CN107983108A - A kind of preparation method of the special sulphur-fixing agent of flue gas desulfurization - Google Patents
A kind of preparation method of the special sulphur-fixing agent of flue gas desulfurization Download PDFInfo
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- CN107983108A CN107983108A CN201711363192.2A CN201711363192A CN107983108A CN 107983108 A CN107983108 A CN 107983108A CN 201711363192 A CN201711363192 A CN 201711363192A CN 107983108 A CN107983108 A CN 107983108A
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- 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
- B01D53/50—Sulfur oxides
- B01D53/508—Sulfur oxides by treating the gases with solids
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2258/00—Sources of waste gases
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- B01D2258/0283—Flue gases
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Abstract
The invention discloses a kind of preparation method of the special sulphur-fixing agent of flue gas desulfurization, belongs to environment-friendly materials technical field.The present invention is first by lime stone grinding and sieving, freeze-thaw circulation is carried out after being mixed again with water, and through drying, lime stone must be pre-processed, after pretreatment lime stone and urea liquid are stirred again, add metal salt solution and Bacillus pasteurii bacterium solution, constant temperature stirring reaction, concentration, it is dry, obtain dry cake, dry cake is gradually heated up under different temperatures again after being roasted, cool to room temperature with the furnace, obtain roasting material, finally by roasting material, after modified meerschaum and activated carbon mixing, ball milling, up to the special sulphur-fixing agent of flue gas desulfurization, wherein modified meerschaum is by after sepiolite and hydrochloric acid reaction, roasting obtains.The gained special sulphur-fixing agent desulfuration efficiency of flue gas desulfurization of the invention is effectively improved.
Description
Technical field
The invention discloses a kind of preparation method of the special sulphur-fixing agent of flue gas desulfurization, belongs to environment-friendly materials technical field.
Background technology
Sulphur-fixing agent refers generally to remove fuel, raw material or free sulphur or the medicament of sulphur compound in unclassified stores；Polluting
Refer mainly to that removing exhaust gas sulphur oxide can be removed in the control and processing of thing（Including SO2And SO3）Medicament used.Various alkalizations
Compound can all be used as desulfurizing agent.Generally require sulphur-fixing agent raw material sources wide, it is cheap etc..Ore with sulfur capturing capacity（Such as
Lime stone, dolomite）, quick lime, slag and industrial residue be all sulphur-fixing agent raw material.
At present, the sulfur-fixing rate of U.S.'s moulded coal is 87%~90%, and the sulfur-fixing rate of Japanese moulded coal is 80%~90%, China's moulded coal
Sulfur-fixing rate is relatively low, is 50% or so.Brainstrust thinks that China is consolidating for use with the main reason for external sulfur-fixing rate difference
Sulphur agent is different, therefore, develops and develop the key that economic, efficient sulphur-fixing agent is problem.Sulphur-fixing agent is the pass in sulfur solidifying technique
Key, especially in high-temp combustion desulfurization, the quality of desulfurization effect is heavily dependent on the reactivity worth of sulphur-fixing agent.Different
Requirement of the sulfur removal technology to sulphur-fixing agent is not quite similar, as desulphurization during combustion require sulphur-fixing agent there is good temperature characterisitic, make it
Enough scrubbing CO_2s effective at high temperature etc..But regardless of sample sulphur-fixing agent require with good economy, compared with
High desulfuration efficiency, and to environment non-secondary pollution.At present traditional sulphur-fixing agent also there are desulfuration efficiency it is bad the problem of, therefore
Also need to study this.
The content of the invention
The present invention solves the technical problem of：For traditional sulphur-fixing agent desulfuration efficiency it is bad the problem of, there is provided one
The preparation method of the kind special sulphur-fixing agent of flue gas desulfurization.
In order to solve the above-mentioned technical problem, the technical solution adopted in the present invention is：
（1）After lime stone is crushed, sieving, obtains agstone, then by gained agstone and water is 1 in mass ratio：4~1：6
After mixing, freeze-thaw circulation 8~10 times, then through vacuum freeze drying, obtain pretreatment lime stone；
（2）Count in parts by weight, take 10~15 parts of metal salt solutions, 60~80 parts of urea liquids, 8~10 parts of Pasteur's gemma successively
Pretreatment lime stone and urea liquid, are first stirred, add metal salt by bacillus bacterium solution, 40~60 parts of pretreatment lime stones
Solution and Bacillus pasteurii bacterium solution, after 24~36h is reacted in constant temperature stirring, concentrate, dry, obtain dried feed；
（3）Gained dried feed is transferred to tube furnace, is warming up to 110~115 DEG C with 3~5 DEG C/min rate programs, insulation reaction 45
After~60min, continue to be warming up to 190~200 DEG C with 4~6 DEG C/min rate programs, after 45~60min of insulation reaction, continue with
10~20 DEG C/min rate programs are warming up to 800~920 DEG C, after 3~5min of insulation reaction, cool to room temperature with the furnace, discharge, obtain
Roasting material；
（4）Count in parts by weight, take 80~100 parts of roasting materials, 8~10 parts of modified meerschaums, 20~30 parts of activated carbons, ball successively
Mill mixing, up to the special sulphur-fixing agent of flue gas desulfurization.
