CN107159088A - Mercury material is received with lasting absorption property - Google Patents
Mercury material is received with lasting absorption property Download PDFInfo
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- CN107159088A CN107159088A CN201710334404.8A CN201710334404A CN107159088A CN 107159088 A CN107159088 A CN 107159088A CN 201710334404 A CN201710334404 A CN 201710334404A CN 107159088 A CN107159088 A CN 107159088A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
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- 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
- B01D53/64—Heavy metals or compounds thereof, e.g. mercury
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- 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
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
- B01J20/0281—Sulfates of compounds other than those provided for in B01J20/045
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
- B01J20/0288—Halides of compounds other than those provided for in B01J20/046
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2257/00—Components to be removed
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- B01D2257/602—Mercury or mercury compounds
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Abstract
It is a kind of to receive mercury material with lasting absorption property the present invention relates to the depollution of environment and protection field.A kind of compound alumina ceramic material is prepared as carrier using Foam dipping method first, method is then moistened using leaching activating agent is supported in carrier surface and its micropore, the requirement of activating agent area coverage reaches more than 85%.Elemental Mercury is fixed to the oxidation of mercury using chlorion, sulfate radical and nitrate ion in activating agent, glues molten Elemental Mercury using silver and mercury formation amalgam reaction, valence state mercury is adsorbed using the huge surface area of porous ceramics.Mercury is reclaimed finally by Low Temperature Thermal desorption method, and realizes that carrier loop is utilized.The performance such as this material not only has that surface area is big, permeability is strong, compressive strength is high, impact resistance, high temperature resistant, environmentally friendly and chemical stability are high, and carrier can recycle, and mercury reclaims simple and easy to apply, does not result in secondary pollution.In addition, material preparation process is simple, it is with low cost.With good application potential and good economic results in society.
Description
Technical field
The present invention relates to the depollution of environment with protection field, concrete application field be non-ferrous metal metallurgy, PVC chemical industries,
Incineration of waste waste gas, it is coal fire discharged during a kind of persistence of mercurous waste gas pollution control and treatment application receive mercury material.
Background technology
Mercury is to be discharged into one of stronger heavy metal element of air Poisoning, and human health and air quality are endangered very
Greatly.It or a kind of pollutant of global migration, mercury pollution problem have become the focus of global concern.
In order to realize the industries such as chemical industry, mining, smelting, fire coal, hospital, factory or department in production or the course of work to
The waste gas of outer discharge and the reasonable control of mercury in flue gas content, foreign countries have carried out the substantial amounts of research on mercury removal technical elements
Work.The mercury discharged in industrial production mainly includes gaseous elemental mercury Hg, gaseous oxygen compound mercury Hg2+With solid granulates mercury Hg tri-
Plant form.The U.S. uses activated carbon spraying technique（ACI）Remove coal-fired flue-gas in mercury, inhale mercury after activated carbon granule again by except
Dirt device is captured.Because the mercury of activated carbon surface easily evaporates effusion, demercuration efficiency is caused to decline, therefore using halogen, sulphur, metal
And metal oxide etc. is modified processing to activated carbon.Not only mercury is prevented to be desorbed, and in activated carbon surface there is provided more
Mercury bound site, so as to improve demercuration ability.But the activated carbon adsorptive capacity of unit volume is limited, causes activated carbon to consume
Amount is huge, and ACI technologies operation cost of investment is too high.Therefore, cigarette is adsorbed using flying dust or other combustion by-products in part power plant
A part of gaseous mercury in coal combustion, and start to consider to refill the flying dust being collected into flue gas to reach demercuration purpose.
