A CN 113413758A
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- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 64
- 230000023556 desulfurization Effects 0.000 title claims abstract description 64
- 239000000654 additive Substances 0.000 title claims abstract description 48
- 230000000996 additive effect Effects 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 45
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 24
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 20
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 14
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 12
- 239000002131 composite material Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 150000007524 organic acids Chemical class 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 22
- 229910021487 silica fume Inorganic materials 0.000 claims description 17
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 16
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical group [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 16
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 14
- 229940070527 tourmaline Drugs 0.000 claims description 14
- 229910052613 tourmaline Inorganic materials 0.000 claims description 14
- 239000011032 tourmaline Substances 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000001361 adipic acid Substances 0.000 claims description 8
- 235000011037 adipic acid Nutrition 0.000 claims description 8
- 239000005711 Benzoic acid Substances 0.000 claims description 7
- 235000010233 benzoic acid Nutrition 0.000 claims description 7
- 239000001509 sodium citrate Substances 0.000 claims description 7
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 6
- 150000004760 silicates Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 235000013312 flour Nutrition 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 23
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 10
- 239000000920 calcium hydroxide Substances 0.000 description 10
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 235000019738 Limestone Nutrition 0.000 description 9
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 9
- 239000006028 limestone Substances 0.000 description 9
- 230000003009 desulfurizing effect Effects 0.000 description 7
- 238000002485 combustion reaction Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000003245 coal Substances 0.000 description 5
- 239000012467 final product Substances 0.000 description 5
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
- B01D53/8609—Sulfur oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/80—Semi-solid phase processes, i.e. by using slurries
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/40—Alkaline earth metal or magnesium compounds
- B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/60—Inorganic bases or salts
- B01D2251/606—Carbonates
Abstract
The invention discloses a desulfurization additive which comprises 6-12 parts by weight of silica flour; 40-60 parts of calcium carbonate; 18-30 parts of an organic acid; 5-6 parts of modified manganese oxide. The invention also discloses a preparation method of the desulfurization additive, which comprises the following steps: (1) mixing the silica powder with water, and heating to 60-90 ℃; (2) under the negative pressure condition of-0.65 to-0.85 MPa, adding calcium carbonate to obtain a modified silicate-calcium carbonate combined composite material; (3) when the temperature is reduced to below 40 ℃, adding organic acid, stirring and mixing, adding sodium carbonate, and drying; (4) and (3) adding the modified manganese oxide after drying, and uniformly mixing to obtain the desulfurization additive. The desulfurization additive disclosed by the invention is high in desulfurization efficiency, simple to prepare, pollution-free in production process and environment-friendly.
Description
Technical Field
The invention relates to the field of waste gas treatment, in particular to a desulfurization additive and a preparation method thereof.
Background
Coal is a main energy source in our country, has wide application fields, and is industrially used for power plant power generation, industrial boiler heat energy combustion and the like. Sulfur dioxide, nitrogen oxides and smoke emitted during coal combustion are the most major pollutants in the atmosphere. The sulfur dioxide discharged into the atmosphere is oxidized into sulfur trioxide by the photosynthesis, and the sulfur trioxide is combined with water vapor and smoke dust to form acid rain, which is a worldwide environmental pollution problem at present. The method has important practical application significance for combustion desulfurization aiming at the coal utilization condition of China. The combustion desulfurization refers to a process of adding a desulfurizing agent into coal in a combustion process, reacting the desulfurizing agent with sulfur dioxide generated by combustion to generate sulfate, and leaving sulfur in ash. At present, factories burning coal have implemented ultra-low emission, equipment cost investment is high due to ultra-low emission, and efficiency of desulfurization equipment is reduced year by year, so that novel material products with low cost and desulfurization assisting efficiency are urgently needed in the market, and the materials cannot cause water pollution or air pollution of the environment in the manufacturing process.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide the desulfurization additive which has high desulfurization efficiency, simple preparation and no pollution in the production process.
The invention also aims to provide a preparation method of the desulfurization additive.