Step（1）The freeze-thaw circulation is：Under the conditions of temperature is -20~-30 DEG C, after freezing 4~6h, in temperature
Under the conditions of 45~50 DEG C, thaw 3~5h.
Step（2）The metal salt solution is formed by the configuration of following parts by weight raw material：10~15 parts of calcium nitrate, 20~
30 parts of magnesium nitrates, 150~200 parts of water.
Step（2）The Bacillus pasteurii bacterium solution is formed by the configuration of following parts by weight raw material：3~5 parts of Pasteur's buds
Spore bacillus, 0.1~0.2 part of glucose, 4~8 parts of glycerine, 6~8 parts of ethylene glycol, 100~150 parts of deionized waters.
Step（4）The modified meerschaum modifying process is：It is 1 in mass ratio by sepiolite and hydrochloric acid：10~1：15 is mixed
After conjunction, ultrasonic reaction, then filtered, washing, dry and roasting, obtain modified meerschaum.
Step（4）The activated carbon is any one in powdered activated carbon, granular activated carbon or spherical activated charcoal.
The beneficial effects of the invention are as follows：
（1）Technical solution of the present invention is first handled the mixture of agstone and water using freeze-thaw circulation, is being located
During reason, moisture penetration enters in lime stone pore structure, in refrigerating process, volumetric expansion after water freezing, and to lime
Stone pore structure produces pressure, widens hole, after defrosting, moisture is further penetrated into inside pore structure, with freezing
The progress of thaw cycles, hole gradually increase and deepen, and isolate hole number and reduce, lime stone is fragmented into the pre- place of loose structure
Reason stone lime stone, increasing and deepening for pore structure, is conducive in follow-up roasting process, reduces the partial pressure at endoporus, reduces
The influence of sintering, while can effectively improve in sweetening process, diffusion of the sulfur dioxide gas to reaction interface, so as to improve calcium profit
With rate and desulfuration efficiency；
（2）Technical solution of the present invention in preparation process by adding metal salt solution, urea liquid and Bacillus pasteurii bacterium
Liquid, in processing procedure, Bacillus pasteurii can break down urea into ammonium ion and carbanion, and due to Pasteur's gemma
Bacilli-cell cornice has negative electrical charge, can be by adsorption of metal ions in system around thalline, with carbonate around somatic cells
Ion concentration increase, generation metal carbonate is combined with metal ion, and the carbonate of generation disperses using somatic cells as nucleus
Inside system, in follow-up roasting process, metal carbonate, which decomposes, produces carbon dioxide, and as thalline was roasting
It is burned out in journey, system porosity is further lifted, so as to be conducive to further improve calcium utilization and the desulfurization of product
Efficiency, and metal carbonate decompose after effectively scattered inside system of the metal oxide that produces can also effectively improve product
Desulfuration efficiency.
