CN104436995B - A kind of method based on Sargassum Jiao's desulfurization denitration demercuration and the preparation method of Sargassum Jiao - Google Patents
A kind of method based on Sargassum Jiao's desulfurization denitration demercuration and the preparation method of Sargassum Jiao Download PDFInfo
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Abstract
A kind of method that the present invention relates to double spouted bed simultaneous SO_2 and NO removal demercuration burnt based on Sargassum, described method is to use Sargassum pyrolysis to produce biomass char as flue gas desulfurization and denitrification demercuration adsorbent, real simultaneous SO_2 and NO removal demercuration in spouted bed reactor；Sulfur nitrogen hydrargyrum resource reproducing adsorbent is reclaimed in membrane separator.The method and utilize Sargassum pyrolysis to produce biomass char simultaneous SO_2 and NO removal demercuration, subtractive process non-secondary pollution, and adsorbent raw material to be a kind of reserves Renewable resource widely, there is wide development and application prospect.
Description
Technical field
The present invention relates to combustion product gases pollutant catabolic gene field, be specifically related to a kind of double spouted bed burnt based on Sargassum desulfurization simultaneously
The method of denitration demercuration.
Background technology
Oxysulfide, nitrogen oxides and the hydrargyrum produced in combustion process can cause acid rain, photochemical fog and carcinogenic
With serious harms such as teratogenesis.Therefore, researching and developing effective flue gas desulfurization and denitrification demercuration method is the important of various countries' environmental protection scientific and technical personnel
One of task.
In the last few years, although being developed substantial amounts of flue gas desulfurization and denitrification demercuration technology, but due to the office of human cognitive process
Sex-limited and scientific technological advance gradual, existing various desulfurization denitration demercuration technology in research and development originally only for Single Pollution
Thing is removing target, removes while typically cannot realizing flue gas multiple pollutant.Such as, more flue gas desulfurization is applied at present
Denitration technology is mainly wet method limestone-gypsum method flue gas desulfurization technology and ammine selectivity catalytic reduction method.Though both approaches
So can individually desulphurization denitration, but all cannot realize removing in a reactor simultaneously.The associating superposition of two kinds of techniques
Can realize simultaneous SO_2 and NO removal although using, but to also result in whole system complicated simultaneously, floor space is big, invests and runs
High in cost of production is not enough.
It addition, along with environmental requirement is improved constantly by the mankind, the laws and regulations for mercury in flue gas emission control the most gradually go out
Platform, but there is presently no a kind of cost-effective flue gas demercuration technology and obtain large-scale commercial applications application.If in existing desulfurization
Again increase single flue gas mercury removal system with denitrating system afterbody, then certainly will will result in initial outlay and the operation of whole system
Expense sharply increases further, is finally difficult to obtain large-scale commercial applications application in developing country.
In sum, if it is possible to realize removing by oxysulfide, nitrogen oxides and hydrargyrum in a reactor simultaneously, then have
Hope complexity and the floor space of the system that is substantially reduced, and then reduce investment and the operating cost of system.Absorption method gas cleaning
Technology is a kind of traditional fume treatment technology, has that initial cost is little, technological process simple and is easily achieved multi-pollutant simultaneously
The features such as removing, are a kind of flue gases purifications with good development and application prospect, but traditional absorption method gas cleaning
The progress of technology is the slowest, and its main cause has three: first, existing ripe adsorbent, the most alive
Property charcoal, application cost is high, it is difficult to realize heavy industrialization application；Secondly, most Novel adsorptions of research at present
Generally there is the deficiencies such as cost height, poor stability and multi-pollutant removing ability in agent；Again, it is currently used for adsorbent
Reactor mainly have fixed bed and fluidized-bed reactor, the mass transfer rate of two kinds of reactors is the most relatively low.
But, many studies have shown that, the prevailing rate rate-determining steps of gas-solid reaction process is mass transport process.Therefore, develop low
Cost, good stability and there is the removal methods of multi-pollutant absorbability and to have the gas-solid adsorption of efficient mass transfer speed anti-
Answering device is one of key solving this problem.