The purpose of the invention is realized by the following technical scheme:
a desulfurization additive which comprises the following components in parts by weight
The silica fume is a mixture of silica fume and tourmaline powder, wherein the mass ratio of the silica fume to the tourmaline powder is 1: 0.9-1.1;
the modified manganese oxide is manganese oxide calcined at a high temperature of more than 800 ℃ for 6-7 hours.
Preferably, the organic acid is a crystalline powder organic complex acid, which comprises
75-85% of adipic acid
7.5 to 12.5 percent of sodium citrate
7.5-12.5% of benzoic acid.
Preferably, the particle size of the silica powder is more than 800 meshes.
Preferably, the particle size of the calcium carbonate is 500-1200 meshes.
Preferably, the particle size of the sodium carbonate is 200 meshes or more.
The preparation method of the desulfurization additive comprises the following steps:
(1) mixing the silica powder and water under the pressure of 0.2-3.50 MPa, and heating to 60-90 ℃;
(2) under the negative pressure condition of-0.65 to-0.85 MPa, adding calcium carbonate to obtain a modified silicate-calcium carbonate combined composite material;
(3) when the temperature is reduced to below 40 ℃, adding organic acid into the modified silicate-bound calcium carbonate composite material obtained in the step (2) under the pressure of 0.2-3.50 MPa, stirring and mixing, adding sodium carbonate, and drying;
(4) and under the condition that the pressure is 0.2-3.50 MPa, drying, adding the modified manganese oxide, and uniformly mixing to obtain the desulfurization additive.
Preferably, the weight ratio of the silica powder to the water in the step (1) is as follows: (6-12) and (20-35).
Preferably, the stirring and mixing in the step (3) are specifically: stirring for 30-40 minutes.
Preferably, the mixing in step (4) is specifically: mixing for 0.8-1.2 hours.
Preferably, the drying in the step (3) is heating drying at 55-65 ℃.
The desulfurization additive can accelerate the high alkalinity activity of the silicate-bonded calcium carbonate because the tourmaline powder carries far infrared energy, and can generate discharge to provide energy when the tourmaline powder exists with organic and inorganic matters together because the tourmaline powder has a certain function of releasing negative micro-ions, so that the desulfurization additive can generate catalytic action on the organic and inorganic matters, and the desulfurization efficiency is improved.
Compared with common manganese oxide, the modified manganese oxide added in the invention has the advantages of gamma-type crystal structure, large specific surface area, good liquid absorption performance, high discharge activity and the like, so that the effect of catalytic oxidation-reduction reaction in desulfurization can be improved.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the desulfurization additive accelerates the reaction process of substances by the fact that tourmaline powder carries far infrared energy and has certain load ionization reaction. In the desulfurization process, calcium carbonate is insoluble in water, so that the dispersion solubility is poor, in the desulfurization process, due to the action of load ionization, after the desulfurization additive is added, due to the action of tourmaline powder and adipic acid, the water solubility of calcium carbonate and water is improved, the separation of calcium and water is reduced, so that sulfur dioxide gas can be effectively dispersed and captured, and the desulfurization efficiency is improved.
(2) The preparation method of the desulfurization additive disclosed by the invention has the advantages of no waste water and waste discharge in the production process and environmental friendliness.
(3) The preparation method of the desulfurization additive has the advantages of simple preparation process and low production cost.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
The desulfurization additive of this example was prepared as follows:
firstly, 80g of silica powder and 300g of water are mixed and added into a reaction kettle, the mixture is heated to 70 ℃, 500g of calcium hydroxide is added under the condition of negative pressure of-0.8 MPa, 250g of organic composite acid is added when the temperature is reduced to be below 40 ℃, 100g of sodium carbonate is added after the reaction kettle is stirred and mixed for 30 minutes, finally, the mixture is heated to 55 ℃ in the reaction kettle and dried to form powder, 80g of modified manganese oxide is added, and the mixture is mixed for 1 hour to finally form the high-efficiency desulfurization additive of the final product.