Embodiment
It is 1 in mass ratio：10~1：15 pour into sepiolite and mass fraction in beaker for 10~15% hydrochloric acid, and will
Beaker is transferred to sonic oscillation instrument, and under the conditions of supersonic frequency is 45~50kHz, after sonic oscillation reacts 2~4h, filtering, must filter
Slag, and filter residue is washed with deionized 3~5 times, then the filter residue after washing is transferred in baking oven, in temperature be 105~110 DEG C of bars
Dried under part to constant weight, obtain dry filter residue, then gained drying filter residue is transferred to tube furnace, in temperature be 260~280 DEG C of conditions
Under, after 2~4h of insulation roasting, cool to room temperature with the furnace, discharge, obtain modified meerschaum；Lime stone is poured into pulverizer, is crushed
40~120 mesh sieves are crossed afterwards, obtain agstone, then by gained agstone and water are 1 in mass ratio：4~1：Plastics are poured into 6 mixing
In beaker, then by plastic beaker immigration refrigerator, moved after 4~6h is freezed under the conditions of temperature is -20~-30 DEG C, then by beaker
Enter in thermostat water bath, under the conditions of temperature is 45~50 DEG C, thaw 3~5h, and such freeze-thaw circulation 8~10 times, is collected
Material in plastic beaker after last time is thawed, then through vacuum freeze drying, obtain pretreatment lime stone；Count in parts by weight, according to
It is secondary to take 10~15 parts of metal salt solutions, 60~80 parts of urea liquids, 8~10 parts of Bacillus pasteurii bacterium solutions, 40~60 parts of pre- places
Reason stone lime stone, after being first stirred pretreatment lime stone and urea liquid, is poured into fermentation tank, then is added successively into fermentation tank
Enter metal salt solution and Bacillus pasteurii bacterium solution, in temperature be 30~32 DEG C, it is permanent under the conditions of rotating speed is 180~200r/min
Temperature stirring 24~36h of reaction, discharging, obtains fermentation material, and gained fermentation material is moved into Rotary Evaporators, in pressure for 600~
700kPa, under the conditions of temperature is 65~70 DEG C, be concentrated under reduced pressure 2~4h, obtains concentrate feed, then by gained concentrate feed in temperature for 75~
Dry 12~24h under the conditions of 80 DEG C, discharging, obtains dried feed；Gained dried feed is then transferred to tube furnace, with 3~5 DEG C/min speed
Rate temperature programming after 45~60min of insulation reaction, continues to be warming up to 190 with 4~6 DEG C/min rate programs to 110~115 DEG C
~200 DEG C, after 45~60min of insulation reaction, continue to be warming up to 800~920 DEG C with 10~20 DEG C/min rate programs, insulation is anti-
After answering 3~5min, room temperature is cooled to the furnace, discharge, obtain roasting material；Count in parts by weight, take 80~100 parts of roasting materials successively, 8
~10 parts of modified meerschaums, 20~30 parts of activated carbons, add in ball grinder, and are 10 by ball material mass ratio：1~20：1 adds oxygen
Change zirconium ball milling pearl, after 2~4h of ball milling mixing, discharging, up to the special sulphur-fixing agent of flue gas desulfurization.The metal salt solution is by following
The configuration of parts by weight raw material forms：10~15 parts of calcium nitrate, 20~30 parts of magnesium nitrates, 150~200 parts of water.Pasteur's gemma
Bacillus bacterium solution is formed by the configuration of following parts by weight raw material：3~5 parts of Bacillus pasteuriis, 0.1~0.2 part of glucose, 4~8
Part glycerine, 6~8 parts of ethylene glycol, 100~150 parts of deionized waters.The activated carbon is powdered activated carbon, granular activated carbon or ball
Any one in shape activated carbon.
Example 1
It is 1 in mass ratio：15 pour into sepiolite and mass fraction in beaker for 15% hydrochloric acid, and beaker is transferred to ultrasound and is shaken
Instrument is swung, under the conditions of supersonic frequency is 50kHz, after sonic oscillation reaction 4h, filtering, obtains filter residue, and filter is washed with deionized
Slag 5 times, then the filter residue after washing is transferred in baking oven, dried under the conditions of being 110 DEG C in temperature to constant weight, obtain dry filter residue, then
Gained drying filter residue is transferred to tube furnace, under the conditions of temperature is 280 DEG C, after insulation roasting 4h, room temperature is cooled to the furnace, goes out
Material, obtains modified meerschaum；Lime stone is poured into pulverizer, 120 mesh sieves are crossed after crushing, obtain agstone, then by gained lime
Mountain flour and water are 1 in mass ratio：6 mixing pour into plastic beaker, then by plastic beaker move into refrigerator in, in temperature be -30 DEG C
Under the conditions of freeze 6h after, then by beaker move into thermostat water bath in, in temperature be 50 DEG C under the conditions of, defrosting 5h, so freezing solution
Freeze circulation 10 times, material in plastic beaker after collection last time is thawed, then through vacuum freeze drying, obtain pretreatment lime stone；
Count in parts by weight, take 15 parts of metal salt solutions, 80 parts of urea liquids, 10 parts of Bacillus pasteurii bacterium solutions, 60 parts of pre- places successively
Reason stone lime stone, after being first stirred pretreatment lime stone and urea liquid, is poured into fermentation tank, then is added successively into fermentation tank
Enter metal salt solution and Bacillus pasteurii bacterium solution, be 32 DEG C in temperature, under the conditions of rotating speed is 200r/min, constant temperature stirring is reacted
36h, discharging, obtains fermentation material, and gained fermentation material is moved into Rotary Evaporators, is 700kPa in pressure, temperature is 70 DEG C of conditions
Under, be concentrated under reduced pressure 4h, obtains concentrate feed, then gained concentrate feed is dried 24h under the conditions of temperature is 80 DEG C, and discharging, obtains dried feed；
Gained dried feed is then transferred to tube furnace, 115 DEG C are warming up to 5 DEG C/min rate programs, after insulation reaction 60min, is continued
200 DEG C are warming up to 6 DEG C/min rate programs, after insulation reaction 60min, continue to be warming up to 920 with 20 DEG C/min rate programs
DEG C, after insulation reaction 5min, cool to room temperature with the furnace, discharge, obtain roasting material；Count in parts by weight, take 100 parts of roastings successively
Material, 10 parts of modified meerschaums, 30 parts of activated carbons, add in ball grinder, and are 20 by ball material mass ratio：1 adds zirconium oxide ball milling
Pearl, after ball milling mixing 4h, discharging, up to the special sulphur-fixing agent of flue gas desulfurization.The metal salt solution is former by following parts by weight
Material configuration forms：15 parts of calcium nitrate, 30 parts of magnesium nitrates, 200 parts of water.The Bacillus pasteurii bacterium solution is by following parts by weight
Raw material configuration forms：5 parts of Bacillus pasteuriis, 0.2 part of glucose, 8 parts of glycerine, 8 parts of ethylene glycol, 150 parts of deionized waters.It is described
Activated carbon is powdered activated carbon.