Summary of the invention
In order to solve above-mentioned technical problem, the invention provides a kind double spouted bed desulfurization denitration demercuration based on Sargassum Jiao
Method, this method is to use Sargassum pyrolysis to produce biomass char as flue gas desulfurization and denitrification demercuration adsorbent, reacts at spouted bed
Reality simultaneous SO_2 and NO removal demercuration in device；Sulfur, nitrogen, hydrargyrum resource reproducing adsorbent is reclaimed in membrane separator.
The subtractive process principle of the present invention:
Shown in Fig. 1 and Fig. 5, the Sargassum coke adsorbent produced with Thallus Laminariae (Thallus Eckloniae), as representative, uses scanning electron microscope (SEM), X
Ray fluorescence spectra (XRF) and nitrogen adsorption method determine the surface appearance feature of adsorbent, main component and and content respectively
And the crucial thing chemical parameters such as the specific surface area of adsorbent and pore-size distribution, and the preliminary examinations absorption property of adsorbent.
Result shows, is alkali metal salt SiO2, the Al2O3 such as K, Ca with the Sargassum coke adsorbent main component that Thallus Laminariae (Thallus Eckloniae) is produced
Deng metal-oxide, adsorbent has bigger specific surface area and flourishing gap structure.These compositions are all good hydrargyrum
Adsorbing and removing material.Therefore, use Sargassum Jiao to adsorb de-desulfurization denitration demercuration, at technical method, there is feasibility.
For realizing object above, according to above-mentioned principle, the technical solution used in the present invention is as follows:
A kind of method of double spouted bed desulfurization denitration demercuration burnt based on Sargassum, adds Sargassum Jiao absorption in spouted bed reactor
Agent；Contain sulfur from burner, nitrogen, the flue gas of hydrargyrum are sprayed into spouted bed reactor by swirl nozzle, with spouted after supercooling
Sargassum coke adsorbent in bed reactor collides adsorption reaction；When a spouted bed reactor regeneration, from burner
Flue gas by automatic switchover flow into another spouted bed reactor, two spouted bed reactors intersect and use and regenerate.
Sargassum coke adsorbent is added by spouted bed reactor inlet a, and is discharged by spouted bed reactor outlet b；Burner
Being provided with two exhanst gas outlets, each exhanst gas outlet connects a spouted bed reactor in double spouted bed, and double spouted beds are by two
Individual identical spouted bed reactor is constituted, and two exhanst gas outlets are equipped with the flow direction valve for switching flue gas
V3, flue collector is provided with provides driven fan into flow of flue gas.
Flue gas is passed through swirl nozzle by spouted bed reactor inlet c and is sprayed into spouted bed after gas cooler cooling homoiothermic
Reactor, collides adsorption reaction with the Sargassum coke adsorbent in spouted bed reactor；Clean flue gas after purification passes through
It is passed through chimney and enters air after the electric scraping device of spouted bed reactor head, core separating plate and outlet g；Absorption is full
After Sargassum coke adsorbent after with is sucked membrane separator regeneration by spouted bed reactor outlet d by blower fan, then by spouted bed
Reactor inlet e is passed through spouted bed reactor cycles and uses；It is passed through nitrogen at membrane separator entrance f and rinses and carry Sargassum Jiao
Sulfur on adsorbent, nitrogen, hydrargyrum.
Spouted bed reactor head is provided with core separating plate, is mainly used in realizing the separation of adsorbent and flue gas, core separating plate
Average pore size require less than 50 microns, to prevent adsorbent from escaping with flue gas.Core separating plate bottom is provided with electric scraping
Plate, is made up of a word hairbrush and drive shaft, can be driven rotation by motor and move, and is mainly used in striking off the accumulation of core separating plate bottom
Adsorbent, prevent blocking.Swirl nozzle in spouted bed reactor use all swirl nozzles be arranged in have identical in
The radius of heart angle D with on the cross point of the concentric round wires of equidistant C.The model of nozzle or big I are according in reactor
The mixing uniformity scene of Gas-solid Two-phase Flow determines.
