CN114558442A - Preparation method and application of high-activity nano calcium-based desulfurizer - Google Patents
Preparation method and application of high-activity nano calcium-based desulfurizer Download PDFInfo
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- 239000011575 calcium Substances 0.000 title claims abstract description 30
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 29
- 230000000694 effects Effects 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 28
- 238000001035 drying Methods 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 238000010521 absorption reaction Methods 0.000 claims abstract description 16
- 238000001746 injection moulding Methods 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 238000001179 sorption measurement Methods 0.000 claims abstract description 12
- 239000011230 binding agent Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 239000012716 precipitator Substances 0.000 claims abstract description 6
- 238000001125 extrusion Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 25
- 230000003009 desulfurizing effect Effects 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 6
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 5
- 235000019353 potassium silicate Nutrition 0.000 claims description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 5
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910001424 calcium ion Inorganic materials 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 238000006477 desulfuration reaction Methods 0.000 description 24
- 230000023556 desulfurization Effects 0.000 description 24
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 13
- 239000003546 flue gas Substances 0.000 description 13
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 239000003245 coal Substances 0.000 description 5
- 150000004763 sulfides Chemical class 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000003463 sulfur Chemical class 0.000 description 3
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 238000003916 acid precipitation Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- 239000011686 zinc sulphate Substances 0.000 description 2
- 235000009529 zinc sulphate Nutrition 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- JGIATAMCQXIDNZ-UHFFFAOYSA-N calcium sulfide Chemical compound [Ca]=S JGIATAMCQXIDNZ-UHFFFAOYSA-N 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 229910001610 cryolite Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002699 waste material Substances 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
- B01D53/81—Solid phase processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
-
- 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
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Abstract
The invention discloses a preparation method of a high-activity nano calcium-based desulfurizer, which comprises the following steps: s1: pouring the raw material liquid into a self-absorption stirring type reactor for reaction, introducing a precipitator into the self-absorption stirring type reactor, and stirring and reacting to obtain a first product; s2: placing the first product on the surface of a suction filter for adsorption filtration, and washing the first product by pure water during adsorption filtration to obtain a second product; s3: introducing the second product into an injection molding machine, and adding a binder into the injection molding machine to enable the second product to be subjected to extrusion injection molding to obtain a third product; s4: putting the third product into a drying box for drying treatment; s5: placing the dried third product in a shady and cool place away from light and cooling to room temperature; s6: and after the surface temperature of the third product is reduced to room temperature, putting the third product into a roasting furnace for roasting to obtain the desulfurizer.
Description
Technical Field
The invention relates to a preparation method of a desulfurizer, in particular to a preparation method and application of a high-activity nano calcium-based desulfurizer, belonging to the technical field of desulfurizers.
Background
The flue gas generated in coal combustion or industrial manufacturing often contains sulfide, the sulfide is mainly derived from coal or petroleum and sulfur substances contained in industrial raw materials prepared from the coal or petroleum, and the sulfur substances are reacted in the combustion process or the industrial manufacturing process and converted into sulfide to be released. Sulfides, particularly hydrogen sulfide, sulfur dioxide and the like, can often cause catalyst poisoning and inactivation in a production process, waste gas containing the sulfides is directly discharged, the environment is easily polluted, air problems such as haze and the like are generated, in addition, the sulfides in the flue gas are also main substances for forming acid rain, and the acid rain not only seriously corrodes buildings and public facilities, but also destroys forests and crops in large areas, and seriously affects the health and property safety of human beings.
With the stricter requirements of national standard and industrial standard and the stricter and stricter awareness and intensification of public environmental protection, the control of the sulfide content of flue gas discharged into the environment is stricter and stricter, and meanwhile, in the chemical production process of industrial raw materials, in order to ensure the use efficiency of a catalyst, improve the product quality and prevent equipment corrosion, fine desulfurization is required to be carried out on raw material gas or waste gas generated in the production process. China is the largest coal producing country and consuming country in the world at present, 80% of coal yield is directly used for combustion, sulfide emission amount is the first place in the world, and the treatment and emission reduction of the sulfide emission amount are imminent, so that the development and development of the desulfurization technology suitable for the economic development condition of China have very important practical significance.
