CN103388078A - Fly ash utilization method and remover for removing dioxin homologue and soluble heavy metal from fly ash - Google Patents

Fly ash utilization method and remover for removing dioxin homologue and soluble heavy metal from fly ash Download PDF

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CN103388078A
CN103388078A CN2012101414217A CN201210141421A CN103388078A CN 103388078 A CN103388078 A CN 103388078A CN 2012101414217 A CN2012101414217 A CN 2012101414217A CN 201210141421 A CN201210141421 A CN 201210141421A CN 103388078 A CN103388078 A CN 103388078A
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梁明在
梁克源
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Taiwan Supercritical Technology Co Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/10—Reduction of greenhouse gas [GHG] emissions
    • Y02P10/122—Reduction of greenhouse gas [GHG] emissions by capturing or storing CO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
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Abstract

The invention relates to a fly ash utilization method, comprises a flow washing step: putting the fly ash in a container and introducing a remover into the container to flow wash the fly ash, wherein a pressure of the container is 200-350 bars, a temperature of the container is 40-120 DEG C; the remover comprises a supercritical carbon dioxide fluid, an assist solvent and a metal adsorbent; and a replacement and separation step: introducing a replacement fluid into the container to replace the remover in the container and then separating the fluid from the fly ash. The remover for removing dioxin homologue and a soluble heavy metal from the fly ash comprises 1.0-20.0% by weight of the assist solvent, 0.1-3.0% by weight of the metal absorbent and 79.9-98.9% by weight of the supercritical carbon dioxide fluid.

Description

The flying dust method of resource, and in order to remove the remover of dioxin homologue and leachable heavy metal in flying dust
Technical field
The present invention is relevant for a kind of flying dust method of resource, be particularly to a kind ofly can process dioxin homologue in flying dust and the method for leachable heavy metal simultaneously, in the reduction flying dust, the content of dioxin homologue and leachable heavy metal, make the contained dioxin homologue of flying dust and leachable heavy metal concentration can be recycled lower than statutory standard.
Background technology
Prior art is with solid waste incinerator (Municipal solid waste incinerators, abbreviation MSWI) process the mode of solid waste, though can be by solid waste reducing, yet it burns in the flying dust (Fly ash) produced and contains multiple toxic substance, as dioxin homologue or leachable heavy metal, add the processing flying dust if be not good at and spread in environment or this flying dust do not carried out to recycling treatment and direct recycling, pollute the environment, and have a strong impact on the health of organism.The dioxin homologue, make a general reference many chlorine biphenyl dioxin (Polychlorinated dibenzo-p-dioxins, abbreviation PCDDs), many chlorine biphenyl furans (Polychlorinated dibenzofurans, be called for short PCDFs) and copline polychlorobiphenyl (Partially coplanar polychlorinated biphenyls) etc. there is the toxic chemical substance of biological accumulation, and the heavy metal general reference has metallic element or the metalloid element of overt toxicity to biology, as cobalt, tin, cadmium, chromium, lead, arsenic, mercury, nickel, zinc or copper.
In order to reduce in flying dust the threat that toxic substance produces organism, the toxic substance that correlation standard solid waste incinerator discharges in flying dust must be lower than concentration as shown in table 1, just flying dust can be recycled.
Table 1: each toxicant statutory standard of assert standard according to harmful cause waste
Figure BDA00001617255600021
Because the physicochemical characteristic difference of dioxin homologue and leachable heavy metal is large, therefore, must be to the flying dust that contains dioxin homologue or leachable heavy metal, carry out respectively different recycling treatment programs, could improve the processing efficiency of dioxin homologue in flying dust or leachable heavy metal, in order to carry out the recycling of flying dust.
The processing of existing dioxin homologue be in the high temperature incineration mode by the dioxin homologue thermo-cracking in flying dust, can make the direct scission of link of dioxin homologue and destroy its structure, and reducing the toxic equivalent of this flying dust.Yet the existing method of processing the dioxin homologue must provide mass energy to process more than 800 ℃ up to temperature, can effectively destroy the chemical structure of dioxin homologue to reduce its toxic equivalent.In addition, although thermal-cracking method can impel the leachable heavy metal in organism to dissociate out, but can't make the leachable heavy metal of ionic state further decompose, therefore, the existing method of processing the dioxin homologue can't reduce the solvable output of leachable heavy metal in flying dust.