Flue-gas temperature from burner is cooled to 40 DEG C-150 DEG C by flue gas thermoregulator；SO in burner flue gas2、
NOx5000ppm, 2000ppm and 500 μ g/m it are not more than respectively with the entrance concentration of hydrargyrum3；The dosage of adsorbent
1kg-6kg is added by every cubic metre of spouted bed reactor volume.
Described membrane separator is a kind of membrane type gaseous jet simulation device, membrane material by polyacids amine, polyimide class, polysulfones,
One or more in the materials such as polyethylene acids, propylene analog derivative polymer and cellulose family are compound to be made.
The preparation method of a kind of Sargassum coke adsorbent, the method preparing adsorbent mainly comprises the steps that
Step 1: Sargassum dries under ventilation state and is ground into the Sargassum powder of 50-200 mesh naturally, is then placed in temperature control
In stirred tank, stir 2 hours at 60-90 DEG C with water, repeat five times；
Step 2: with water and nitric acid as mixed solvent, stirs 6 hours at 40-90 DEG C, is being ventilated by Sargassum powder after filtration
Naturally dry under state 240 hours.Naturally the Sargassum dried is dried 8 hours with 105 DEG C in temperature control drying baker, obtains
Obtain anhydrous Sargassum；
Step 3: anhydrous Sargassum is ground to form the Sargassum powder that particle diameter is 50-300 mesh and is placed in tube furnace, at 400-900 DEG C
CO is compared with certain volume2And N2Mixed atmosphere under be pyrolyzed 5-25 minute, be cooled to room temperature, obtain Sargassum biomass
Burnt；
Step 4: Sargassum biomass char grinds to form 50-300 mesh granule, soaks 12 in finite concentration vanadic salts solution
Hour, naturally dry under ventilation state after filtration 240 hours, be then dried with 110-220 DEG C in temperature control drying baker
6 hours, i.e. can get the demercuration adsorbent that Sargassum Jiao produces.
In described step 2, in mixed solvent, the mass percent of nitric acid is 2%-30%；CO in gaseous mixture2And N2Body
Long-pending ratio is 1: 1-1: 5；Vanadic salts refer in ammonium metavanadate, sodium metavanadate, potassium metavanadate, sodium vanadate one or both with
On mixture, in solution, the mass concentration of vanadic salts is 1%-15%.
Described Sargassum refer to the one in Thallus Laminariae (Thallus Eckloniae), Thallus Porphyrae, Thallus Laminariae, Gracilaria tenuistipitata, Alga Sgrgassi Enerves, Entermorpha and Thallus Gracilariae or
Two or more mixture.
Advantages of the present invention and remarkable result:
The method using the present invention, i.e. uses Sargassum pyrolysis to produce biomass char as flue gas demercuration adsorbent, anti-at spouted bed
Answer and device adsorbs demercuration (spouted bed reactor has high mass-transfer efficiency)；In membrane separator, reclaim hydrargyrum resource and regenerate
Adsorbent.It is former owing to the exploitation of current biomass resource are mainly with crops or the ground such as straw, timber biomass
On the one hand material, its result is to result in and the situation of the resource contention such as grain, arable land, water；On the other hand, above-mentioned raw materials
Development space is limited, and especially China's terrestrial life matter resource is extremely disperseed, and extensive focus utilization will cause manpower and fortune
Defeated cost sharply increases, and is difficult to meet the large-scale application demand of future market in the long run.
The exploitation of marine biomass resource provides a possible effective way for solving the problems referred to above.With Sargassum as representative
Marine biomass has following plurality of advantages: (1) yield is high, and available beachhead or salt-soda soil are cultivated on a large scale, it is simple to existing
Scale processing and transport are concentrated in field；(2) soil and freshwater resources it are not take up；(3) be conducive to protecting the marine environment,
Prevention Oceanic disasters (cultivation of Sargassum can effectively absorb eutrophication element, and suppression red tide occurs)；(4) light can be passed through
Cooperation is with absorbing CO2, produce significant reduction of greenhouse gas discharge benefit.Therefore, active development and utilize marine biomass resource
There is important theory significance and actual industrial is worth.
