CN108421523A - A kind of preparation method for inhaling mercury porous ceramics block materials - Google Patents
A kind of preparation method for inhaling mercury porous ceramics block materials Download PDFInfo
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- CN108421523A CN108421523A CN201810281531.0A CN201810281531A CN108421523A CN 108421523 A CN108421523 A CN 108421523A CN 201810281531 A CN201810281531 A CN 201810281531A CN 108421523 A CN108421523 A CN 108421523A
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 229910052753 mercury Inorganic materials 0.000 title claims abstract description 86
- 239000000919 ceramic Substances 0.000 title claims abstract description 58
- 239000000463 material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000011257 shell material Substances 0.000 claims abstract description 25
- 238000005495 investment casting Methods 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims description 28
- 239000012286 potassium permanganate Substances 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000012190 activator Substances 0.000 claims description 6
- 239000002699 waste material Substances 0.000 claims description 6
- 239000002351 wastewater Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 235000011164 potassium chloride Nutrition 0.000 claims description 5
- 239000001103 potassium chloride Substances 0.000 claims description 5
- 239000008399 tap water Substances 0.000 claims description 5
- 235000020679 tap water Nutrition 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000000428 dust Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 5
- 238000004064 recycling Methods 0.000 abstract description 5
- 230000003213 activating effect Effects 0.000 abstract description 3
- 230000035699 permeability Effects 0.000 abstract description 2
- -1 Manganate ions Chemical class 0.000 abstract 1
- 238000001802 infusion Methods 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 238000007598 dipping method Methods 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 7
- 239000003345 natural gas Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000003546 flue gas Substances 0.000 description 4
- 230000008676 import Effects 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 238000005272 metallurgy Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 239000003570 air Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002802 bituminous coal Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 235000012241 calcium silicate Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000000254 damaging effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 231100000241 scar Toxicity 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000000192 social effect Effects 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present invention relates to a kind of preparation methods for inhaling mercury porous ceramics block materials, the type shell material that hot investment casting factory discards is rolled to the block for being broken into 2 5mm grain sizes in pulverizer first, finally activating agent is supported in block surface and its micropore using infusion process, Elemental Mercury is fixed to the oxidation of mercury using Manganate ions in activating agent, valence state mercury is adsorbed using the huge surface area of porous ceramics block.Not only surface area is big, permeability is strong, environmentally friendly for suction mercury porous ceramics block materials provided by the invention, but also recycles, and recycling is simple and practicable, it will not cause secondary pollution, material preparation process is simple, of low cost, has good application prospect and good economic results in society.
Description
Technical field
The present invention relates to air environmental pollutions to administer field, is specifically used for a kind of economic ring that atmosphere pollution mercury administers application
The efficient suction mercury block materials protected.
Background technology
If the mercury in coal-fired flue-gas, non-ferrous metal metallurgy exhaust gas is before discharging without reasonably being removed, Jiu Huijin
Enter ambient air and in so enter water body and ecological environment, finally influence survival and development of mankind.Mercury has stronger toxicity, right
Human body and animals and plants constitute injury.Mercury has strong migration, is very easy to diffusion, is a kind of global contaminant, to ecological ring
Border generates damaging effect.