And the existing method of processing leachable heavy metal, to coordinate the leachable heavy metal in organic removal of solvents flying dust with metal chelator (as EDTA), leachable heavy metal is dissolved in to organic layer, then, after organic solvent is removed, can obtains the flying dust through resource utilization.
Although the existing method of processing leachable heavy metal is used a large amount of organic solvents (as alcohols), yet, because the polarity difference of the polarity of organic solvent and dioxin homologue is very large, still can't extract dioxin homologue in flying dust to organic layer, therefore, the existing method of processing leachable heavy metal also can't be processed the dioxin homologue simultaneously; In addition, this metal chelator adds in this organic solvent, in order to help this metal chelator and leachable heavy metal chelating, and by leachable Extraction of Heavy Metals to organic layer, effectively to reduce the leachable leaching ability of heavy metal amount in this flying dust, yet this metal chelator but can reduce the solubleness of dioxin homologue in this organic solvent.
Therefore, no matter be the existing method of processing the dioxin homologue, or the existing method of processing leachable heavy metal, all can't make dioxin homologue and leachable heavy metal content in flying dust be reduced to below statutory standard simultaneously.
Please refer to TaiWan, China and disclose " waste that polluted by heavy metal or dioxin or the treatment process of soil " Patent Case No. 201016342, a kind ofly can, simultaneously by the dioxin homologue in flying dust and leachable heavy metal removal method, comprise an acid solution mixing step S91 as shown in Figure 1, a microwave heating step S92 and a water-washing step S93.
This acid solution mixing step S91 is to get the acid solutions such as sulfuric acid, hydrochloric acid or nitric acid to mix with this flying dust; This microwave heating step S92, with microwave heating Stable Release heat energy, accelerate the decomposition efficiency of acid solution to described various toxic substances, and the dioxin homologue in the destruction flying dust, simultaneously by leachable heavy metal extraction in acid solution, make toxic substance content in flying dust lower than statutory standard; Again with this water-washing step S93 by the remaining acid dilution in flying dust or the neutralization after, flying dust can be recycled.
Yet, this microwave heating step S92 must provide the energy to heat the acid solution of large volume, and this water-washing step S93 must expend a large amount of water resourcess, and still must process leachable heavy metal wherein with settling step for treated acid solution, can reclaim acid solution and use, or the acid solution that will remove leachable heavy metal is disposed in environment after diluting with water.Therefore, the treatment process that this Patent Case discloses, still must expend mass energy or water resources, and reality does not meet modern carbon reduction and treasures the environmental protection concept of water resources.
Accordingly, be necessary to provide a kind of dioxin homologue and the leachable heavy metal that can simultaneously process in flying dust, and can reduce the flying dust method of resource of the energy and water resources consumption.
Summary of the invention
Main purpose of the present invention is to provide a kind of flying dust method of resource, and it can improve the processing efficiency to dioxin homologue and leachable heavy metal in flying dust.
Of the present invention time a purpose is to provide a kind of flying dust method of resource, and it can reduce the consumption of organic solvent and water resources.
Another purpose of the present invention is to provide a kind of in order to remove the remover of dioxin homologue and leachable heavy metal in flying dust, and it can remove dioxin homologue and leachable heavy metal concentration in flying dust simultaneously.
The present invention's " flying dust ", refer to flying dust, the soil that contains dioxin homologue and leachable heavy metal or the end slag produced through thermal treatment.
For reaching aforementioned goal of the invention, flying dust method of resource of the present invention, comprise: a stream is washed step, that flying dust is placed in a room, a kind of remover passes into this room to carry out stream to flying dust and washes, and wherein, the pressure in this room is 200 ~ 350 bar, temperature in this room is 40 ~ 120 ℃, and this remover comprises supercritical carbon dioxide fluid, a kind of auxiliary solvent and a kind of metal absorbent; And a separation by displacement step, be that a kind of displacement fluid is passed into to this room, to replace the remover in this room, then this displacement fluid is separated with flying dust.