The present invention utilizes Sargassum to prepare Sargassum Jiao's flue gas to take off desulfurization denitration demercuration adsorbent simultaneously, the method cheaper starting materials is easy to get,
Wide material sources, technique are simple, non-secondary pollution, especially raw material are Renewable resources, inexhaustible, tool
There are good exploitation and industrial value.The present invention has good flue gas simultaneously by adsorbent prepared by certain technique and parameter
Desulfurization denitration demercuration performance.It is used in combination in conjunction with the spouted bed reactor with high mass-transfer efficiency, simultaneous SO_2 and NO removal demercuration
Efficiency is the highest can reach 98.6%, 92.3% and 100% respectively, is a kind of Novel flue gas with great development and application value
Desulfurization denitration demercuration method and device.
Accompanying drawing explanation
Fig. 1 is scanning electron microscope (SEM) figure of Sargassum coke adsorbent.
Fig. 2 is the process chart of the inventive method and device.
Fig. 3 is the layout drawing of swirl nozzle in the present invention spouted bed reactor.
Fig. 4 a be electric scraping plate of the present invention and the top view of core separating plate.
Fig. 4 b be electric scraping plate of the present invention and the front view of core separating plate.
The specific surface area of the nitrogen adsorption method test that Fig. 5 plant ash adsorbent uses and aperture result.
Detailed description of the invention
Below in conjunction with the accompanying drawings, the detailed description of the invention of the present invention is further described.
As in figure 2 it is shown, add Sargassum coke adsorbent in spouted bed reactor 3；Sulfur, nitrogen, hydrargyrum is contained from burner
Flue gas after supercooling, sprayed into spouted bed reactor 3 by swirl nozzle 7, with in spouted bed reactor 3 Sargassum Jiao inhale
The attached dose of adsorption reaction that collides；When a spouted bed reactor 3 regenerates, the flue gas from burner will automatically switch
Flowing into another spouted bed reactor 3, two spouted bed reactors 3 intersect and use and regenerate.
Sargassum coke adsorbent is added by spouted bed reactor inlet a, and is discharged by spouted bed reactor outlet b；Burner
Being provided with two exhanst gas outlets, each exhanst gas outlet connects a spouted bed reactor 3 in double spouted bed, two exhanst gas outlets
On be equipped with the flow direction valve V3 for switching flue gas, flue collector be provided with into flow of flue gas provide driven fan.
Flue gas is passed through swirl nozzle 7 by spouted bed reactor inlet c and is sprayed into spray after gas cooler 2 cools down homoiothermic
Movable bed reactor 3, collides adsorption reaction with the Sargassum coke adsorbent in spouted bed reactor 3；Cleaning after purification
Flue gas is by being passed through chimney side by side after the electric scraping device 5 at spouted bed reactor 3 top, core separating plate 6 and outlet g
Enter air；Adsorb saturated after Sargassum coke adsorbent by spouted bed reactor outlet d by blower fan suck membrane separator 4 again
After life, then it is passed through the use of spouted bed reactor cycles by spouted bed reactor inlet e；It is passed through nitrogen at membrane separator entrance f
Rinse and carry the sulfur on Sargassum coke adsorbent, nitrogen, hydrargyrum.
As shown in figures 4 a and 4b, spouted bed reactor head is provided with core separating plate, be mainly used in realizing adsorbent and
The separation of flue gas, the average pore size of core separating plate requires less than 50 microns, to prevent adsorbent from escaping with flue gas.Core
Separating plate bottom is provided with electric scraping plate, is made up of a word hairbrush and drive shaft, can be driven rotation by motor and move, be mainly used in
Strike off the adsorbent of core separating plate bottom accumulation, prevent blocking.
As it is shown on figure 3, the arrangement that the swirl nozzle in spouted bed reactor uses, the most all swirl nozzles are all arranged
On the cross point of the concentric round wires of the radius with equidistant C with identical central angle D.The model of nozzle or big I
Determine according to the mixing uniformity scene of Gas-solid Two-phase Flow in reactor.