Example 2
It is 1 in mass ratio：15 pour into sepiolite and mass fraction in beaker for 15% hydrochloric acid, and beaker is transferred to ultrasound and is shaken
Instrument is swung, under the conditions of supersonic frequency is 50kHz, after sonic oscillation reaction 4h, filtering, obtains filter residue, and filter is washed with deionized
Slag 5 times, then the filter residue after washing is transferred in baking oven, dried under the conditions of being 110 DEG C in temperature to constant weight, obtain dry filter residue, then
Gained drying filter residue is transferred to tube furnace, under the conditions of temperature is 280 DEG C, after insulation roasting 4h, room temperature is cooled to the furnace, goes out
Material, obtains modified meerschaum；Count in parts by weight, take 15 parts of metal salt solutions, 80 parts of urea liquids, 10 parts of Pasteur's gemma bars successively
Bacterium bacterium solution, 60 parts of lime stones, after being first stirred lime stone and urea liquid, is poured into fermentation tank, then into fermentation tank according to
Secondary addition metal salt solution and Bacillus pasteurii bacterium solution, are 32 DEG C in temperature, under the conditions of rotating speed is 200r/min, constant temperature stirs
36h is reacted, discharging, obtains fermentation material, and gained fermentation material is moved into Rotary Evaporators, is 700kPa in pressure, temperature is 70 DEG C
Under the conditions of, be concentrated under reduced pressure 4h, obtains concentrate feed, then gained concentrate feed is dried 24h under the conditions of temperature is 80 DEG C, and discharging, obtains dry
Dry material；Gained dried feed is then transferred to tube furnace, 115 DEG C are warming up to 5 DEG C/min rate programs, after insulation reaction 60min,
Continue to be warming up to 200 DEG C with 6 DEG C/min rate programs, after insulation reaction 60min, continue to be warming up to 20 DEG C/min rate programs
920 DEG C, after insulation reaction 5min, cool to room temperature with the furnace, discharge, obtain roasting material；Count in parts by weight, take 100 parts of roastings successively
Imitation frosted glass, 10 parts of modified meerschaums, 30 parts of activated carbons, add in ball grinder, and are 20 by ball material mass ratio：1 adds zirconia ball
Pearl is ground, after ball milling mixing 4h, discharging, up to the special sulphur-fixing agent of flue gas desulfurization.The metal salt solution is by following parts by weight
Raw material configuration forms：15 parts of calcium nitrate, 30 parts of magnesium nitrates, 200 parts of water.The Bacillus pasteurii bacterium solution is by following parts by weight
Number raw material configuration forms：5 parts of Bacillus pasteuriis, 0.2 part of glucose, 8 parts of glycerine, 8 parts of ethylene glycol, 150 parts of deionized waters.Institute
It is powdered activated carbon to state activated carbon.