In flying dust method of resource of the present invention, this metal absorbent can be chosen as: two-tri-fluoridize dithiocarbamate salt (Bis-trifluoroethyldithiocarbamate, be called for short FDDC), diethyldithiocar bamic acid (Diethyldithiocarbamate, be called for short DDC), dipropyl disulfide is for carbaminate (Dipropyldithiocarbamate, be called for short P3DC), dibutyl dithiocaarbamate salt (Dibutyldithiocarbamate, be called for short BDC), diamyl dithiocarbamate salt (Dipentyldithiocarbamate, be called for short P5DC), dihexyl dithiocar-bamate (Dihexyldithiocarbamate, be called for short HDC), pyrrolidine dithiocarbamate (Pyrrolidinedithiocarbamate, be called for short PDC), 2, 4-diacetylmethane (Acetylacetone, be called for short AA), 1, 1, 1-tri-fluoro-2, 4-diacetylmethane (Trifluoroacetylacetone, be called for short TFA), hexafluoroacetylacetone (Hexafluoroacetylacetone, be called for short HFA), 2-thenoyltrifluoroacetone (Thenoyltrifluoroacetone, be called for short TTA), 2, 2-dimethyl-6, 6, 7, 7, 8, 8, 8,-seven fluoro-3, 5-diketone octane (Heptafluorobutanoyl-pivaroylmethane, be called for short FOD), tributyl phosphate (Tributylphosphate, be called for short TBP), tributylphosphine oxide (TBPO) (Tributylphosphine oxide, be called for short TBPO), trioctyl-phosphine oxide (Trioctylphosphine oxide, be called for short TOPO), triphenylphosphine oxide (Triphenylphosphine oxide, be called for short TPPO), two (2, 4, the 4-tri-methyl-amyl) (Bis (2 for phosphonic acids, 4, 4,-trimethylpentyl) phosphinic acid, be called for short Cyanex 272), 2, 4, (Bis (2 for 4-tri-methyl-amyl phosphonodithioic acid, 4, 4,-trimethylpentyl) dithio-phosphinic acid, be called for short Cyanex 301), two (2, 4, the 4-tri-methyl-amyl) (Bis (2 for phosphonothionic acid, 4, 4,-trimethyl-pentyl) monothiophosphinic acid, be called for short Cyanex302), di-(2-ethylhexyl)phosphoric acid (Di (2-ethylhexyl) phosphoric acid, be called for short D2EHPA) or dicyclohexyl 18 hat 6(dicyclohexyl-18-crown-6, be called for short DCH18C6).
In flying dust method of resource of the present invention, this metal absorbent is more preferred from Di (2-ethylhexyl) phosphoric acid.
In flying dust method of resource of the present invention, this auxiliary preferred solvents is low carbon number alkanes or alcohols, and its carbon number is 1 to 6, more preferably is chosen as methyl alcohol or normal hexane.
In flying dust method of resource of the present invention, the weight percent that this auxiliary solvent accounts for this remover is preferably 1.0 ~ 20.0%, the weight percent that this metal absorbent accounts for this remover is preferably 0.1 ~ 3.0%, and the weight percent that this supercritical carbon dioxide fluid accounts for this remover is preferably 79.9 ~ 98.9%.
A kind of in order to remove the remover of dioxin homologue and leachable heavy metal in flying dust, comprise: the auxiliary solvent that weight percent is 1.0 ~ 20.0%; The metal absorbent that weight percent is 0.1 ~ 3.0%; And the weight percent supercritical carbon dioxide fluid that is 79.9 ~ 98.9%.