The silica fume powder of this example is formed by mixing silica fume and tourmaline powder in a ratio of 1: 1.
The organic complex acid of this example was a crystalline powder mixture of 80 wt% adipic acid, 10 wt% sodium citrate and 10 wt% benzoic acid.
The modified manganese oxide of this example was prepared by calcining 99.9% pure manganese oxide at 800 ℃ for 7 hours.
Except the step of adding the calcium hydroxide, the pressure of the reaction kettle is kept between 0.2 and 3.50MPa in other steps.
In order to illustrate the effects of the present invention, the desulfurization additive prepared in this example was used in actual industrial production, and compared with a production process using only limestone as a desulfurizing agent. The specific process and results are as follows:
taking the actual application of the limestone wet desulphurization system in a 135MW coal-fired power plant of North Power Generation, Qinghai Ning, as an example, the specific parameters are as follows: the slurry volume is about 700m3Inlet S02Concentration: 1200mg/m31800mg/m3And the configuration of a desulfurization system: 3 circulating pumps with work power of 550KW run two times and one standby at ordinary times; before the experiment, the density of the absorption tower is controlled to 1090kg/m3(ii) a The pH value of the absorption tower is controlled to be 4.88; the density of the limestone slurry tank is controlled to be 1200kg/m3-1250kg/m3Left and right; the operating liquid level of the absorption tower is controlled between 6.3m and 6.8 m; the content of chloride ions in the slurry of the absorption tower is controlled within 30000mg/L during the test.
The test parameters of the desulfurizer limestone powder used are shown in table 1.
TABLE 1
Test 1: the environmental protection data of the desulfurizing tower of the desulfurization system of this embodiment for 7 days is shown in table 2, using only limestone as the desulfurizing agent.
TABLE 2
Test 2: limestone is used as a desulfurizing agent, and the addition amount of the desulfurizing additive is about 1000ppm, except that other test conditions are the same as those of the test 1, and the specific operation process is as follows:
1. day 1, 11 am 28 min test the first day of the test a desulfurization additive was added to 500 kg in the pit of the absorber.
2. At 11 am on days 2 and 3, 50 kg of the desulfurization additive was added to the pit, for a total of 100 kg.
3. At 11 am on days 4 to 7, 25 kg of each of the pellets was added, and the total amount was 100 kg.
4. On day 8, 11 am, the addition was stopped.
5. Test time: for 7 days, the total amount of the additive is added for 7 times, and 700 kg is added in total.
Environmental data for the 7 day period of the desulfurization tower are shown in table 3.
TABLE 3
Summary of the test:
under the same operation condition of the unit, the desulfurization efficiency is improved by 8 percent after the desulfurization additive is added, and the effect is obvious.
Example 2
Firstly, 100g of silica powder and 300g of water are mixed and added into a reaction kettle, the mixture is heated to 70 ℃, 450g of calcium hydroxide is added under the condition of negative pressure of-0.8 MPa, 200g of organic composite acid is added when the temperature is reduced to be below 40 ℃, 120g of sodium carbonate is added after the reaction kettle is stirred and mixed for 30 minutes, finally, the mixture is heated to 60 ℃ in the reaction kettle and dried to form powder, 100g of modified manganese oxide is added, and the mixture is mixed for 1 hour to finally form the high-efficiency desulfurization additive of the final product.
The silica fume powder of this example is formed by mixing silica fume and tourmaline powder in a ratio of 1: 1.
The organic complex acid of this example was a crystalline powder mixture of 75 wt% adipic acid, 12.5 wt% sodium citrate and 12.5 wt% benzoic acid.
The modified manganese oxide of this example was prepared by calcining 99.9% pure manganese oxide at 900 ℃ for 6 hours.
Except the step of adding the calcium hydroxide, the pressure of the reaction kettle is kept between 0.2 and 3.50MPa in other steps.
The test result shows that: under the same operation condition of the unit, the desulfurization efficiency is improved by 10% after the desulfurization additive is added, and the effect is obvious.