Mercury In The Air exists in the form of three kinds of Elemental Mercury, valence state mercury and particulate Hg, and wherein Elemental Mercury is most difficult to remove.Oil and day
Mercury in right gas mainly exists with simple substance form, although content is very low（1~200μg/m3）, but easily formed by atmospheric circulation
Global contact scar, and the residence time is long（0.5 ~ 2 year）.In addition, mercury forms organic mercury in vivo, can not rule out.At present
Hydrargyrum-removing technology mainly has chemisorption, solution absorption, cryogenic separation etc., wherein chemisorption economically, demercuration effect
There is advantage with environmental protection etc..Common chemical demercuration adsorbent mainly has load sulphur/active carbon loading silver, carried metal both at home and abroad
Sulfide and metal oxide and the molecular sieve etc. for carrying silver.Such as UOP（UOP）Silver molecular sieve demercuration
Agent removal effect is good, and renewable, but expensive；The load type metal sulfide molecules sieve adsorbant of French Axens companies,
It can be used for dry gas and moisture demercuration, but non-renewable；Calgon Carbon Corporation of the U.S.（Calgon Carbon Corporation）
Sulfur loading active carbon and China Nanjing Zhengsen Chemical Industry Co., Ltd. production ZS-08 types carry sulphur special-purpose active carbon for removing mercury,
It is only applicable to processing dry gas, lean gas demercuration；Also Britain village letter Wan Feng companies（Johnson Matthey Catalysts）Research and development
The natural gas mercury-removing agent of different performance, the demercuration tower equipped with adsorbent is added in natural gas processing flow realizes natural gas
Demercuration.Natural gas after processing, mercury concentration are down to 0.01 μ g/m3Below.The AxTrap series of French Axens companies production
Catalysis demercuration adsorbent is answered in the oil gas field of multiple countries such as Germany, Japan, Indonesia, Malaysia, China
With for removing the mercury in the logistics such as natural gas, condensate.Songyuan City of Jilin Oil Field company gas production factory director ridge natural gas purification station day
Mercury content is 360 μ g/m in right gas unstripped gas3, start in November, 2010 to handle natural gas using 271 mercury removal agents of AxTrap, it will
Adsorption tower is placed in molecular sieve dehydration device downstream, and device normal operation is after 1 year, mercury content in demercuration tower export gas
It is reduced to 493ng/m3。
Mercury emissions in coal-fired industry, non-ferrous metal metallurgy industry tail gas are also one of source of atmospheric pollution, universal both at home and abroad
Mercury is inhaled using activated carbon or modified activated carbon, activated carbon consumption is huge at present, and cost is higher.It is secondary using flying dust or other burnings
Product may only adsorb a part of gaseous mercury in bituminous coal combustion.Shanghai Communications University finds manganese base composite oxidate to nonvalent mercury
With good absorption property.In recent years someone works out a kind of zeolite and calcium silicates of calcium base mercury removal agent-load halogen, to valence
State mercury has significant adsorption effect, but does not have obvious effect to nonvalent mercury.
The present invention considers economic cost and manufacture complexity and resource under the premise of ensure that the depollution of environment
The case where recycle etc., simply handles the used shell residuum of industrial hot investment casting, develops one kind
Economic and environment-friendly efficient suction mercury block materials achieve the purpose that the useless pollution treatment of profit.
Invention content
In order to make up above-mentioned the deficiencies in the prior art, the purpose of the present invention is to propose to a kind of suction mercury porous ceramics block materials
Preparation method, which has compared with high absorption capacity the mercury in non-ferrous metal metallurgy and coal-fired industry, PVC production flue gases,
Not only have that surface area is big, permeability is strong, can recycle, mercury recycling is simple and practicable, will not cause secondary pollution；And it uses
Industrial refuse as waste is as raw material, and preparation process is simple, low production cost has broad application prospects
With great social effect.
The purpose of the present invention is what is be achieved through the following technical solutions, a kind of preparation side for inhaling mercury porous ceramics block materials
Method is characterized in that：Include the following steps：
1）The waste ceramic shell relic tap water or industrial cycle cooling waste water that hot investment casting is generated rinse, and remove shell
The dust on surface and other burs dry under sunlight, the ceramic shell relic dried are broken into grain size with jaw crusher
The fritter of 10 ~ 50mm；
2）The fritter of 10 ~ 50mm of grain size is put into roller and is ground into powder, leaves that ceramic block granularity is 2 ~ 5 mm
Grain；
3）Step 2 is washed with water）Middle ceramic block particle（2~5mm）, after natural drying, it is small that 0.5 ~ 3 is roasted at 900-1100 DEG C
When；
4）It will be dried 1-3 hours at 80 DEG C of ceramic block particle after roasting, immerse the activator solution of 2 ~ 8g/100ml of concentration
In 2 ~ 8 hours, take out, heated 1-3 hours at 70-150 DEG C；
5）Repeat step 4）It gets product for 1 ~ 3 time.