Of the present invention in order in the remover of removing dioxin homologue and leachable heavy metal in flying dust, this metal absorbent can be chosen as: two-tri-fluoridize dithiocarbamate salt (Bis-trifluoroethyldithiocarbamate, be called for short FDDC), diethyldithiocar bamic acid (Diethyldithiocarbamate, be called for short DDC), dipropyl disulfide is for carbaminate (Dipropyldithiocarbamate, be called for short P3DC), dibutyl dithiocaarbamate salt (Dibutyldithiocarbamate, be called for short BDC), diamyl dithiocarbamate salt (Dipentyldithiocarbamate, be called for short P5DC), dihexyl dithiocar-bamate (Dihexyldithiocarbamate, be called for short HDC), pyrrolidine dithiocarbamate (Pyrrolidinedithiocarbamate, be called for short PDC), 2, 4-diacetylmethane (Acetylacetone, be called for short AA), 1, 1, 1-tri-fluoro-2, 4-diacetylmethane (Trifluoroacetylacetone, be called for short TFA), hexafluoroacetylacetone (Hexafluoroacetylacetone, be called for short HFA), 2-thenoyltrifluoroacetone (Thenoyltrifluoroacetone, be called for short TTA), 2, 2-dimethyl-6, 6, 7, 7, 8, 8, 8,-seven fluoro-3, 5-diketone octane (Heptafluorobutanoyl-pivaroylmethane, be called for short FOD), tributyl phosphate (Tributylphosphate, be called for short TBP), tributylphosphine oxide (TBPO) (Tributylphosphine oxide, be called for short TBPO), trioctyl-phosphine oxide (Trioctylphosphine oxide, be called for short TOPO), triphenylphosphine oxide (Triphenylphosphine oxide, be called for short TPPO), two (2, 4, the 4-tri-methyl-amyl) (Bis (2 for phosphonic acids, 4, 4,-trimethylpentyl) phosphinic acid, be called for short Cyanex 272), 2, 4, (Bis (2 for 4-tri-methyl-amyl phosphonodithioic acid, 4, 4,-trimethylpentyl) dithio-phosphinic acid, be called for short Cyanex 301), two (2, 4, the 4-tri-methyl-amyl) (Bis (2 for phosphonothionic acid, 4, 4,-trimethyl-pentyl) monothiophosphinic acid, be called for short Cyanex302), di-(2-ethylhexyl)phosphoric acid (Di (2-ethylhexyl) phosphoric acid, be called for short D2EHPA) or dicyclohexyl 18 hat 6(dicyclohexyl-18-crown-6, be called for short DCH18C6).
Of the present invention in order in the remover of removing dioxin homologue and leachable heavy metal in flying dust, this metal absorbent is more preferred from Di (2-ethylhexyl) phosphoric acid.
Of the present invention in order in the remover of removing dioxin homologue and leachable heavy metal in flying dust, this auxiliary preferred solvents is low carbon number alkanes or alcohols, and its carbon number is 1 to 6, and better is to be chosen as methyl alcohol or normal hexane.
Flying dust method of resource of the present invention, can be by this supercritical carbon dioxide fluid, auxiliary solvent and metal absorbent, provide than at the temperature and pressure condition of low power consuming, by the dioxin homologue in waste and leachable heavy metal, there is the effect of the processing efficiency that improves dioxin homologue and leachable heavy metal simultaneously.
Flying dust method of resource of the present invention, it can reduce the consumption of organic solvent and water resources, to reach effect friendly to environment and that economize on resources.
Of the present invention in order to remove the remover of dioxin homologue and leachable heavy metal in flying dust, can remove dioxin homologue and leachable heavy metal concentration in flying dust simultaneously, there is effect that improve to remove dioxin homologue and leachable heavy metal efficiency in flying dust.
The accompanying drawing explanation
Fig. 1: the step functional diagram of existing dioxin homologue and leachable heavy metal removal method.
Fig. 2: the step functional diagram of flying dust method of resource of the present invention.
Fig. 3: the super critical fluid apparatus configuration schematic diagram that the present embodiment provides.
Fig. 4: the dioxin homologue clearance broken line graph of the present embodiment C1 to C3 group.
Fig. 5: the dioxin homologue clearance broken line graph of the present embodiment C4 to C6 and C9 group.Wherein:
[the present invention]
S1 stream is washed step S2 separation by displacement step 1 electric hybrid module
Auxiliary solvent trough 13 rooms of 11 carbonic acid gas groove 12
2 pressure assembly 21 first back pressure valve 22 second back pressure valves
3 separator tank 31 first outlet 32 second outlets
C water cooler F flow regulator H well heater P infusion pump
[prior art]
S91 mixing step S92 microwave heating step S93 water-washing step.
Embodiment
For above-mentioned and other purpose of the present invention, feature and advantage can be become apparent, preferred embodiment of the present invention cited below particularly, and coordinate accompanying drawing, be described in detail below:
Please refer to shown in Fig. 2, flying dust method of resource of the present invention comprises: a stream is washed step S1 and a separation by displacement step S2.