Flue gas desulfurization is the most effective method for controlling sulfide pollution, and is also a desulfurization technology commonly applied in the current market. Flue gas desulfurization methods are broadly classified into three categories: wet method, that is, liquid absorbent such as water or alkali liquor is used to wash the flue gas; dry process, which means that both the absorption process and the treatment of the product are carried out in an anhydrous state; the semi-dry method refers to that the desulfurizing agent is desulfurized in a dry state and regenerated in a wet state, or desulfurized in a wet state and desulfurized products are treated in a dry state, and has the characteristics of a wet method and a dry method. Although the wet desulphurization process can obtain higher desulphurization efficiency, the method is mostly a foreign technology repeatedly introduced, the equipment localization is low, the process system is complex and the equipment is huge, and the defects of secondary pollution, serious corrosion, high investment and power consumption, large system abrasion, high operation and maintenance cost and the like exist, so that the desulphurization treatment of small and medium-sized units cannot be met. The dry and semi-dry desulfurization technology has the advantages of simple process flow, small occupied area and low investment and operation cost, is particularly suitable for the desulfurization treatment of medium and small-sized units and middle-low sulfur flue gas, has good development prospect, and is a research hotspot of the current desulfurization technology.
More than 90% of commercial flue gas desulfurization in the world adopts a calcium desulfurization technology, and calcium desulfurizer is widely researched from the 20 th century to the 70 th century due to rich source, low price and simple process, and is still a main component of dry-based desulfurizer at present. The activity of the calcium-based desulfurizer is mainly determined by the particle size, the specific surface area, the size of gaps, the diffusion rate of reactants through a sulfide product layer and the like, the reaction activity of the desulfurizer is one of key factors influencing the flue gas desulfurization effect, and the higher the activity of the desulfurizer, the easier the desulfurization efficiency and the utilization rate of the desulfurizer are obtained, so that the lower the desulfurization cost is. However, the existing calcium-based desulfurizing agents for dry and semi-dry processes mainly have the following problems: in order to meet the emission requirement of sulfides, the defect of low utilization rate of the calcium-based desulfurizing agent has to be compensated by increasing the calcium-sulfur ratio, so that the waste of the desulfurizing agent is caused, and the running cost is increased; poor mechanical strength and difficult regeneration. Therefore, the sulfur fusion desulfurization precision of the existing calcium-based desulfurizer for the dry method and the semi-dry method is still low, the requirements of flue gas desulfurization on efficiency and economy are difficult to meet, the utilization rate of the calcium-based desulfurizer is improved, the cost of the desulfurizer is reduced, and the improvement of the regeneration performance of the desulfurizer is a key breakthrough point for popularization and application of dry method and semi-dry method desulfurization technologies.
At present, an economic, efficient and renewable calcium-based desulfurizer is needed for removing sulfides in flue gas by a dry method and a semi-dry method so as to meet the urgent needs of the industrial and civil fields for flue gas desulfurization.
Disclosure of Invention
The invention aims to provide a preparation method and application of a high-activity nano calcium-based desulfurizer, and aims to solve the problems in the prior art.
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of a high-activity nano calcium-based desulfurizer comprises the following steps:
s1: pouring the raw material liquid into a self-absorption stirring type reactor for reaction, introducing a precipitator into the self-absorption stirring type reactor, and stirring and reacting to obtain a first product;
s2: placing the first product on the surface of a suction filter for adsorption filtration, and washing the first product by pure water during adsorption filtration to obtain a second product;
s3: introducing the second product into an injection molding machine, and adding a binder into the injection molding machine to enable the second product to be subjected to extrusion injection molding to obtain a third product;
s4: putting the third product into a drying box for drying treatment;
s5: placing the dried third product in a shady and cool place away from light and cooling to room temperature;
s6: and after the surface temperature of the third product is reduced to room temperature, putting the third product into a roasting furnace for roasting, thereby obtaining the desulfurizer.
In some preferred embodiments, the raw material liquid in the S1 step includes Ca2+、Zn2+And Fe3+(ii) a Wherein, Ca2 +、Zn2+And Fe3+The molar ratio of (3.5-4.2) to (1.8-2.1) to 1.
In some preferred embodiments, the precipitant in step S1 is Na2CO3And (3) solution.
In some preferred embodiments, the stirring power of the self-priming stirring reactor in the step S1 is 1.0472M · N × 10-1The reaction temperature is 40-50 ℃.
In some preferred embodiments, the number of times of pure water washing in the S2 step is 3 to 6 times; the binder in the step S3 is water glass, and the using amount of the binder is 40-80% of the mass ratio of the raw material liquid.
In some preferred embodiments, the drying temperature of the drying oven in the step S4 is 150 ℃ and the drying time is 4 to 6 hours.