Example 3
It is 1 in mass ratio：15 pour into sepiolite and mass fraction in beaker for 15% hydrochloric acid, and beaker is transferred to ultrasound and is shaken
Instrument is swung, under the conditions of supersonic frequency is 50kHz, after sonic oscillation reaction 4h, filtering, obtains filter residue, and filter is washed with deionized
Slag 5 times, then the filter residue after washing is transferred in baking oven, dried under the conditions of being 110 DEG C in temperature to constant weight, obtain dry filter residue, then
Gained drying filter residue is transferred to tube furnace, under the conditions of temperature is 280 DEG C, after insulation roasting 4h, room temperature is cooled to the furnace, goes out
Material, obtains modified meerschaum；Lime stone is poured into pulverizer, 120 mesh sieves are crossed after crushing, obtain agstone, then by gained lime
Mountain flour and water are 1 in mass ratio：6 mixing pour into plastic beaker, then by plastic beaker move into refrigerator in, in temperature be -30 DEG C
Under the conditions of freeze 6h after, then by beaker move into thermostat water bath in, in temperature be 50 DEG C under the conditions of, defrosting 5h, so freezing solution
Freeze circulation 10 times, material in plastic beaker after collection last time is thawed, then through vacuum freeze drying, obtain pretreatment lime stone；
Count in parts by weight, take 15 parts of calcium nitrate solutions, 80 parts of urea liquids, 10 parts of Bacillus pasteurii bacterium solutions, 60 parts of pre- places successively
Reason stone lime stone, after being first stirred pretreatment lime stone and urea liquid, is poured into fermentation tank, then is added successively into fermentation tank
Enter calcium nitrate solution and Bacillus pasteurii bacterium solution, be 32 DEG C in temperature, under the conditions of rotating speed is 200r/min, constant temperature stirring is reacted
36h, discharging, obtains fermentation material, and gained fermentation material is moved into Rotary Evaporators, is 700kPa in pressure, temperature is 70 DEG C of conditions
Under, be concentrated under reduced pressure 4h, obtains concentrate feed, then gained concentrate feed is dried 24h under the conditions of temperature is 80 DEG C, and discharging, obtains dried feed；
Gained dried feed is then transferred to tube furnace, 115 DEG C are warming up to 5 DEG C/min rate programs, after insulation reaction 60min, is continued
200 DEG C are warming up to 6 DEG C/min rate programs, after insulation reaction 60min, continue to be warming up to 920 with 20 DEG C/min rate programs
DEG C, after insulation reaction 5min, cool to room temperature with the furnace, discharge, obtain roasting material；Count in parts by weight, take 100 parts of roastings successively
Material, 10 parts of modified meerschaums, 30 parts of activated carbons, add in ball grinder, and are 20 by ball material mass ratio：1 adds zirconium oxide ball milling
Pearl, after ball milling mixing 4h, discharging, up to the special sulphur-fixing agent of flue gas desulfurization.The Bacillus pasteurii bacterium solution is by following weight
The configuration of number raw material forms：5 parts of Bacillus pasteuriis, 0.2 part of glucose, 8 parts of glycerine, 8 parts of ethylene glycol, 150 parts of deionized waters.
The activated carbon is powdered activated carbon.
Example 4
It is 1 in mass ratio：15 pour into sepiolite and mass fraction in beaker for 15% hydrochloric acid, and beaker is transferred to ultrasound and is shaken
Instrument is swung, under the conditions of supersonic frequency is 50kHz, after sonic oscillation reaction 4h, filtering, obtains filter residue, and filter is washed with deionized
Slag 5 times, then the filter residue after washing is transferred in baking oven, dried under the conditions of being 110 DEG C in temperature to constant weight, obtain dry filter residue, then
Gained drying filter residue is transferred to tube furnace, under the conditions of temperature is 280 DEG C, after insulation roasting 4h, room temperature is cooled to the furnace, goes out
Material, obtains modified meerschaum；Lime stone is poured into pulverizer, 120 mesh sieves are crossed after crushing, obtain agstone, then by gained lime
Mountain flour and water are 1 in mass ratio：6 mixing pour into plastic beaker, then by plastic beaker move into refrigerator in, in temperature be -30 DEG C
Under the conditions of freeze 6h after, then by beaker move into thermostat water bath in, in temperature be 50 DEG C under the conditions of, defrosting 5h, so freezing solution
Freeze circulation 10 times, material in plastic beaker after collection last time is thawed, then through vacuum freeze drying, obtain pretreatment lime stone；
Count in parts by weight, take 15 parts of metal salt solutions, 80 parts of urea liquids, 10 parts of Bacillus pasteurii bacterium solutions, 60 parts of pre- places successively
Reason stone lime stone, after being first stirred pretreatment lime stone and urea liquid, is poured into fermentation tank, then is added successively into fermentation tank
Enter metal salt solution and Bacillus pasteurii bacterium solution, be 32 DEG C in temperature, under the conditions of rotating speed is 200r/min, constant temperature stirring is reacted
36h, discharging, obtains fermentation material, and gained fermentation material is moved into Rotary Evaporators, is 700kPa in pressure, temperature is 70 DEG C of conditions
Under, be concentrated under reduced pressure 4h, obtains concentrate feed, then gained concentrate feed is dried 24h under the conditions of temperature is 80 DEG C, and discharging, obtains dried feed；
Gained dried feed is then transferred to tube furnace, 115 DEG C are warming up to 5 DEG C/min rate programs, after insulation reaction 60min, is continued
200 DEG C are warming up to 6 DEG C/min rate programs, after insulation reaction 60min, continue to be warming up to 920 with 20 DEG C/min rate programs
DEG C, after insulation reaction 5min, cool to room temperature with the furnace, discharge, obtain roasting material；Count in parts by weight, take 100 parts of roastings successively
Material, 10 parts of modified meerschaums, 30 parts of activated carbons, add in ball grinder, and are 20 by ball material mass ratio：1 adds zirconium oxide ball milling
Pearl, after ball milling mixing 4h, discharging, up to the special sulphur-fixing agent of flue gas desulfurization.The metal salt solution is former by following parts by weight
Material configuration forms：15 parts of calcium chloride, 30 parts of magnesium chlorides, 200 parts of water.The Bacillus pasteurii bacterium solution is by following parts by weight
Raw material configuration forms：5 parts of Bacillus pasteuriis, 0.2 part of glucose, 8 parts of glycerine, 8 parts of ethylene glycol, 150 parts of deionized waters.It is described
Activated carbon is powdered activated carbon.