Further, the waste ceramic type shell material that hot investment casting generates includes Ludox, the 20 ~ 30wt% of 50 ~ 70wt%
Gangue, 10 ~ 20wt% pure schmigel.
Further, the mercury activator solution is the potassium permanganate or potassium chloride of pH 12 ~ 14,2 ~ 8g/100ml of concentration
One or both of aqueous solution, pH value can pass through add potassium permanganate adjust, 20 ~ 35 DEG C of the temperature of mercury activator solution.
Further, the solvent of the mercury absorbent is one or more of tap water, river water or industrial cycle waste water.
Advantages of the present invention and advantageous effect：
（1）The present invention provides a kind of economic and environment-friendly efficient suction mercury block materials, using strong basicity liquor potassic permanganate to block
Surface carries out activation process, develop a kind of mercury in non-ferrous metal metallurgy and coal-fired industry, PVC production flue gases have it is higher
The porous ceramics block materials of adsorption capacity are turned waste into wealth, no using the shell residuum of hot investment casting industrial waste as raw material
But the suction mercurial that can be made into useful environment, can also reduce the stacking of the industrial refuses such as shell residuum；
（2）The present invention is by potassium ion, the hole of chlorion, high manganese ion, value Mn ion precipitation to ceramic shell surface
In, only by it is simply broken, cleaning, roasting, dipping, the processes such as heating, you can be made.Finished product is porous ceramic particles, just
In being installed in various pipelines and device；There is micro hole construction, can accommodate to the maximum extent can inhale mercury in shell tissue
Crystal（Potassium permanganate and potassium chloride）, and can lock it in micropore or hole after receiving mercury, avoid noxious material
Outflow；
（3）The raw material for preparing of the present invention easily obtains, and for the shell residuum discarded after industrial application, activating agent solvent is selected originally
The waste water of water, river water or industrial cycle cooling, greatly reduces production cost, by controlling ceramic block granularity, both ensure that
The enough adsorption areas of ceramic particle in turn ensure the unobstructed of air-flow, and crushing, cleaning, the drying of ceramic particle can be under normal pressure
It carries out, not only preparation process is simple, but also of low cost, free from environmental pollution, has good application potential and good society
Economic benefit.
Description of the drawings
Fig. 1 is ceramic shell relic discarded after industry spot use；
Fig. 2 is the microscopic appearance of particle surface made of ceramic shell relic；
Fig. 3 is the microscopic appearance of ceramic grain surface after dipping；
Fig. 4 is the EDS collection of illustrative plates of ceramic grain surface after dipping.
Specific implementation mode
Ceramic block material is made of the ceramic shell residuum of industrial waste.The high-quality gangue of precision casting shell selection,
Pure schmigel and import high quality silicon colloidal sol as raw material, by the Ludox of 50 ~ 70wt% and the gangue of 20 ~ 30wt% and
The pure schmigel of 10 ~ 20wt% is made.Fig. 1 is the pattern of shell residuum, it through being blended, coat, drying, roasting, pour steel
After preceding pre-burning and the heat effect of molten steel, ceramic structure is stablized, and most of impurity elements, elemental gas and low melting point element can be waved
It sends out, Ludox decomposes substantially, and sintering forms the reticulated macroporous of space connection on the surface of gangue and corundum ceramic particle
Structure.Since shell interior is little by heat effect, Ludox sintering is incomplete, impurity element, elemental gas and low melting point element
It volatilizing insufficient, microcellular structure is imperfect, and is easy to block, therefore is ground into the particle of 2 ~ 5mm, and microstructure is shown in Fig. 2, and
It is roasted at 900 ~ 1100 DEG C, Ludox is made fully to decompose, substantially increase particle porosity.Mercury activator solution is pH value 12
~ 14, aqueous solution one or two kinds of in the potassium permanganate or potassium chloride of 2 ~ 8g/100ml of concentration.Tap water or river can be selected in solvent
Water or industrial cycle cooling waste water.The ceramic block suction mercurial that by said ratio can be prepared by that there is microcellular structure, micro- group
It knits and sees Fig. 3, Fig. 4 with EDS collection of illustrative plates.