In some preferred embodiments, the roasting temperature of the roasting furnace in the step S6 is 600-800 ℃, and the roasting time is 8-10 h.
The high-activity nano calcium-based desulfurizer prepared by the method is particularly suitable for semi-dry and dry desulfurization processes.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention adopts the nano active calcium as the main component in the desulfurizer, so that the desulfurizer has smaller particle size and larger specific surface area, thereby increasing the saturated sulfur capacity, being beneficial to enhancing the desulfurization effect and being effectively applied to removing free sulfur or sulfide in flue gas.
2. After the calcium-based desulfurizer prepared by the method is repeatedly used for 10 times, the sulfur capacity can reach more than 90% of that of the desulfurizer used for the first time, and the calcium-based desulfurizer has good regeneration performance, can be repeatedly used and reduces the cost.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The preparation method of the high-activity nano calcium-based desulfurizer comprises the following steps:
preparing a raw material liquid, wherein the raw material liquid contains CaO, ZnSO4 and Fe2O3And CaO, ZnSO4 and Fe2O3Is 4.2:2.1:1, and the desulfurizing agent A is obtained by sequentially passing through the steps of S1, S2, S3, S4, S5 and S6.
S1: pouring the raw material liquid into a self-absorption stirring type reactor for reaction, and introducing a precipitator Na into the self-absorption stirring type reactor2CO3Stirring and reacting the solution to obtain a first product, wherein the stirring power of the self-absorption stirring type reactor is 1.0472 M.N 10-1The reaction temperature is 40-50 ℃;
s2: placing the first product on the surface of a suction filter for adsorption filtration, and washing the first product for 3 times by pure water during adsorption filtration to obtain a second product;
s3: introducing the second product into an injection molding machine, and adding binder water glass with 55% of raw material liquid by mass into the injection molding machine to extrude, injection mold and form the second product to obtain a third product;
s4: putting the third product into a drying box for drying treatment; the drying temperature is 150 ℃ and the drying time is 4 h.
S5: cooling the dried third product to room temperature in a shady and cool place;
s6: and after the surface temperature of the third product is reduced to room temperature, putting the third product into a roasting furnace for roasting, thereby obtaining the desulfurizer. The roasting temperature is 600 ℃, and the roasting time is 8 h.
Example 2:
the preparation method of the high-activity nano calcium-based desulfurizer comprises the following steps:
preparing a raw material liquid containing CaO, ZnO and Fe2O3And CaO, ZnO and Fe2O3With a molar ratio of 3.8:1.9:1, followed by steps S1, S2, S3, S4, S5 and S6 to obtain desulfurizing agent B.
S1: pouring the raw material liquid into a self-absorption stirring type reactor for reaction, and introducing a precipitator Na into the self-absorption stirring type reactor2CO3Stirring and reacting the solution to obtain a first product, wherein the stirring power of the self-absorption stirring type reactor is 1.0472 M.N 10-1The reaction temperature is 40-50 ℃;
s2: placing the first product on the surface of a suction filter for adsorption filtration, and washing the first product for 4 times by pure water during adsorption filtration to obtain a second product;
s3: introducing the second product into an injection molding machine, and adding 65% by mass of binder water glass into the injection molding machine to extrude and injection mold the second product to obtain a third product;
s4: putting the third product into a drying box for drying treatment; the drying temperature is 150 ℃, and the drying time is 5 h.
S5: placing the dried third product in a shady and cool place away from light and cooling to room temperature;
s6: and after the surface temperature of the third product is reduced to room temperature, putting the third product into a roasting furnace for roasting, thereby obtaining the desulfurizer. The roasting temperature is 700 ℃, and the roasting time is 9 h.
Example 3:
the preparation method of the high-activity nano calcium-based desulfurizer comprises the following steps:
preparing a raw material liquid containing CaO, ZnO and Fe2O3And CaO, ZnO and Fe2O3Is 3.5:1.8:1, and the desulfurizing agent C is obtained by sequentially passing through the steps of S1, S2, S3, S4, S5 and S6.
S1: pouring the raw material liquid into a self-absorption stirring type reactor for reaction, and introducing a precipitator Na into the self-absorption stirring type reactor2CO3Stirring and reacting the solution to obtain a first product, wherein the stirring power of the self-absorption stirring type reactor is 1.0472 M.N 10-1The reaction temperature is 40-50 ℃;
s2: placing the first product on the surface of a suction filter for adsorption filtration, and washing the first product for 6 times by pure water during adsorption filtration to obtain a second product;
s3: introducing the second product into an injection molding machine, and adding binder water glass with the mass percent of 70% of the raw material liquid into the injection molding machine to extrude, injection mold and form the second product to obtain a third product;
s4: putting the third product into a drying box for drying treatment; the drying temperature is 150 ℃, and the drying time is 6 h.