For example, Ya Fudun companies use certain emission in burner to remove mercurous material, General Corporation utilizes the coal of partial gasification
The removal of mercury is carried out, The Board of Control for Michigan Technological Univ. controls mercury emissions using unburned charcoal in combustion by-products.It is overall
From the point of view of, carbon-supported catalyst mercury removal efficiency is not high, and can have a negative impact to the comprehensive utilization of coal-fired power station boiler flying dust.And
Calcium radical species are easily obtained, cheap, while being SO in removing flue gas again2Effective desulfurizing agent.PSI mechanisms of the U.S. are found
Zeolitic material has the ability of Adsorption of Mercury, and the adsorbent of mercury emissions is controlled as Industrial Boiler.But, due to zeolite sheet
Body is not strong to the adsorption capacity of mercury, for improve unit volume zeolite removal efficiency of mercury, then can by additive to zeolite at
Reason, to increase substantially the adsorption capacity to mercury.But the easy moisture absorption of calcium radical species comes off, laboratory research rank is still at present
Section, and it is introduced into the commercial Application stage.HIT uses SCR（SCR）Denitrating catalyst is to coal-fired electricity
Mercury in factory's tail gas is removed, it is found that SCR denitration has oxidability to the mercury in power-plant flue gas, can be by Hg0
It is oxidized to Hg2+, the clearance of mercury is reached more than 75%.Meanwhile, SCR catalyst is improved, removal of mercury rate is more than 85%.This
Plant catalyst to use after 9500h, the oxidation activity of mercury is still more than 0.85.
China starts to pay attention to mercury pollution and control problem in recent years, has carried out the research in terms of some mercury improvement.Hand in Shanghai
Lead to university research manganese base composite oxidate and its absorption property to nonvalent mercury.It was found that the Mn oxide prepared with different manganese sources
There are different absorption properties to nonvalent mercury, wherein the Mn oxide prepared by manganese source of manganese nitrate has higher absorption property
（10h adsorption capacities are about 2.1mg/g at 100 DEG C）, and the structure and manganese valence of absorption property and adsorbent exist and associate
Property, the manganese of high-valence state is more beneficial for the adsorption and oxidation of mercury.But have the disadvantage in SO2Desorption performance under existence condition after Adsorption of Mercury compared with
Difference.It has been proposed that load NaI, CuCl2、CuBr2、FeCl3Zeolite, calcium silicates and neutral alumina there is very high mercury removal
Efficiency.Some scholars use Ca-base adsorbent (CaO, Ca (OH)2、CaCO3、CaSO4·2H2O) make a return journey the removal of mercury, it is found that calcium base is inhaled
The attached dose of adsorption capacity to compound state mercury is better than activated carbon, but to be weaker than activated carbon to the adsorption capacity of element mercury.SO2And height
Temperature is conducive to absorption of the Ca-base adsorbent to element mercury, but to HgCl2Absorption contrast.Ca-base adsorbent is to Hg2+Suction
Attached efficiency is higher, but very low to HgO removal efficiency, can combine oxidation catalyst and carry out cooperation-removal, but mercury reduction is asked
Topic can not still be solved.Someone absorbs mercury using a kind of chloride oxides, but chlorion easily corrodes metal fittings.Someone adopts
With the multi-stage combination desulfurization denitration process removal of mercury of lime stone and gypsum and oxidant, but bring secondary pollution and mercury to discharge again and ask
Topic.
Gangue is the solid waste discharged during coal mining process and coal washing, be one kind in coalification course with coal seam companion
A kind of relatively low, harder than the coal black gray expandable rock of raw phosphorus content.Its main component is Al2O3、SiO2, quantity is also contained in addition
The Fe not waited2O3、CaO、MgO、Na2O、K2O、P2O5、SO3And trace rare-earth element.But at present, due to technology imperfection, ground
Area's disparate development, the availability of gangue is extremely low.Gangue air storage can produce a large amount of airborne dusts, and gangue water suction is easily collapsed
Solution, and produce a large amount of dust.Under the action of the forces of the wind, it will deteriorate the quality of mining area air.Contain residual coal, carbonaceous in gangue
The combustible such as mud stone and culled wood, easy spontaneous combustion during air storage, and produce toxic gas pollution environment.