Embodiment 1
In the present embodiment, being prepared according to the method described in technical solution of the present invention has economic and environment-friendly efficient suction mercury porous
Ceramic block material, by industrial hot investment casting ceramic shell residuum（By the Ludox of 50 ~ 70wt% and the coal of 20 ~ 30wt%
The pure schmigel of spoil and 10 ~ 20wt% form, and are made by being blended, coating, dry, roast, have passed through before pour steel in advance
Burn the heat effect with molten steel）It is ground into the particle of 2 ~ 5mm.After over cleaning, roasted 0.5 hour at 1080 DEG C, it is air-cooled to arrive room
Ceramic particle of the grain size in 2 ~ 5mm of microcellular structure is made in temperature.50g ceramic particles are weighed, 2g/100ml is respectively put into after drying
Potassium permanganate originally in aqueous（pH=13）After impregnating 2h, spontaneously dry.It is placed on after sample is assembled in high concentration mercury vapour atmosphere
It is tested, it is 15 minutes 1 hour that sample, which persistently inhales the mercury time, and it is 0.121 μ g that sample, which always inhales mercury quantity, and design parameter is shown in Table 1.
It is dense at mercury import and export in the ceramic particle experimental atmosphere of 1 a concentration of 2g/100ml potassium permanganate solutions of table dipping
The parameters such as degree, adsorption rate, sample mercury capacity change with time situation
Embodiment 2
In the present embodiment, being prepared according to the method described in technical solution of the present invention has economic and environment-friendly efficient suction mercury porous
Industrial hot investment casting is ground into the particle of 2 ~ 5mm by ceramic block material with ceramic shell residuum.After over cleaning,
It is roasted 0.5 hour at 1080 DEG C, it is air-cooled to arrive room temperature, ceramic particle of the grain size in 2 ~ 5mm of microcellular structure is made.Weigh 1000g
Ceramic particle is respectively put into the potassium permanganate of 5g/100ml originally in aqueous after drying（pH=13）Dipping is naturally dry after 2 hours
It is dry.Be placed in high concentration mercury vapour atmosphere and tested after sample is assembled, sample persistently inhale the mercury time be 43 minutes 3 hours, sample
It is 0.140 μ g that product, which always inhale mercury quantity, and design parameter is shown in Table 2.
It is dense at mercury import and export in the ceramic particle experimental atmosphere of 2 a concentration of 5g/100ml potassium permanganate solutions of table dipping
The parameters such as degree, adsorption rate, sample mercury capacity change with time situation
Embodiment 3
In the present embodiment, being prepared according to the method described in technical solution of the present invention has economic and environment-friendly efficient suction mercury porous
Industrial hot investment casting is ground into the particle of 2 ~ 5mm by ceramic block material with ceramic shell residuum.After over cleaning,
It is roasted 0.5 hour at 1080 DEG C, it is air-cooled to arrive room temperature, ceramic particle of the grain size in 2 ~ 5mm of microcellular structure is made.Weigh 500g potteries
Porcelain particle is respectively put into the potassium permanganate of 8g/100ml originally in aqueous after drying（pH=14）Dipping spontaneously dries after 2 hours.
Be placed in high concentration mercury vapour atmosphere and tested after sample is assembled, sample persistently inhale the mercury time be 50 minutes 3 hours, sample is total
Suction mercury quantity is 0.305 μ g, and design parameter is shown in Table 3.
It is dense at mercury import and export in the ceramic particle experimental atmosphere of 3 a concentration of 8g/100ml potassium permanganate solutions of table dipping
The parameters such as degree, adsorption rate, sample mercury capacity change with time situation.
Embodiment the result shows that, efficiently inhale mercury block materials in the present invention and can effectively remove mercury, using potassium permanganate
Solution carries out intensive treatment to material surface, it will be apparent that improves unit adsorbance and total suction mercury quantity.