To better illustrate the effect of the desulfurization additive of this example, the following tests were performed on the desulfurization additive of this example:
a small sample of 500g of water containing 10% of limestone powder is taken, 800ppm of material is added, detection and analysis are carried out according to a test method of DL/T943-2005 determination of limestone powder reaction rate for wet flue gas desulfurization, and the results are shown in Table 2:
TABLE 2
As can be seen from the above, the limestone dissolution time is improved by more than 50% after the desulfurization additive of the present embodiment is added, and therefore, the desulfurization efficiency can be improved in practical industrial use.
Example 3
Firstly, 100g of silica powder and 300g of water are mixed and added into a reaction kettle, the mixture is heated to 70 ℃, 450g of calcium hydroxide is added under the condition of negative pressure of-0.8 MPa, 200g of organic composite acid is added when the temperature is reduced to be below 40 ℃, 120g of sodium carbonate is added after the reaction kettle is stirred and mixed for 30 minutes, finally, the mixture is heated to 60 ℃ in the reaction kettle and dried to form powder, 100g of modified manganese oxide is added, and the mixture is mixed for 1 hour to finally form the high-efficiency desulfurization additive of the final product.
The silica fume powder of this embodiment is formed by mixing silica fume and tourmaline powder in a ratio of 1: 0.9.
The organic complex acid of this example was a crystalline powder mixture of 85 wt% adipic acid, 7.5 wt% sodium citrate and 7.5 wt% benzoic acid.
The modified manganese oxide of this example was prepared by calcining 99.9% pure manganese oxide at 850 deg.C for 6 hours.
Except the step of adding the calcium hydroxide, the pressure of the reaction kettle is kept between 0.2 and 3.50MPa in other steps.
The test result shows that: under the same operation condition of the unit, the desulfurization efficiency is improved by 9 percent after the desulfurization additive is added, and the effect is obvious.
Example 4
Firstly, 125g of silica powder and 300g of water are mixed and added into a reaction kettle, the mixture is heated to 70 ℃, 480g of calcium hydroxide is added under the condition of negative pressure of-0.8 MPa, 230g of organic composite acid is added when the temperature is reduced to below 40 ℃, 150g of sodium carbonate is added after the reaction kettle is stirred and mixed for 30 minutes, finally, the mixture is heated and dried in the reaction kettle to form powder, 130g of modified manganese oxide is added, and the mixture is mixed for 1 hour to finally form the high-efficiency desulfurization additive of the final product.
The silica fume powder of this example is formed by mixing silica fume and tourmaline powder in a ratio of 1: 1.
The organic complex acid of this example was a crystalline powder mixture of 85 wt% adipic acid, 7.5 wt% sodium citrate and 7.5 wt% benzoic acid.
The modified manganese oxide of this example was prepared by calcining 99.9% pure manganese oxide at 850 deg.C for 6 hours.
Except the step of adding 500g of calcium hydroxide, the pressure of the reaction kettle is kept between 0.2 and 3.50MPa in other steps.
The test result shows that: under the same operation condition of the unit, after the desulfurization additive is added, the desulfurization efficiency is improved by 11 percent, and the effect is obvious.
Example 5
Firstly, 135g of silica powder and 300g of water are mixed and added into a reaction kettle, the mixture is heated to 70 ℃, 550g of calcium hydroxide is added under the condition of negative pressure of-0.8 MPa, 180g of organic composite acid is added when the temperature is reduced to below 40 ℃, 125g of sodium carbonate is added after the reaction kettle is reacted, stirred and mixed for 30 minutes, finally, the mixture is heated and dried in the reaction kettle to form powder, 125g of modified manganese oxide is added, and the mixture is mixed for 1 hour to finally form the high-efficiency desulfurization additive of the final product.
The silica fume powder of the embodiment is formed by mixing silica fume and tourmaline powder according to the proportion of 1: 1.2.
The organic complex acid of this example was a crystalline powder mixture of 85 wt% adipic acid, 7.5 wt% sodium citrate and 7.5 wt% benzoic acid.