This stream is washed step S1, flying dust is placed in a room, a kind of remover passes into this room to carry out stream to flying dust and washes, wherein, pressure in this room is 200 ~ 350 bar, temperature in this room is 40 ~ 120 ℃, and this remover comprises supercritical carbon dioxide fluid, a kind of auxiliary solvent and a kind of metal absorbent.In more detail, the pressure of this room and temperature condition contribute to maintain polarity (Polarity) characteristic of the contained supercritical carbon dioxide fluid of this remover, to dissolve the dioxin homologue in flying dust, the contained auxiliary solvent of this remover contributes to dissolve this metal absorbent, and by the temperature in this room, pressure condition, help this metal absorbent that the leachable heavy metal ion in flying dust is dissolved in this auxiliary solvent, make whereby dioxin homologue and leachable heavy metal ion desorption in flying dust, the dioxin homologue and the leachable heavy metal content that make to be adsorbed on flying dust reduce.
For example, this auxiliary solvent is as the diluting soln of this metal absorbent, this auxiliary preferred solvents be alkanes or the alcohols of low carbon number (C1 ~ C6), particularly methyl alcohol or normal hexane are as the diluting soln of metal absorbent, not only contribute to improve the adsorptivity of metal absorbent, can help to change again the polar character of this supercritical carbon dioxide fluid; This metal absorbent can be chosen as the organic compound of metal-chelating or coordination, and metal absorbent can be divided into four classes haply: (1) dithiocarbamate(s) (dithiocarbamate) metal absorbent, (2) diketone class (diketone) metal absorbent, (3) organic phosphates metal absorbent and (4) large lopps metal absorbent.
The dithiocarbamate(s) metal absorbent comprise as: Bis-trifluoroethyldithiocarbamate(is called for short FDDC), Diethyl-dithiocarbamate(is called for short DDC), Dipropyldithiocarbamate(is called for short P3DC), Dibutyldithiocarbamate(is called for short BDC), Dipentyl-dithiocarbamate(is called for short P5DC), Dihexyldithiocarbamate(is called for short HDC) or Pyrrolidinedithiocarbamate(abbreviation PDC).
Diketone metalloid sorbent material comprise be called for short AA as Acetylacetone(), Trifluoroacetylacetone(is called for short TFA), Hexafluoroacetylacetone(is called for short HFA), Thenoyltrifluoroacetone(is called for short TTA) or Heptafluorobutanoyl-pivaroylmethane(abbreviation FOD).
The organic phosphates metal absorbent comprises as Tributylphosphate(abbreviation TBP), Tributylphosphine oxide(is called for short TBPO), Trioctylphosphine oxide(is called for short TOPO), Triphenylphosphine oxide(is called for short TPPO), Bis (2, 4, 4,-trimethylpentyl) phosphinic acid(is called for short Cyanex 272), Bis (2, 4, 4,-trimethylpentyl) dithio-phosphinic acid(is called for short Cyanex 301), Bis (2, 4, 4,-trimethyl-pentyl) monothiophosphinic acid(is called for short Cyanex 302) or Di (2-ethylhexyl) phosphoric acid(abbreviation D 2eHPA).
Large lopps metal absorbent, as Crown ether.
The present invention can according to the heavy metal kind processed of wish select suitable metal absorbent; The present embodiment is chosen as D 2eHPA, can be with supercritical carbon dioxide fluid and this auxiliary solvent mating reaction the leachable heavy metal on flying dust, and can not reduce the effect that supercritical carbon dioxide fluid dissolves the dioxin homologue originally, can maintain again the efficiency of adsorbing metal ions own.
The present invention selects the carbonic acid gas that the above-critical state maintenance condition is lower (31.1 ℃ of emergent pressure 72bar and critical temperatures), as the primary solvent that dissolves the dioxin homologue, can reduce the energy expenditure for preparing supercutical fluid, and by pressure and the temperature (pressure is that 200 ~ 350bar, temperature are 40 ~ 120 ℃) of controlling this supercritical carbon dioxide fluid, adjust the polar character of this supercritical carbon dioxide fluid, and can be effectively and tool optionally dissolve the dioxin homologue; In addition, because carbonic acid gas is obtained easily, and it is colourless, tasteless, nontoxicity, explosive, the nonflammable also non-corrosiveness of tool not, therefore safe.