Example 5
It is 1 in mass ratio：15 pour into sepiolite and mass fraction in beaker for 15% hydrochloric acid, and beaker is transferred to ultrasound and is shaken
Instrument is swung, under the conditions of supersonic frequency is 50kHz, after sonic oscillation reaction 4h, filtering, obtains filter residue, and filter is washed with deionized
Slag 5 times, then the filter residue after washing is transferred in baking oven, dried under the conditions of being 110 DEG C in temperature to constant weight, obtain dry filter residue, then
Gained drying filter residue is transferred to tube furnace, under the conditions of temperature is 280 DEG C, after insulation roasting 4h, room temperature is cooled to the furnace, goes out
Material, obtains modified meerschaum；Lime stone is poured into pulverizer, 120 mesh sieves are crossed after crushing, obtain agstone, then by gained lime
Mountain flour and water are 1 in mass ratio：6 mixing pour into plastic beaker, then by plastic beaker move into refrigerator in, in temperature be -30 DEG C
Under the conditions of freeze 6h after, then by beaker move into thermostat water bath in, in temperature be 50 DEG C under the conditions of, defrosting 5h, so freezing solution
Freeze circulation 10 times, material in plastic beaker after collection last time is thawed, then through vacuum freeze drying, obtain pretreatment lime stone；
Count in parts by weight, take 15 parts of metal salt solutions, 80 parts of urea liquids, 10 parts of Bacillus pasteurii bacterium solutions, 60 parts of pre- places successively
Reason stone lime stone, after being first stirred pretreatment lime stone and urea liquid, is poured into fermentation tank, then is added successively into fermentation tank
Enter metal salt solution and Bacillus pasteurii bacterium solution, be 32 DEG C in temperature, under the conditions of rotating speed is 200r/min, constant temperature stirring is reacted
36h, discharging, obtains fermentation material, and gained fermentation material is moved into Rotary Evaporators, is 700kPa in pressure, temperature is 70 DEG C of conditions
Under, be concentrated under reduced pressure 4h, obtains concentrate feed, then gained concentrate feed is dried 24h under the conditions of temperature is 80 DEG C, and discharging, obtains dried feed；
Gained dried feed is then transferred to tube furnace, 920 DEG C are warming up to 20 DEG C/min rate programs, after insulation reaction 5min, with stove
It is cooled to room temperature, discharges, obtain roasting material；Count in parts by weight, take 100 parts of roasting materials, 10 parts of modified meerschaums, 30 parts of work successively
Property charcoal, add ball grinder in, and by ball material mass ratio be 20：1 adds zirconium oxide ball milling pearl, after ball milling mixing 4h, discharging, to obtain the final product
The special sulphur-fixing agent of flue gas desulfurization.The metal salt solution is formed by the configuration of following parts by weight raw material：15 parts of calcium nitrate, 30 parts
Magnesium nitrate, 200 parts of water.The Bacillus pasteurii bacterium solution is formed by the configuration of following parts by weight raw material：5 parts of Pasteur's gemma bars
Bacterium, 0.2 part of glucose, 8 parts of glycerine, 8 parts of ethylene glycol, 150 parts of deionized waters.The activated carbon is powdered activated carbon.