The Sargassum coke adsorbent used is to be passed through furnace high-temperature cracking by the Sargassum that China's Coastal Areas is widely distributed.Described
Sargassum refer to the one in Thallus Laminariae (Thallus Eckloniae), Thallus Porphyrae, Thallus Laminariae, Gracilaria tenuistipitata, Alga Sgrgassi Enerves, Entermorpha and Thallus Gracilariae or two or more
Mixture.The method preparing adsorbent mainly comprises the steps that step 1: naturally dried under ventilation state by Sargassum
And it is ground into the Sargassum powder of 50-200 mesh, it is then placed in temperature control stirred tank, stirs 2 hours at 60-90 DEG C with water,
Repeat five times；Step 2: with water and nitric acid as mixed solvent, stirs 6 hours, by Sargassum powder after filtration at 40-90 DEG C
Naturally dry under ventilation state 240 hours.Naturally the Sargassum dried is dried 8 with 105 DEG C in temperature control drying baker little
Time, it is thus achieved that anhydrous Sargassum；Step 3: anhydrous Sargassum is ground to form the Sargassum powder that particle diameter is 50-300 mesh and is placed in tube furnace,
CO is compared at 400-900 DEG C and certain volume2And N2Mixed atmosphere under be pyrolyzed 5-25 minute, be cooled to room temperature, obtain
Sargassum biomass char；Step 4: Sargassum biomass char is ground to form 50-300 mesh granule, molten at finite concentration vanadic salts
Liquid soaks 12 hours, under ventilation state, after filtration, naturally dries 240 hours, then in temperature control drying baker with
110-220 DEG C is dried 6 hours, i.e. can get the demercuration adsorbent that Sargassum Jiao produces；Nitric acid in described mixed solvent
Mass percent is 2%-30%, CO in gaseous mixture2And N2Volume ratio be 1: 1-1: 5, vanadic salts refer to ammonium metavanadate,
In one or more mixture solution in sodium metavanadate, potassium metavanadate, sodium vanadate, the mass concentration of vanadic salts is
1%-15%.
Embodiment one
Sargassum dries under ventilation state and is chopped into the Sargassum powder of 100 mesh naturally, is then placed in temperature control stirred tank,
Stir 2 hours at 60 DEG C with water, repeat five times.(the quality of nitric acid in mixed solvent with water and nitric acid as mixed solvent
Percent is 10%), stir 6 hours at 40 DEG C, after filtration, Sargassum is dried 240 hours under ventilation state naturally.
Naturally the Sargassum dried is dried 8 hours with 105 DEG C in temperature control drying baker, it is thus achieved that anhydrous Sargassum.By anhydrous Sargassum powder
It is broken into the Sargassum powder that particle diameter is 100 mesh to be placed in tube furnace, at CO2And N2Volume ratio is under the mixed atmosphere of 1: 2,
It is pyrolyzed 15 minutes with 500 DEG C, is cooled to room temperature, obtains Sargassum biomass char.Sargassum biomass char is ground into
100 mesh granules, soak 12 hours, in gravity-flow ventilation condition after filtration in the ammonium metavanadate solution that mass fraction is 10%
Under dry 240 hours, be then dried with 120 DEG C in temperature control drying baker and within 6 hours, i.e. can get the suction of Sargassum flue gas demercurations
Attached dose.The dosage of adsorbent adds 2kg by every cubic metre of spouted bed reactor volume, and flue-gas temperature is 80 DEG C.Inhale
Attached dose of performance test shows: simultaneous SO_2 and NO removal demercuration efficiency is respectively 78.6%, 60.3% and 89.8%.
Embodiment two
Sargassum dries under ventilation state and is chopped into the Sargassum powder of 100 mesh naturally, is then placed in temperature control stirred tank,
Stir 2 hours at 80 DEG C with water, repeat five times.(the quality of nitric acid in mixed solvent with water and nitric acid as mixed solvent
Percent is 20%), stir 6 hours at 60 DEG C, after filtration, Sargassum is dried 240 hours under ventilation condition naturally.