In addition, this supercritical carbon dioxide fluid contributes to flying dust, to contact equably, and, by the polarity of supercritical carbon dioxide fluid, by the Metal ion release of organic out, the metal ion that this metal absorbent captures in flying dust also is dissolved in this auxiliary solvent.So, flying dust method of resource of the present invention not only can effectively dissolve the dioxin homologue in flying dust, also can, by the effect of this metal absorbent and this supercritical carbon dioxide fluid, improve the effect to the adsorption of metal ions efficiency in flying dust.
This separation by displacement step S2, be that a kind of displacement fluid is passed into to this room, to replace the remover in this room, this displacement fluid separated with flying dust.In more detail, this displacement fluid can be chosen as supercutical fluid, the present embodiment is selected to replace the remover in this room with supercritical carbon dioxide fluid, relend and help the pressure reduced in this room, make this supercritical carbon dioxide fluid become gas phase, recycle after can selecting directly to drain in external environment by carbon dioxide or reclaiming this carbon dioxide; It is identical that the present embodiment is reduced to the temperature, pressure outer with room by this volume pressure, and carbon dioxide is directly discharged outside room, and the flying dust in this room has completed the removal of dioxin homologue and leachable heavy metal.
So, flying dust method of resource of the present invention, can reduce the use of organic solvent, and not needing to expend excessive power is heated flying dust and this remover, need to be by a large amount of aqueous cleaning flying dusts yet, in addition, this can't residual organic solvent in the flying dust of resource utilization, and can really reduce dioxin homologue and the leachable heavy metal content in flying dust.
For confirming flying dust method of resource of the present invention, really can process dioxin homologue and leachable heavy metal in flying dust simultaneously, and effectively reduce dioxin homologue content contained in flying dust, and the leachable heavy metal in the reduction flying dust, the present embodiment is obtained the flying dust sample that contains dioxin homologue and several leachable heavy metals from incinerator, and carry out following test: (A) the dioxin homologue content analysis of flying dust sample, (B) the leachable Analysis of Heavy Metals of flying dust sample, (C) the dioxin homologue test in different parameters condition removal flying dust sample reaches (D) different parameters condition and removes the leachable heavy metal test in the flying dust sample.
(A) the dioxin homologue content analysis of flying dust sample
The present embodiment is analyzed 17 kinds of dioxin homologue content in this flying dust sample with reference to TaiWan, China Environmental Protection Administration bulletin " dioxin and furans detection method (NIEAM801.12B) ", and this detection method borrows high-res gas chromatography mass spectrograph (GC/MS) to analyze with isotropic substance flag dilution method (Isotope dilution method).
Please refer to table 2, wherein, PeCDFs accounts for 10% of this flying dust sample, HxCDFs accounts for 19%, HpCDFs and accounts for 22%, OCDF and account for 8.97%, HpCCDs accounts for approximately 7.53%, and OCDD accounts for 25%, and this result shows that the contained dioxin homologue of this flying dust sample mainly take 5 to 8 chlorine atoms as main.The toxic equivalent of the dioxin homologue of this flying dust sample accounts for 35% of total toxic equivalent, is about 6.49ng I-Teq/g.
Table 2: content and the toxic equivalent of 17 kinds of dioxin homologues of the present embodiment
Figure BDA00001617255600111
Figure BDA00001617255600121
Stationary source dioxin emission standard (No. 0940093326th, ring administration empty word) according to 94 years bulletins of TaiWan, China Environmental Protection Administration, the contained dioxin homologue of per unit weight flying dust must, lower than 1ng/g, can be poured in environment by this flying dust or be recycled.
(B) the leachable Analysis of Heavy Metals of flying dust sample
The present embodiment is with reference to TaiWan, China Environmental Protection Administration bulletin " cause waste toxicity characteristic stripping program (NIEA R201.14C) ", and changes to respond to coupled plasma Anlysis of Emission spectrometry (ICP-OES) the leachable heavy metal content in this flying dust sample is analyzed.In more detail, get 25 gram flying dust samples and shake extraction after 18 hours with 250 milliliters of acetic acid (pH 2.88) in room temperature, flying dust is filtered, and carry out microwave digestion after getting the 1ml extraction liquid and 4ml nitric acid (69%) and 3ml hydrogen peroxide mixing, analyze the leachable heavy metal content such as its cadmium, chromium, lead, arsenic, mercury, nickel, zinc and copper with ICP-OES after obtaining a Digestive system.