Example 6
Lime stone is poured into pulverizer, 120 mesh sieves are crossed after crushing, obtain agstone, then gained agstone and water are pressed into matter
Amount is than being 1：6 mixing are poured into plastic beaker, then plastic beaker is moved into refrigerator, and 6h is freezed under the conditions of being -30 DEG C in temperature
Afterwards, then by beaker move into thermostat water bath, under the conditions of temperature is 50 DEG C, defrosting 5h, such freeze-thaw circulation 10 times, is received
Material in plastic beaker after collection last time is thawed, then through vacuum freeze drying, obtain pretreatment lime stone；Count in parts by weight,
15 parts of metal salt solutions are taken successively, and 80 parts of urea liquids, 10 parts of Bacillus pasteurii bacterium solutions, 60 parts of pretreatment lime stones, first will
After pretreatment lime stone and urea liquid are stirred, pour into fermentation tank, then metal salt solution is sequentially added into fermentation tank
It it is 32 DEG C in temperature, under the conditions of rotating speed is 200r/min, constant temperature stirring reaction 36h, discharging, obtains with Bacillus pasteurii bacterium solution
Fermentation material, and gained fermentation material is moved into Rotary Evaporators, it is 700kPa in pressure, under the conditions of temperature is 70 DEG C, is concentrated under reduced pressure
4h, obtains concentrate feed, then gained concentrate feed is dried 24h under the conditions of temperature is 80 DEG C, and discharging, obtains dried feed；Then by gained
Dried feed is transferred to tube furnace, and 115 DEG C are warming up to 5 DEG C/min rate programs, after insulation reaction 60min, continues with 6 DEG C/min speed
Rate temperature programming after insulation reaction 60min, continues to be warming up to 920 DEG C with 20 DEG C/min rate programs, insulation reaction to 200 DEG C
After 5min, room temperature is cooled to the furnace, discharge, obtain roasting material；Count in parts by weight, take 100 parts of roasting materials, 10 parts of Hai Pao successively
Stone, 30 parts of activated carbons, add in ball grinder, and are 20 by ball material mass ratio：1 adds zirconium oxide ball milling pearl, after ball milling mixing 4h,
Discharging, up to the special sulphur-fixing agent of flue gas desulfurization.The metal salt solution is formed by the configuration of following parts by weight raw material：15 parts of nitre
Sour calcium, 30 parts of magnesium nitrates, 200 parts of water.The Bacillus pasteurii bacterium solution is formed by the configuration of following parts by weight raw material：5 parts
Bacillus pasteurii, 0.2 part of glucose, 8 parts of glycerine, 8 parts of ethylene glycol, 150 parts of deionized waters.The activated carbon is powdered activated
Charcoal.
Example 7
It is 1 in mass ratio：15 pour into sepiolite and mass fraction in beaker for 15% hydrochloric acid, and beaker is transferred to ultrasound and is shaken
Instrument is swung, under the conditions of supersonic frequency is 50kHz, after sonic oscillation reaction 4h, filtering, obtains filter residue, and filter is washed with deionized
Slag 5 times, then the filter residue after washing is transferred in baking oven, dried under the conditions of being 110 DEG C in temperature to constant weight, obtain dry filter residue, then
Gained drying filter residue is transferred to tube furnace, under the conditions of temperature is 280 DEG C, after insulation roasting 4h, room temperature is cooled to the furnace, goes out
Material, obtains modified meerschaum；Lime stone is poured into pulverizer, 120 mesh sieves are crossed after crushing, obtain agstone, then by gained lime
Mountain flour and water are 1 in mass ratio：6 mixing pour into plastic beaker, then by plastic beaker move into refrigerator in, in temperature be -30 DEG C
Under the conditions of freeze 6h after, then by beaker move into thermostat water bath in, in temperature be 50 DEG C under the conditions of, defrosting 5h, so freezing solution
Freeze circulation 10 times, material in plastic beaker after collection last time is thawed, then through vacuum freeze drying, obtain pretreatment lime stone；
Count in parts by weight, take 15 parts of metal salt solutions, 80 parts of urea liquids, 10 parts of Bacillus pasteurii bacterium solutions, 60 parts of pre- places successively
Reason stone lime stone, after being first stirred pretreatment lime stone and urea liquid, is poured into fermentation tank, then is added successively into fermentation tank
Enter metal salt solution and Bacillus pasteurii bacterium solution, be 32 DEG C in temperature, under the conditions of rotating speed is 200r/min, constant temperature stirring is reacted
36h, discharging, obtains fermentation material, and gained fermentation material is moved into Rotary Evaporators, is 700kPa in pressure, temperature is 70 DEG C of conditions
Under, be concentrated under reduced pressure 4h, obtains concentrate feed, then gained concentrate feed is dried 24h under the conditions of temperature is 80 DEG C, and discharging, obtains dried feed；
Gained dried feed is then transferred to tube furnace, 115 DEG C are warming up to 5 DEG C/min rate programs, after insulation reaction 60min, is continued
200 DEG C are warming up to 6 DEG C/min rate programs, after insulation reaction 60min, continue to be warming up to 920 with 20 DEG C/min rate programs
DEG C, after insulation reaction 5min, cool to room temperature with the furnace, discharge, obtain roasting material；Count in parts by weight, take 100 parts of roastings successively
Material, 10 parts of modified meerschaums, add in ball grinder, and are 20 by ball material mass ratio：1 adds zirconium oxide ball milling pearl, ball milling mixing
After 4h, discharging, up to the special sulphur-fixing agent of flue gas desulfurization.The metal salt solution is formed by the configuration of following parts by weight raw material：
15 parts of calcium nitrate, 30 parts of magnesium nitrates, 200 parts of water.The Bacillus pasteurii bacterium solution be by following parts by weight raw material configuration and
Into：5 parts of Bacillus pasteuriis, 0.2 part of glucose, 8 parts of glycerine, 8 parts of ethylene glycol, 150 parts of deionized waters.