The modified manganese oxide of this example was prepared by calcining 99.9% pure manganese oxide at 850 deg.C for 6 hours.
Except the step of adding the calcium hydroxide, the pressure of the reaction kettle is kept between 0.2 and 3.50MPa in other steps.
The test result shows that: under the same operation condition of the unit, the desulfurization efficiency is improved by 12% after the desulfurization additive is added, and the effect is obvious.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. The desulfurization additive is characterized by comprising the following components in parts by weight
The silica fume is a mixture of silica fume and tourmaline powder, wherein the mass ratio of the silica fume to the tourmaline powder is 1: 0.9-1.1;
the modified manganese oxide is manganese oxide calcined at a high temperature of more than 800 ℃ for 6-7 hours.
2. The additive according to claim 1, wherein the organic acid is a crystalline powder-like organic complex acid comprising, by weight
75-85% of adipic acid
7.5 to 12.5 percent of sodium citrate
7.5-12.5% of benzoic acid.
3. The desulfurization additive according to claim 1, wherein the silica powder has a particle size of 800 mesh or more.
4. The additive according to claim 1, wherein the calcium carbonate has a particle size of 500-1200 mesh.
5. The additive according to claim 1, wherein the particle size of the sodium carbonate is 200 mesh or larger.
6. The method for preparing the desulfurization additive according to any one of claims 1 to 5, characterized by comprising the steps of:
(1) mixing the silica powder and water under the pressure of 0.2-3.50 MPa, and heating to 60-90 ℃;
(2) under the negative pressure condition of-0.65 to-0.85 MPa, adding calcium carbonate to obtain a modified silicate-calcium carbonate combined composite material;
(3) when the temperature is reduced to below 40 ℃, adding organic acid into the modified silicate-bound calcium carbonate composite material obtained in the step (2) under the pressure of 0.2-3.50 MPa, stirring and mixing, adding sodium carbonate, and drying;
(4) and under the condition that the pressure is 0.2-3.50 MPa, drying, adding the modified manganese oxide, and uniformly mixing to obtain the desulfurization additive.
7. The method for preparing desulfurization additive according to claim 6, wherein the weight ratio of the silica fume powder and water in the step (1) is: (6-12) and (20-35).
8. The method for preparing desulfurization additive according to claim 6, wherein the stirring and mixing in step (3) are specifically: stirring for 30-40 minutes.
9. The method for preparing desulfurization additive according to claim 6, wherein the mixing in step (4) is specifically: mixing for 0.8-1.2 hours.
10. The method for preparing the desulfurization additive according to claim 6, wherein the drying in the step (3) is heating drying at 55 to 65 ℃.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102145252A (en) * | 2011-01-31 | 2011-08-10 | 浙江润丰能源工程有限公司 | Synergist for limestone-gypsum wet flue gas desulfurization |
| CN103432894A (en) * | 2013-08-30 | 2013-12-11 | 杨子江 | Synergist for assisting wet-process desulphurization of thermal power plant, and application method of synergist |
| CN103495407A (en) * | 2013-08-30 | 2014-01-08 | 蚌埠凤凰滤清器有限责任公司 | Bamboo-based modified activated carbon desulfurization adsorbent and its preparation method |
| CN107497282A (en) * | 2017-10-14 | 2017-12-22 | 胡健 | A kind of desulfurization catalyst improves synergist |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102145252A (en) * | 2011-01-31 | 2011-08-10 | 浙江润丰能源工程有限公司 | Synergist for limestone-gypsum wet flue gas desulfurization |
| CN103432894A (en) * | 2013-08-30 | 2013-12-11 | 杨子江 | Synergist for assisting wet-process desulphurization of thermal power plant, and application method of synergist |
| CN103495407A (en) * | 2013-08-30 | 2014-01-08 | 蚌埠凤凰滤清器有限责任公司 | Bamboo-based modified activated carbon desulfurization adsorbent and its preparation method |
| CN107497282A (en) * | 2017-10-14 | 2017-12-22 | 胡健 | A kind of desulfurization catalyst improves synergist |
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