The content of the invention
The present invention has the porous material of the compound alumina ceramic of honeycomb or web frame based on above mentioned problem there is provided a kind of
Material carries out activation process to carrier surface using highly acid Ag-containing solution, developed a kind of to air, industrial waste gas as carrier
With the mercury in coal-fired flue-gas has a lasting absorption property receives mercury material.The material is not only with surface area is big, permeability is strong, pressure
The performance such as contracting intensity height, impact resistance, high temperature resistant, environmentally friendly and chemical stability be high, and carrier can recycle, mercury
Reclaim simple and easy to apply, do not result in secondary pollution.By the use of discarded gangue as raw material, turn waste into wealth, not only can be made into
The adsorbent of beneficial environment, can also reduce the accumulating amount of gangue.As a result of the gangue as discarded object, changing waste into valuables,
It can also further reduce production cost.In addition, preparation process is simple, it is with low cost, with good application potential and well
Economic results in society.
To achieve the above object, the invention provides following technical scheme：
What this had a lasting absorption property receives mercury material, is characterized in that：By 92 ~ 98wt% composite ceramics carrier and 2 ~
10wt% activating agents are prepared from.
Further, the composite ceramics carrier according to weight by comparing 1：3 main material and Ludox is made, main material bag
Include 30 ~ 35wt% Al2O3, 55 ~ 60wt% gangue and 5 ~ 10wt% charcoal powder or starch forms.
Further, the gangue includes SiO252~55wt%、Al2O316 ~ 36wt% and Fe2O32~14wt%。
Further, the mercury absorbent solution is pH 1 ~ 5,0.1 ~ 0.5mol/L of concentration（With Ag+Ionometer）Sulfuric acid
More than one the aqueous solution of silver, silver chlorate or silver nitrate.PH can be adjusted by hydrochloric acid or nitric acid.It is preferred that, mercury absorbent is molten
20 ~ 35 DEG C of the temperature of liquid.
Further, the solvent of the mercury absorbent is running water.
Further, the composite ceramics carrier compressive strength is 3.0 ~ 5.0Mpa, and surface roughness is 0.3 ~ 0.8mm.
There is the preparation method of mercury material received of lasting absorption property to comprise the following steps for this：
Step 1）30 ~ 35wt% Al will be included2O3, 55 ~ 60wt% gangue, the main material of 5 ~ 10wt% charcoal powders or starch
After well mixed, compare 1 according to weight under stirring：In 3 input Ludox, slurry is persistently uniformly mixing to obtain standby；
Step 2）By in the polyurethane foam immersion slurry with loose structure, drying is taken out；
Step 3）Repeat step 2）, until being full of slurry in the hole of polyurethane foam, obtain ceramic blank；
Step 4）Ceramic blank is placed at 1280 ~ 1390 DEG C and is calcined 4h, room temperature is naturally cooled to after taking-up, is obtained with porous knot
The composite ceramics carrier of structure；
Step 5）The attachment of composite ceramics carrier surface is washed with water, 2h ~ 4h is spontaneously dried；
Step 6）Composite ceramics carrier is immersed to 2 ~ 8h in 0.1 ~ 0.5mol/L of concentration mercury absorbent solution to be full of into space
After mercury absorbent, composite ceramics carrier is taken out, 2 ~ 6h is spontaneously dried；
Step 7）Repeat step 6）1 ~ 5 time；
Step 8）By 80 DEG C of 2 ~ 6h of drying of composite ceramics carrier；Or adsorb carrier impregnation to concentration for 0.1 ~ 0.5mol/L mercury
In agent solution, mercury absorbent solution will be evaporated at 80 DEG C, will be got product.
Further, the mercury absorbent solution be mercury absorbent be pH 1 ~ 5,0.1 ~ 0.5mol/L of concentration silver sulfate,
More than one the aqueous solution of silver chlorate or silver nitrate.
Further, the polyurethane foam is netted or cellular.