Comparative example：The sulphur-fixing agent of Beijing Environmental Protection Technology Co., Ltd production.
The gained of example 1 to 7 sulphur-fixing agent and comparative example product are subjected to performance detection, specific testing result is as shown in table 1：
Table 1
| Detection content | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | Comparative example |
| Desulfuration efficiency/% | 87 | 73 | 68 | 70 | 75 | 72 | 67 | 50 |
From 1 testing result of table, the present invention gained special sulphur-fixing agent desulfuration efficiency of flue gas desulfurization is effectively improved.
Claims (6)
1. a kind of preparation method of the special sulphur-fixing agent of flue gas desulfurization, it is characterised in that specifically preparation process is：
（1）After lime stone is crushed, sieving, obtains agstone, then by gained agstone and water is 1 in mass ratio：4~1：6
After mixing, freeze-thaw circulation 8~10 times, then through vacuum freeze drying, obtain pretreatment lime stone；
（2）Count in parts by weight, take 10~15 parts of metal salt solutions, 60~80 parts of urea liquids, 8~10 parts of Pasteur's gemma successively
Pretreatment lime stone and urea liquid, are first stirred, add metal salt by bacillus bacterium solution, 40~60 parts of pretreatment lime stones
Solution and Bacillus pasteurii bacterium solution, after 24~36h is reacted in constant temperature stirring, concentrate, dry, obtain dried feed；
（3）Gained dried feed is transferred to tube furnace, is warming up to 110~115 DEG C with 3~5 DEG C/min rate programs, insulation reaction 45
After~60min, continue to be warming up to 190~200 DEG C with 4~6 DEG C/min rate programs, after 45~60min of insulation reaction, continue with
10~20 DEG C/min rate programs are warming up to 800~920 DEG C, after 3~5min of insulation reaction, cool to room temperature with the furnace, discharge, obtain
Roasting material；
（4）Count in parts by weight, take 80~100 parts of roasting materials, 8~10 parts of modified meerschaums, 20~30 parts of activated carbons, ball successively
Mill mixing, up to the special sulphur-fixing agent of flue gas desulfurization.
A kind of 2. preparation method of the special sulphur-fixing agent of flue gas desulfurization according to claim 1, it is characterised in that：Step（1）
The freeze-thaw circulation is：In temperature be -20~-30 DEG C under the conditions of, freeze 4~6h after, in temperature be 45~50 DEG C of conditions
Under, thaw 3~5h.
A kind of 3. preparation method of the special sulphur-fixing agent of flue gas desulfurization according to claim 1, it is characterised in that：Step（2）
The metal salt solution is formed by the configuration of following parts by weight raw material：10~15 parts of calcium nitrate, 20~30 parts of magnesium nitrates, 150
~200 parts of water.
A kind of 4. preparation method of the special sulphur-fixing agent of flue gas desulfurization according to claim 1, it is characterised in that：Step（2）
The Bacillus pasteurii bacterium solution is formed by the configuration of following parts by weight raw material：3~5 parts of Bacillus pasteuriis, 0.1~0.2
Part glucose, 4~8 parts of glycerine, 6~8 parts of ethylene glycol, 100~150 parts of deionized waters.
A kind of 5. preparation method of the special sulphur-fixing agent of flue gas desulfurization according to claim 1, it is characterised in that：Step（4）
The modified meerschaum modifying process is：It is 1 in mass ratio by sepiolite and hydrochloric acid：10~1：After 15 mixing, ultrasonic reaction, then
Filtered, washing, dry and roasting, obtain modified meerschaum.
A kind of 6. preparation method of the special sulphur-fixing agent of flue gas desulfurization according to claim 1, it is characterised in that：Step（4）
The activated carbon is any one in powdered activated carbon, granular activated carbon or spherical activated charcoal.
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