Table 3: the content of 8 kinds of leachable heavy metals of the present embodiment
Project Content (mg/Kg) * Project Content (mg/Kg) *
Cadmium ND Mercury 422.80
Chromium ND Nickel ND
Plumbous 445.25 Zinc 17.88
Arsenic 0.08 Copper 5.52
* ND represents that this value is lower than detecting limit.
(C) the different parameters condition is removed the dioxin homologue test in the flying dust sample
The present embodiment provides a super critical fluid apparatus as shown in Figure 3, it comprises an electric hybrid module 1, pressure assembly 2 and a separator tank 3, and this electric hybrid module 1 and this separator tank 3 are interconnected, and control the internal pressure of these electric hybrid modules 1 and this separator tank 3 with this pressure assembly 2.
This electric hybrid module 1 is provided with a carbonic acid gas groove 11, auxiliary solvent trough 12 and a room 13, this carbonic acid gas groove 11 and this auxiliary solvent trough 12 are communicated with this room 13, this carbonic acid gas groove 11 is in order to accommodating supercritical carbon dioxide fluid, this auxiliary solvent trough 12 in order to accommodating this auxiliary solvent (as methyl alcohol or normal hexane) and this metal absorbent (as E 2dHPA), this room 13 is processed sample in order to an accommodating wish, this carbonic acid gas groove 11 and this auxiliary solvent trough 12 have the function (as heater H or the water cooler C of graphic sign) of regulating tank internal temperature and pressure, all be connected with separately infusion pump P and flow regulator F internal solution is delivered in this room 13.
This pressure assembly 2 comprises first back pressure valve 21 and second back pressure valve 22, and wherein this first back pressure valve 21 is controlled the internal pressure of this room 13, and this second back pressure valve 22 is controlled the internal pressure of this separator tank 3.
This separator tank 3 includes 31 and one second outlets 32 of one first outlet, these the first outlet 31 supplied gas loss to environment or gathering barrel groove (figure does not illustrate), the auxiliary solvents outflows that this second 32 of outlet can make this mix with waste.
The operation instructions of the present embodiment super critical fluid apparatus is as follows: by a waste sample (the present embodiment is a flying dust sample) as in this room 13, make temperature and the pressure condition of this room 13 reach preset value, adjusting the flow velocity that this operating fluid flows into this room 13 is 4.5ml/min again, and the setting operation time (as 3 ~ 6 hours) starts to remove dioxin homologue and the leachable heavy metal of this sample; This operating fluid flow in this separator tank 3 from this room 13, and the pressure decreased of this separator tank 3, to 40bar, is made to this supercritical carbon dioxide fluid gasification, and this carbon dioxide can reclaim and re-use, or directly drains in environment; These separator tank 3 inside are left extract remainder and are included the toxic substances such as dioxin homologue and leachable heavy metal, and the flying dust in this room 13 has been removed the toxic substances such as dioxin homologue and leachable heavy metal, and can be recycled.
For example, the present embodiment first is placed in this room 13 by this flying dust sample (approximately 110 grams), and, with the blending ratio shown in table 4, this supercritical carbon dioxide fluid (is called for short to CO afterwards 2 (sf)), after this auxiliary solvent and this metal absorbent mix, with the flow velocity of 4.5ml/min this room 13 of flowing through, the time to be mixed finishes to take out this flying dust sample, total toxic equivalent of more treated and undressed flying dust sample, calculate each group dioxin clearance.
Treatment condition and the dioxin clearance (%) of table 4: C1 to C8 group
Figure BDA00001617255600141
Figure BDA00001617255600151
* the auxiliary solvent of C1 to C7 group is methyl alcohol, and the C8 group is normal hexane.