Advantages of the present invention and beneficial effect are：The present invention is by silver ion, chlorion, sulfate ion, nitrate ion
In the composite ceramics carrier surface and hole that crystallize netted cell structure or honeycomb, only by simply soaking, being evaporated,
The cyclic process several times soak again, being evaporated again, you can make the area coverage of adsorbent reach more than 85%.One side ceramic body
It is made into loose structure, the flue gas for the mercury that is easy to carry passes through；On the other hand, ceramics itself have microcellular structure, can be maximum
The receiving of limit can inhale the adsorbent crystal of mercury（Silver sulfate, silver chlorate, silver nitrate）, and can be locked after mercury is received
In micropore or hole, it is to avoid the outflow of noxious material.It is preferably 0.1 ~ 0.5mol/L by the concentration of activating agent, can ensureing to live
Cost is saved on the premise of agent coverage rate and adsorption effect.It is living although can be regarded as under normal circumstances in the concentration range
Agent coverage rate and concentration are linear, i.e. concentration more high coverage rate is higher.When in minimum critical concentration, i.e. 0.1mol/L
When, 85% coverage rate has been can reach on the surface of ceramic channel walls（The coverage rate usually using when can reach it is good
Adsorption effect, but according to the difference of mercury content, for extension replacement frequency, will certainly have further to the adsorbance of unit volume
Demand）If ample time can be achieved to be completely covered.And concentration is less than 0.1mol/L, activator solution can be with ceramic monolith phase
The active group mutually grabbed in activating agent, causes always to be unable to reach 85% coverage rate, and the adsorption effect of unit volume ceramics
It is decreased obviously.
And from metallographic observation, when in highest critical concentration, i.e. 0.5mol/L, though area coverage is up to 100%, but
Due to the effect of molecular separating force, the activating agent after crystallization still may proceed to the active group in adsorption activity agent so that ceramic monolith
In hypersaturated state, so as to further improve active group capacity, the ion exchange between ceramic monolith and activator solution is put down
Weighing apparatus.Now, even if improving surfactant concentration, unnecessary active group also can only be existed in solution with free state, Bu Huiyu
Obvious change will not occur for ceramic monolith formation bonding, metallurgical states.
And in actual production, it is difficult to by technological means by concentration maintain above and below between critical value it is a certain numerically,
It is typically to preset a concentration range, according to the height of yield, determines sampling frequency, is less than in concentration under the setting concentration
In limited time, surfactant concentration is adjusted to the upper limit while pH is adjusted.
Mercury is main in the offgas to be existed in three kinds of forms, i.e. mercury simple substance steam, mercury simple substance particle and valence state mercury.Will attachment
The silver sulfate of crystalline state in composite ceramics carrier micropore, silver chlorate, silver nitrate are anti-with mercury simple substance steam as adsorbent
Should after be fixed in the microcellular structure of carrier.And on the one hand the silver-colored simple substance produced after being calcined can form amalgam with mercury simple substance steam,
Amalgam is scattered to be sticked in the microcellular structure of ceramic monolith, will not be gathered, will not be spilt from microcellular structure；On the other hand
Using the micro pore surface area of porous ceramics, adsorptivity adsorbs valence state mercury and particle mercury paved set in micropore well, most at last
Mercury vapour, mercury simple substance particle and the complete adsorption removal of valence state mercury.Key reaction principle：2Ag++Hg→2Ag+Hg2+, the master being related to
React as follows：①Hg+2AgNO3→Hg(NO3)2+2Ag；②Hg+Ag2SO4→2Ag+ HgSO4；③Hg+2AgCl→2Ag+
HgCl2；④xHg+yAg→HgxAgy。
The preparing raw material of the present invention is easily obtained, specifically, and ceramic main material selects the gangue frequently as discarded object, can
Play the purpose of the useless pollution treatment of profit；Activating agent solvent is from running water without considering free chloro concentration therein；Driving body is selected
Easily prepared cellular polyurethane foam, greatly reduces production cost；Viscosity agent is from the high Ludox of stability, it is ensured that
The product quality of composite ceramics carrier.The drying of ceramic body, roasting, activation can be carried out at ambient pressure, to sealing requirements compared with
It is low, it is possible to decrease to prepare cost.Composite ceramic body obtained by preparation is grand hole ceramics, and aperture is 500nm ~ 800nm.