Naturally the Sargassum dried is dried 8 hours with 105 DEG C in temperature control drying baker, it is thus achieved that anhydrous Sargassum.By anhydrous Sargassum powder
It is broken into the Sargassum powder that particle diameter is 100 mesh to be placed in tube furnace, at CO2And N2Volume ratio is under the mixed atmosphere of 1: 1,
It is pyrolyzed 15 minutes with 500 DEG C, is cooled to room temperature, obtains Sargassum biomass char.Sargassum biomass char is ground into
100 mesh granules, soak 12 hours in the sodium metavanadate solution that mass fraction is 5%, and at gravity-flow ventilation bar after filtration
Dry under part 240 hours, be then dried with 130 DEG C in temperature control drying baker and i.e. can get Sargassum flue gas demercuration in 6 hours
Adsorbent.The dosage of adsorbent adds 3kg by every cubic metre of spouted bed reactor volume, and flue-gas temperature is 80 DEG C.
Performance of the adsorbent test shows: simultaneous SO_2 and NO removal demercuration efficiency is respectively 84.6%, 63.3% and 92.7%.
Embodiment three
Sargassum dries under ventilation state and is chopped into the Sargassum powder of 150 mesh naturally, is then placed in temperature control stirred tank,
Stir 2 hours at 80 DEG C with water, repeat five times.(the quality of nitric acid in mixed solvent with water and nitric acid as mixed solvent
Percent is 25%), stir 6 hours at 80 DEG C, after filtration, Sargassum is dried 240 hours under ventilation state naturally.
Naturally the Sargassum dried is dried 8 hours with 105 DEG C in temperature control drying baker, it is thus achieved that anhydrous Sargassum.By anhydrous Sargassum powder
It is broken into the Sargassum powder that particle diameter is 100 mesh to be placed in tube furnace, at CO2And N2Volume ratio is under the mixed atmosphere of 1: 2,
It is pyrolyzed 15 minutes with 700 DEG C, is cooled to room temperature, obtains Sargassum biomass char.Sargassum biomass char is ground into
150 mesh granules, soak 12 hours in the sodium metavanadate solution that mass fraction is 10%, and at gravity-flow ventilation bar after filtration
Dry under part 240 hours, be then dried with 150 DEG C in temperature control drying baker and i.e. can get Sargassum flue gas demercuration in 6 hours
Adsorbent.The dosage of adsorbent adds 4kg by every cubic metre of spouted bed reactor volume, and flue-gas temperature is 80 DEG C.
Performance of the adsorbent test shows: simultaneous SO_2 and NO removal demercuration efficiency is respectively 91.6%, 70.9% and 95.5%.
Embodiment four
Sargassum dries under ventilation state and is chopped into the Sargassum powder of 100 mesh naturally, is then placed in temperature control stirred tank,
Stir 2 hours at 60 DEG C with water, repeat five times.(the quality of nitric acid in mixed solvent with water and nitric acid as mixed solvent
Percent is 20%), stir 6 hours at 70 DEG C, after filtration, Sargassum is dried 240 hours under ventilation state naturally.
Naturally the Sargassum dried is dried 8 hours with 105 DEG C in temperature control drying baker, it is thus achieved that anhydrous Sargassum.By anhydrous Sargassum powder
It is broken into the Sargassum powder that particle diameter is 200 mesh to be placed in tube furnace, at CO2And N2Volume ratio is under the mixed atmosphere of 1: 4,
It is pyrolyzed 20 minutes with 600 DEG C, is cooled to room temperature, obtain Sargassum biomass char and inhale.Sargassum biomass char is ground into
200 mesh granules, soak 12 hours in the ammonium metavanadate solution that mass fraction is 15%, and at gravity-flow ventilation bar after filtration
Dry under part 240 hours, be then dried with 160 DEG C in temperature control drying baker and i.e. can get Sargassum flue gas demercuration in 6 hours
Adsorbent.The dosage of adsorbent adds 5kg by every cubic metre of spouted bed reactor volume, and flue-gas temperature is 80 DEG C.
Performance of the adsorbent test shows: simultaneous SO_2 and NO removal demercuration efficiency is respectively 96.5%, 80.1% and 100%.