The principle of the present invention：In the offgas, mercury exists in the form of simple substance, particle and valence state, and wherein Elemental Mercury is most difficult to
It removes.Using be attached to the crystalline state in shell granule pores potassium permanganate and potassium chloride as adsorbent, potassium permanganate is adding
Main decomposition goes out manganese dioxide and oxygen in thermal process, and mercury is fixed on ceramic particle by manganese dioxide with after mercury simple substance vapor reaction
Surface on and micropore in.Because mercury is adhered on ceramic particle by chemisorption, mercury will not occur to be desorbed and leak
Go out；Valence state mercury and particle mercury are captured in micropore using porous ceramics huge micro pore surface area simultaneously, finally steam mercury
Gas, mercury simple substance particle and valence state mercury adsorb removing completely.The key reaction being related to is as follows：6KMnO4→2K2MnO2+K2Mn4O8+
4O2And KMnO4→KMnO2+O2； 2Hg+MnO2→2HgO+Mn ；Hg+MnO2→Hg2MnO2（500 DEG C or more high-temperature flue gas）.
Inhale mercury after material can utilize in, Low Temperature Thermal desorption method recycling mercury（400~600℃）, renewable recycling, by
This reduces use cost, realizes energy-saving and environment-friendly purpose.Since the mercury accumulation adsorbed in porous ceramics is big, convenient for concentrating
Recycling, the mercury after being recycled by Low Temperature Thermal desorption method can also be recycled.Reduce manufacturing cost and use cost simultaneously.This is existing
It is not easily accomplished in technology.
In addition, when in use, inhale the entire ceramics of mercury process and have apparent weightening process, and when ceramic body reaches saturation shape
When state, then weight will not change substantially, can also coordinate gravity sensor to use the mercury absorbing material using this phenomenon, with
The saturation state of mercury material is received in detection, to be replaced in due course.It avoids when that can not observe use state in kind, Wu Fazhang
Control the adsorption activity of material.It will be apparent that the usage can not be applicable in non-solid material.
Claims (4)
1. a kind of preparation method for inhaling mercury porous ceramics block materials, it is characterized in that：Include the following steps：
1）The waste ceramic shell relic tap water or industrial cycle cooling waste water that hot investment casting is generated rinse, and remove shell
The dust on surface and other burs dry under sunlight, the ceramic shell relic dried are broken into grain size with jaw crusher
The fritter of 10 ~ 50mm；
2）The fritter of 10 ~ 50mm of grain size is put into roller and is ground into powder, leaves that ceramic block granularity is 2 ~ 5 mm
Grain；
3）Step 2 is washed with water）Middle ceramic block particle（2~5mm）, after natural drying, it is small that 0.5 ~ 3 is roasted at 900-1100 DEG C
When；
4）It will be dried 1-3 hours at 80 DEG C of ceramic block particle after roasting, immerse the activator solution of 2 ~ 8g/100ml of concentration
In 2 ~ 8 hours, take out, heated 1-3 hours at 70-150 DEG C；
5）Repeat step 4）It gets product for 1 ~ 3 time.
2. a kind of preparation method for inhaling mercury porous ceramics block materials according to claim 1, it is characterized in that：The precision
Casting generate waste ceramic type shell material include the Ludox of 50 ~ 70wt%, the gangue of 20 ~ 30wt%, 10 ~ 20wt% it is pure
Schmigel.
3. a kind of preparation method for inhaling mercury porous ceramics block materials according to claim 1, it is characterized in that：The mercury is lived
Property agent solution be pH 12 ~ 14, the potassium permanganate of 2 ~ 8g/100ml of concentration or one or both of potassium chloride aqueous solution, pH
Value can be adjusted by adding potassium permanganate, 20 ~ 35 DEG C of the temperature of mercury activator solution.
4. a kind of preparation method for inhaling mercury porous ceramics block materials according to claim 1, it is characterized in that：The mercury is inhaled
Attached dose of solvent is one or more of tap water, river water or industrial cycle waste water.
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