Although the preparation method prior art wet method foaming of the present invention, which prepares porous ceramics technique, has similarity,
It is that in the prior art, the surface active of porous ceramics is to improve its inherent characteristic mostly, it is CMC for example with various concentrations, wooden
Element, PEI improve the characters such as compression strength, the porosity of ceramic body and are modified.It is micro by adding（0~3wt%）Rare earth element（Such as
Ga、V、Ti、Co）Resistance to compression and the anti-seismic performance of ceramic material can be also improved, and these rare earth elements can be obtained directly from gangue
, without extra addition, preparation component is thereby reduced, production cost is reduced indirectly.
The thermal decomposition of polyurethane foam knowable to prior art is occurred mainly between 240 ~ 440 DEG C, 440 ~ 500 DEG C and
It is in small weightlessness between 500 ~ 600 DEG C, weightlessness is due to that carbon dioxide, carbon monoxide, cyanogen are overflowed in polyurethane burning or thermal decomposition
Change the gas componants such as hydrogen, formaldehyde.After temperature is more than 700 DEG C, weight hardly changes.And gas is in overflow process
In to ceramic body produce stress, easily cause base substrate destruction in addition cave in.Therefore, select slow in 240 ~ 600 DEG C of temperature sections
Heating, and in weld point insulation, to avoid base substrate from being destroyed.
And in the preparation technology of the present invention, by adding a certain amount of charcoal powder or starch in slurry, directly will immediately
Dried hole is put into 1280 ~ 1390 DEG C of roastings full of the polyurethane foam of slurry, although without slow temperature-rise period, but
Still ensure that the stability of base substrate.Without slowly heating or insulating process, preparation time is shortened naturally, energy has been saved, letter
Change technological process, so as to greatly reduce production cost, improve production efficiency.And it is dispersed in the charcoal powder in slurry
Or after starch expanded by heating or burning, ceramic rough degree can be increased, and then increase surface area, so as to increase effective appearance of activating agent
Product.
And high temperature can be utilized by inhaling the material after mercury（400~600℃）Low Temperature Thermal desorption method reclaims mercury, and follows carrier regeneration
Ring is used, and thus reduces use cost, realizes the purpose of energy-conserving and environment-protective.Due to the mercury accumulation of the absorption in porous ceramics
Greatly, it is easy to centralized recovery, the mercury after being reclaimed by Low Temperature Thermal desorption method can also be recycled.Not only reduce manufacture and use
Cost, and the mercury after absorption can be recycled, this is uncommon in the prior art.
In addition, when in use, inhale the whole ceramics of mercury process and have obvious weightening process, and when ceramic body reaches saturation shape
During state, then weight will not be changed substantially, and the mercury material fit gravity sensor that can also be received this using this phenomenon is used, with
The saturation state of mercury material is received in detection, so as to be changed in good time.Avoid when use state in kind can not be observed, it is impossible to slap
Control the adsorption activity of material.It will be apparent that the usage can not be applicable for non-solid material.
In summary, the present invention has preparation process simple, with low cost, and carrier can be recycled, and lasting inhale can be achieved
Attached, free from environmental pollution the characteristics of, with good application potential and good economic results in society.
Brief description of the drawings
Fig. 1 is the microscopic appearance of the pore structure of ceramic monolith；
Fig. 2 is the microscopic appearance on ceramic monolith surface after activation；
Fig. 3 is the microscopic appearance of the surface active area pattern of ceramic monolith after activating；
Fig. 4 is the microscopic appearance of the section of hole beam in ceramic monolith after activating；
Fig. 5 be in 0.15mol/L silver nitrate aqueous solution infused ceramic carrier test atmosphere daily at mercury import and export mean concentration with
The change curve of time；
Fig. 6 is that average adsorption efficiency of the 0.15mol/L silver nitrate aqueous solution infused ceramics carrier daily to mercury changes with time
Curve；
Fig. 7 is the daily average mercury capacity versus time curve of 0.15mol/L silver nitrate aqueous solution infused ceramic carriers.