Embodiment five
Sargassum dries under ventilation state and is chopped into the Sargassum powder of 200 mesh naturally, is then placed in temperature control stirred tank,
Stir 2 hours at 70 DEG C with water, repeat five times.(the quality of nitric acid in mixed solvent with water and nitric acid as mixed solvent
Percent is 5%), stir 6 hours at 70 DEG C, after filtration, Sargassum is dried 240 hours under ventilation state naturally.
Naturally the Sargassum dried is dried 8 hours with 105 DEG C in temperature control drying baker, it is thus achieved that anhydrous Sargassum.By anhydrous Sargassum powder
It is broken into the Sargassum powder that particle diameter is 100 mesh to be placed in tube furnace, at CO2And N2Volume ratio is under the mixed atmosphere of 1: 5,
It is pyrolyzed 5 minutes with 400 DEG C, is cooled to room temperature, obtains Sargassum biomass char.Sargassum biomass char is ground into 100
Mesh granule, soaks 12 hours in the potassium metavanadate solution that mass fraction is 5%, and after filtration under the conditions of gravity-flow ventilation
Dry 240 hours, be then dried with 190 DEG C in temperature control drying baker and within 6 hours, i.e. can get the absorption of Sargassum flue gas demercuration
Agent.The dosage of adsorbent adds 6kg by every cubic metre of spouted bed reactor volume, and flue-gas temperature is 60 DEG C.Absorption
Agent performance test shows: simultaneous SO_2 and NO removal demercuration efficiency is respectively 100%, 87.6% and 100%.
Embodiment six
Sargassum dries under ventilation state and is chopped into the Sargassum powder of 200 mesh naturally, is then placed in temperature control stirred tank,
Stir 2 hours at 80 DEG C with water, repeat five times.(the quality of nitric acid in mixed solvent with water and nitric acid as mixed solvent
Percent is 25%), stir 6 hours at 60 DEG C, after filtration, Sargassum is dried 240 hours under ventilation state naturally.
Naturally the Sargassum dried is dried 8 hours with 105 DEG C in temperature control drying baker, it is thus achieved that anhydrous Sargassum.By anhydrous Sargassum powder
It is broken into the Sargassum powder that particle diameter is 150 mesh to be placed in tube furnace, at CO2And N2Volume ratio is under the mixed atmosphere of 1: 4,
It is pyrolyzed 10 minutes with 700 DEG C, is cooled to room temperature, obtains Sargassum biomass char.Sargassum biomass char is ground into
150 mesh granules, soak 12 hours in the sodium vanadate solution that mass fraction is 20%, and at gravity-flow ventilation bar after filtration
Dry under part 240 hours, be then dried with 200 DEG C in temperature control drying baker and i.e. can get Sargassum flue gas demercuration in 6 hours
Adsorbent.The dosage of adsorbent adds 6kg by every cubic metre of spouted bed reactor volume, and flue-gas temperature is 120 DEG C.
Performance of the adsorbent test shows: simultaneous SO_2 and NO removal demercuration efficiency is respectively 94.8%, 80.6% and 100%.
In sum, the adsorbent preparation parameter in embodiment five and method are Sargassum flue gas demercuration disclosed by the invention absorption
Agent most preferably prepare scheme, prepare adsorbent by the program, simultaneous SO_2 and NO removal demercuration efficiency respectively reaches 100%, 87.6%
With 100%.