S5: placing the dried third product in a shady and cool place away from light and cooling to room temperature;
s6: and after the surface temperature of the third product is reduced to room temperature, putting the third product into a roasting furnace for roasting, thereby obtaining the desulfurizer. The roasting temperature is 800 ℃, and the roasting time is 10 hours.
Comparative example 1:
a commercially available desulfurization agent D comprising: 92% lime, 2% calcium aluminate, 3% cryolite and 3% borax.
The above examples 1 to 3 and comparative example 1 were subjected to mechanical testing and desulfurization effect testing to obtain tables 1 and 2:
table 1 is a mechanical test table for examples 1-3 and comparative example 1:
TABLE 1
| Specific surface area (m)2/g) | Particle size (nm) | Saturated sulfur content (%) | |
| Example 1 | 42.8 | 4059 | 28 |
| Example 2 | 38.7 | 4302 | 26 |
| Example 3 | 35.2 | 4586 | 22 |
| Comparative example 1 | 27.1 | 350847 | 18 |
Table 2 shows the desulfurization effect test results of examples 1 to 3 and comparative example 1:
TABLE 2
| Example 1 | Example 2 | Example 3 | Comparative example 1 | |
| Desulfurization rate | 98.5％ | 97.4％ | 95.6％ | 83.3％ |
As can be seen from tables 1 and 2, the specific surface area and the saturated sulfur capacity of the desulfurizer A, the desulfurizer B and the desulfurizer C prepared by the method of the invention are larger than those of the commercially available product desulfurizer D, the particle size is smaller than that of the existing desulfurizer D, and the desulfurization effect of the desulfurizer A, the desulfurizer B and the desulfurizer C is better than that of the desulfurizer D; researches show that the desulfurizing effect is better along with the increase of the content of calcium ions and zinc ions in the desulfurizing agent.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. A preparation method of a high-activity nano calcium-based desulfurizer is characterized by comprising the following steps:
s1: pouring the raw material liquid into a self-absorption stirring type reactor for reaction, introducing a precipitator into the self-absorption stirring type reactor, and stirring and reacting to obtain a first product;
s2: placing the first product on the surface of a suction filter for adsorption filtration, and washing the first product by pure water during adsorption filtration to obtain a second product;
s3: introducing the second product into an injection molding machine, and adding a binder into the injection molding machine to enable the second product to be subjected to extrusion injection molding to obtain a third product;
s4: putting the third product into a drying box for drying treatment;
s5: placing the dried third product in a shady and cool place away from light and cooling to room temperature;
s6: and after the surface temperature of the third product is reduced to room temperature, putting the third product into a roasting furnace for roasting, thereby obtaining the desulfurizer.
2. The preparation method of the high-activity nano calcium-based desulfurizer according to claim 1, characterized in that: the raw material liquid in the step S1 comprises Ca2+、Zn2+And Fe3+(ii) a Wherein Ca2+、Zn2+And Fe3+The molar ratio of (3.5-4.2) to (1.8-2.1) to 1.
3. The preparation method of the high-activity nano calcium-based desulfurizer according to claim 1, characterized in that: the precipitant in the step S1 is Na2CO3And (3) solution.
4. The preparation method of the high-activity nano calcium-based desulfurizer according to claim 1, characterized in that: the stirring power of the self-priming stirring reactor in the step S1 is 1.0472 M.N × 10-1The reaction temperature is 40-50 ℃.
5. The preparation method of the high-activity nano calcium-based desulfurizer according to claim 1, characterized in that: the number of times of pure water washing in the step S2 is 3-6; the binder in the step S3 is water glass, and the using amount of the binder is 40-80% of the mass ratio of the raw material liquid.
6. The preparation method of the high-activity nano calcium-based desulfurizer according to claim 1, characterized in that: and in the step S4, the drying temperature of the drying oven is 150 ℃, and the drying time is 4-6 h.
7. The preparation method of the high-activity nano calcium-based desulfurizer according to claim 1, characterized in that: the roasting temperature of the roasting furnace in the step S6 is 600-800 ℃, and the roasting time is 8-10 h.
8. Use of the high-activity nano calcium-based desulfurizing agent prepared by the method of any one of claims 1 to 7 in a dry or semi-dry desulfurizing process.
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