Embodiment
Below in conjunction with Fig. 1 ~ 7, the particular content of the present invention is described in detail by specific embodiment.There should be lasting adsorptivity
The mercury material of receiving of energy is prepared from by 90 ~ 98wt% composite ceramics carrier and 2 ~ 10wt% mercury absorbent.Composite ceramics carrier
By comparing 1 according to weight：3 main material and it is made as the Ludox of binding agent, main material includes 30 ~ 35wt% Al2O3、55~
60wt% gangue and 5 ~ 10wt% charcoal powder or starch are formed.Because Ludox viscosity is higher, therefore in mixing process
The middle lasting stirring of needs.Under normal circumstances, the gangue composition of areal exploitation is more fixed, but the present invention is still preferred to use
Contain SiO252~55wt%、Al2O316~36wt%、Fe2O32 ~ 14wt% and the rare earth element of surplus gangue.Mercury absorbent
Solution is pH 1 ~ 5,0.1 ~ 0.5mol/L of concentration（With Ag+ ionometers）Silver sulfate, silver chlorate or silver nitrate more than one
The aqueous solution.Solvent can select running water or distilled water or purified water, because running water materials are more convenient and required containing preparing
Chlorion, therefore be preferred to use running water.3.0 ~ 5.0Mpa of compressive strength, surface roughness can be prepared by by said ratio
0.3 ~ 0.8mm, composite ceramics carrier with loose structure of the mercury absorbent area coverage up to more than 85%.
Its preparation method comprises the following steps：
Embodiment 1
In the present embodiment, composite ceramics carrier is prepared according to the method described in technical solution of the present invention, by including 33wt%'s
Al2O3, 60wt% gangue, the main material of 7wt% charcoal powder and Ludox compare 1 with weight：3 blend together slurry, then by three-dimensional
The polyurethane organic foam immersion slurry of mesh skeleton structure or honeycomb, is then evaporated, is repeated several times, until mesh skeleton
Foam mesopore is full of.4h is finally calcined at 1300 ~ 1390 DEG C, netted or cellular composite ceramic is made to room temperature in air cooling
Ceramic carrier.Support samples are assembled to be placed on mean concentration 0.1mg/m3Mercury vapour atmosphere in carry out application test, sample is persistently inhaled
The mercury time is 10h, and the mean concentration of exit mercury is in 0.08mg/m3Left and right, adsorption rate is about 20%.The hole knot of ceramic monolith
Structure is shown in Fig. 1.
Embodiment 2
In the present embodiment, composite ceramics carrier is prepared first according to the method described in technical solution of the present invention, will be included
35wt% Al2O3, 60wt% gangue, the main material of 5wt% starch and Ludox compare 1 with weight：3 blend together slurry, so
The polyurethane organic foam of three-dimensional netted skeleton structure or honeycomb is immersed into slurry afterwards, then dries, is repeated several times, until
Mesh skeleton foam mesopore is full of.4h is finally calcined at 1280 ~ 1390 DEG C, air cooling is made netted or cellular to room temperature
Composite ceramics carrier.Carrier is used after being cleaned and dried impregnates 1 ~ 2h in the 0.1mol/L silver sulfate aqueous solution, place into 80 DEG C of baking
Dried in case.Sample is assembled to be placed on mercury content 0.1mg/m3Atmosphere in tested, sample persistently inhales the mercury time and is
240h, the mercury concentration in exit is in 0.015 ~ 0.05mg/m3Between, adsorption rate 50 ~ 85%.The surface of ceramic monolith is micro- after activation
See structure and see Fig. 2, active region pattern is shown in Fig. 3, and section microscopic appearance is shown in Fig. 4.