Claims (6)
1. the method for a double spouted bed desulfurization denitration demercuration based on Sargassum Jiao, it is characterised in that add Sargassum coke adsorbent in spouted bed reactor；The flue gas containing sulfur nitrogen hydrargyrum from burner is sprayed into spouted bed reactor by swirl nozzle after supercooling, collides adsorption reaction with the Sargassum coke adsorbent in spouted bed reactor；When a spouted bed reactor regeneration, automatic switchover is flowed into another spouted bed reactor by the flue gas from burner, and two spouted bed reactors intersect and use and regenerate；Sargassum coke adsorbent is added by spouted bed reactor inlet a, and is discharged by spouted bed reactor outlet b；Burner is provided with two exhanst gas outlets, and each exhanst gas outlet connects a spouted bed reactor in double spouted bed, and two exhanst gas outlets are equipped with the flow direction valve V3 for switching flue gas, and flue collector is provided with provides driven fan into flow of flue gas；Flue gas is passed through swirl nozzle by spouted bed reactor inlet c and sprays into spouted bed reactor after the cooling homoiothermic of flue gas thermoregulator, collides adsorption reaction with the Sargassum coke adsorbent in spouted bed reactor；Clean flue gas after purification is by being passed through chimney and enter air after the electric scraping device core separating plate of spouted bed reactor head and outlet g；Adsorb saturated after Sargassum coke adsorbent by spouted bed reactor outlet d by blower fan suck membrane separator regenerate after, then by spouted bed reactor inlet e be passed through spouted bed reactor cycles use；It is passed through the sulfur nitrogen hydrargyrum that nitrogen rinses and carry on Sargassum coke adsorbent at membrane separator entrance f.
The method of a kind of double spouted bed desulfurization denitration demercuration burnt based on Sargassum the most according to claim 1, it is characterised in that: the flue-gas temperature from burner is cooled to 40 DEG C-150 DEG C by flue gas thermoregulator；In burner flue gas, the entrance concentration of SO2, NOx and hydrargyrum is not more than 5000ppm, 2000ppm and 500 respectively；The dosage of Sargassum coke adsorbent adds 1kg-6kg by every cubic metre of spouted bed reactor volume.
The method of a kind of double spouted bed desulfurization denitration demercuration burnt based on Sargassum the most according to claim 1, it is characterized in that: described membrane separator is a kind of membrane type gaseous jet simulation device, membrane material is made by one or more in polyacids amine, polyimide class, polysulfones, polyethylene acids, propylene analog derivative polymer and cellulosic material are compound.
A kind of method of the double spouted bed desulfurization denitration demercuration burnt based on Sargassum, the preparation method of its Sargassum coke adsorbent, it is characterised in that: the method for preparation Sargassum coke adsorbent mainly comprises the steps that
Step 1: Sargassum dries under ventilation state and is ground into the Sargassum powder of 50-200 mesh naturally, is then placed in temperature control stirred tank, stir 2 hours with water at 60-90 DEG C, repeats five times；
Step 2: with water and nitric acid as mixed solvent, stirs 6 hours at 40-90 DEG C, naturally is dried 240 hours by Sargassum powder after filtration under ventilation state, by the Sargassum naturally dried in temperature control drying baker with 105 DEG C dry 8 hours, it is thus achieved that anhydrous Sargassum；
Step 3: anhydrous Sargassum grinds to form the Sargassum powder that particle diameter is 50-300 mesh and is placed in tube furnace, is pyrolyzed 5-25 minute under 400-900 DEG C and the certain volume mixed atmosphere than CO2 and N2, is cooled to room temperature, obtains Sargassum biomass char；
Step 4: Sargassum biomass char is ground to form 50-300 mesh granule, finite concentration vanadic salts solution soaks 12 hours, naturally dry under ventilation state 240 hours after filtration, then it is dried 6 hours with 110-220 DEG C in temperature control drying baker, i.e. can get the Sargassum coke adsorbent of the desulfurization denitration demercuration that Sargassum Jiao produces.
The method of a kind of double spouted bed desulfurization denitration demercuration burnt based on Sargassum the most according to claim 4, it is characterised in that: in described step 2, in mixed solvent, the mass percent of nitric acid is 2%-30%；In gaseous mixture, the volume ratio of CO2 and N2 is 1:1-1:5；Vanadic salts refers to one or more the mixture in ammonium metavanadate sodium metavanadate potassium metavanadate sodium vanadate, and in solution, the mass concentration of vanadic salts is 1%-15%.
6. according to the method for claim 4 one kind double spouted bed desulfurization denitration demercuration based on Sargassum Jiao, it is characterised in that: described Sargassum refers to a kind of or two or more mixture in Thallus Laminariae (Thallus Eckloniae) Thallus Porphyrae Thallus Laminariae Gracilaria tenuistipitata Alga Sgrgassi Enerves Entermorpha and Thallus Gracilariae.
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