Embodiment 3
In the present embodiment, composite ceramics carrier is prepared first according to the method described in technical solution of the present invention, will be included
30wt% Al2O3, 60wt% gangue, the main material of 10wt% charcoal powder and Ludox compare 1 with weight：3 blend together slurry, so
The polyurethane organic foam of three-dimensional netted skeleton structure or honeycomb is immersed into slurry afterwards, then dries, is repeated several times, until
Mesh skeleton foam mesopore is full of.4h is finally calcined at 1280 ~ 1390 DEG C, air cooling is made netted or cellular to room temperature
Composite ceramics carrier.Carrier impregnates 1 ~ 2h after being cleaned and dried with the 0.2mol/L silver chlorates aqueous solution, places into 80 DEG C of baking oven
Middle drying.Sample is assembled to be placed on mercury content 0.1mg/m3Atmosphere in tested, sample persistently inhales the mercury time up to 280h,
The mercury concentration in exit is in 0.01 ~ 0.04mg/m3Between, adsorption rate is 60 ~ 90%.
Embodiment 4
In the present embodiment, composite ceramics carrier is prepared first according to the method described in technical solution of the present invention, will be included
35wt% Al2O3, 55wt% gangue, the main material of 10wt% starch and Ludox compare 1 with weight：3 blend together slurry, then
The polyurethane organic foam of three-dimensional netted skeleton structure or honeycomb is immersed into slurry, then dries, is repeated several times, until net
Shape skeleton foam mesopore is full of.4h is finally calcined at 1280 ~ 1390 DEG C, air cooling is made netted or cellular to room temperature
Composite ceramics carrier.Carrier is impregnated in 1 ~ 2h, the baking oven for placing into 80 DEG C after being cleaned and dried with 0.1mol/L silver nitrate aqueous solutions
Drying.Sample is assembled to be placed on mercury content 0.1mg/m3Atmosphere in carry out experiment 24h, the mercury concentration in exit exists
0.001mg/m3Left and right, adsorption rate is about 99%.
Embodiment 5
In the present embodiment, composite ceramics carrier is prepared first according to the method described in technical solution of the present invention, will be included
32wt% Al2O3, 58wt% gangue, the main material of 10wt% starch and Ludox compare 1 with weight:3 blend together slurry, then
The polyurethane organic foam of three-dimensional netted skeleton structure or honeycomb is immersed into slurry, then dries, is repeated several times, until net
Shape skeleton foam mesopore is full of.4h is finally calcined at 1280 ~ 1390 DEG C, air cooling is made netted or cellular to room temperature
Composite ceramics carrier.Carrier is impregnated in 1 ~ 2h, the baking oven for placing into 80 DEG C after being cleaned and dried with 0.3mol/L sodium sulfide solutions
Drying.Sample is assembled to be placed on mercury content 0.1mg/m3Atmosphere in carry out experiment 24h, exit mercury concentration is about
0.05mg/m3Left and right, adsorption rate about 50%.
Embodiment 6
In the present embodiment, composite ceramics carrier is prepared first according to the method described in technical solution of the present invention, will be included
34wt% Al2O3, 58wt% gangue, the main material of 8wt% starch and Ludox compare 1 with weight：3 blend together slurry, then
The polyurethane organic foam of three-dimensional netted skeleton structure or honeycomb is immersed into slurry, then dries, is repeated several times, until net
Shape skeleton foam mesopore is full of.4h is finally calcined at 1280 ~ 1390 DEG C, air cooling is made netted or cellular to room temperature
Composite ceramics carrier.Carrier is impregnated in 1 ~ 2h, the baking oven for placing into 80 DEG C after being cleaned and dried with 0.15mol/L silver nitrate aqueous solutions
Drying.Sample is assembled to be placed on 0.01 ~ 0.311mg/m of mercury content3Atmosphere in tested, sample persistently inhales mercury 336h,
Exit mercury concentration is in 0 ~ 0.018mg/m3Concentration changes with time situation is shown in Fig. 5 at left and right, mercury import and export, and adsorption rate is at any time
Between situation of change see Fig. 6, adsorbance changes over time situation and sees Fig. 7.
Embodiment result shows that the present invention develops a kind of porous ceramics carrying active substance with lasting absorption property
Receive mercury material.
Claims (9)
1. a kind of receive mercury material with lasting absorption property, it is characterised in that：By 90 ~ 98wt% composite ceramics carrier and 2 ~
10wt% mercury absorbent is prepared from.
2. receive mercury material with lasting absorption property as claimed in claim 1, it is characterised in that：The composite ceramics carrier by
Compare 1 according to weight：3 main material and Ludox is made, and main material includes 30 ~ 35wt% Al2O3, 55 ~ 60wt% gangue with
And 5 ~ 10wt% charcoal powder or starch are formed.
3. receive mercury material with lasting absorption property as claimed in claim 1 or 2, it is characterised in that：The gangue includes
SiO252~55wt%、Al2O316 ~ 36wt% and Fe2O32~14wt%。
4. receive mercury material with lasting absorption property as claimed in claim 3, it is characterised in that：The mercury absorbent solution
For more than one the aqueous solution of pH 1 ~ 5,0.1 ~ 0.5mol/L of concentration silver sulfate, silver chlorate or silver nitrate.
5. receive mercury material with lasting absorption property as claimed in claim 4, it is characterised in that：The solvent of the mercury absorbent
For running water.
6. receive mercury material with lasting absorption property as claimed in claim 5, it is characterised in that：The composite ceramics carrier is
3.0 ~ 5.0Mpa of compressive strength, 0.3 ~ 0.8mm of surface roughness loose structure.
7. a kind of preparation method for receiving mercury material with lasting absorption property, it is characterised in that comprise the following steps：
Step 1）30 ~ 35wt% Al will be included2O3, 55 ~ 60wt% gangue, the main material of 5 ~ 10wt% charcoal powders or starch mix
After closing uniformly, compare 1 according to weight under stirring：In 3 input Ludox, slurry is persistently uniformly mixing to obtain standby；
Step 2）By in the polyurethane foam immersion slurry with loose structure, drying is taken out；
Step 3）Repeat step 2）, until being full of slurry in the hole of polyurethane foam, obtain ceramic blank；
Step 4）Ceramic blank is placed at 1280 ~ 1390 DEG C and is calcined 4h, room temperature is naturally cooled to after taking-up, is obtained with porous knot
The composite ceramics carrier of structure；
Step 5）The attachment of composite ceramics carrier surface is washed with water, 2h ~ 4h is spontaneously dried；
Step 6）By 2 ~ 8h in 0.1 ~ 0.5mol/L of composite ceramics carrier immersion concentration, pH 1 ~ 5 mercury absorbent solution to space
In be full of mercury absorbent after, composite ceramics carrier is taken out, spontaneously dry 2 ~ 6h；
Step 7）Repeat step 6）1 ~ 5 time；
Step 8）By 80 DEG C of 2 ~ 6h of drying of composite ceramics carrier；Or adsorb carrier impregnation to concentration for 0.1 ~ 0.5mol/L mercury
In agent solution, mercury absorbent solution will be evaporated at 80 DEG C, will be got product.
8. receive mercury material with lasting absorption property as claimed in claim 7, it is characterised in that：The mercury absorbent solution
For more than one the aqueous solution that mercury absorbent is pH 1 ~ 5,0.1 ~ 0.5mol/L of concentration silver sulfate, silver chlorate or silver nitrate.
9. receive mercury material with lasting absorption property as described in claim 7 or 8, it is characterised in that：The polyurethane foam
To be netted or cellular.
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| CN108176188A (en) * | 2018-01-09 | 2018-06-19 | 江苏苏净集团有限公司 | Application method and molecular sieve combination body of the molecular sieve combination body in exhaust gas is purified |
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| CN108863431A (en) * | 2018-06-28 | 2018-11-23 | 山西省玻璃陶瓷科学研究所（有限公司） | A kind of removal refrigerator peculiar smell foam pottery and preparation method |
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Application publication date: 20170915 Assignee: Xuzhou Zhongke Zhenfeng environmental science and Technology Research Institute Co.,Ltd. Assignor: XUZHOU ZHENFENG NEW WALL MATERIAL CO.,LTD. Contract record no.: X2021980016168 Denomination of invention: Nanomercury materials with long-lasting adsorption properties Granted publication date: 20200414 License type: Common License Record date: 20220105 |