In the present embodiment, the dioxin clearance of C4 group is eight groups of removal effect preferablies in treatment condition, and its toxic equivalent can be reduced to 0.84ng I-Teq/g.Compare C1 to C3 group, this dioxin clearance is directly proportional with the temperature in this room 13, and temperature is located at more than 40 ~ 120 ℃, and its dioxin clearance can reach more than 65%; Compare C2 and C5 group, its methyl alcohol weight percent changed in this operating fluid when increases mixing time, and its dioxin clearance can both reach more than 80%, then compares the C7 group, the weight percent of its methyl alcohol is only 2.67%, and its dioxin clearance is still suitable with the C5 group; Relatively C5 and C6 group, this dioxin clearance is directly proportional with the pressure in this room 13, and pressure is located at 200 ~ 350bar and can both be made the dioxin clearance reach more than 75%.In the present embodiment, the C8 group is that methyl alcohol is replaced with to normal hexane, and its dioxin clearance also can reach 58.4%.
Please refer to Fig. 4, get the flying dust sample that C1, C2 as shown in table 4 and C3 group are processed, in the mode of test (A), analyze its 17 kinds of dioxin homologue clearances; Hence one can see that, and the interior temperature of this room 13 is located at 40 ~ 120 ℃ of dioxin clearances that can both obtain more than 60%.
Referring again to Fig. 5, get the flying dust sample that C4, C5 as shown in table 4 and C6 group are processed, separately get one group of flying dust sample (110 grams, this is the C9 group) and only with 6 kilograms of methyl alcohol, stir immersion after 18 hours under room temperature, in the mode of test (A), analyze its 17 kinds of dioxin homologue clearances.Hence one can see that soaks and really can't remove the dioxin homologue in the flying dust sample with methyl alcohol merely; And soak the contact efficiency can accelerate this auxiliary solvent and this flying dust with supercritical carbon dioxide fluid, more can help the dioxin homologue in this flying dust to be dissolved in this supercritical carbon dioxide fluid and this auxiliary solvent, in addition, these room 13 internal pressures are located at 200 ~ 350bar and can both be obtained the dioxin clearance more than 70%.
(D) the different parameters condition is removed the leachable heavy metal test in the flying dust sample
The present embodiment is got four groups of flying dust samples and is carried out leachable Analysis of Heavy Metal with the method for test (B), wherein: the D1 group is the handled flying dust sample of condition through table 4 C7 group, the D2 group, it is the condition as the C7 group, but change methyl alcohol into normal hexane as auxiliary solvent, the D3 group is the flying dust sample of processing through the condition of table 4 C4 group, and the D4 group is the flying dust sample of processing through the condition of table 4 C9 group, and its result please refer to the 5th table.
The 5th table: the solvable output of leachable heavy metal (mg/Kg) of the present embodiment D1 to D3 group
Figure BDA00001617255600161
* ND represents that this value is lower than detecting limit.
Via the processing of D1 to D4 group, the stripping because the leachable heavy metal compound of many oxidation state changes leachable heavy metal ion into, so the leachability of the leachable heavy metal of some projects can increase; And, after the processing of the present embodiment D1 and D2 group, really can obviously reduce the solvable output of lead, mercury or zinc.
For flying dust resource utilization recycling, after processing via method of the present invention, the solvable output of whole leachable heavy metal obviously descends, and as shown in the C1 and C2 group result of table 4, the present invention can reduce dioxin homologue and the leachable heavy metal content in this flying dust really simultaneously, and according to contained dioxin homologue and leachable heavy metal content in waste, select to using methyl alcohol or normal hexane as auxiliary solvent, can improve the efficiency of processing dioxin homologue or leachable heavy metal.From the above, flying dust method of resource of the present invention can effectively improve the processing efficiency to dioxin homologue and leachable heavy metal in flying dust really.
Accordingly, flying dust method of resource of the present invention, can be by this supercritical carbon dioxide fluid, auxiliary solvent and metal absorbent, provide than at the temperature and pressure condition of low power consuming, by the dioxin homologue in waste and leachable heavy metal, there is the effect of the processing efficiency that improves dioxin homologue and leachable heavy metal simultaneously.
Flying dust method of resource of the present invention, it can reduce the consumption of organic solvent and water resources, to reach effect friendly to environment and that economize on resources.
Of the present invention in order to remove the remover of dioxin homologue and leachable heavy metal in flying dust, can remove dioxin homologue and leachable heavy metal concentration in flying dust simultaneously, there is effect that improve to remove dioxin homologue and leachable heavy metal efficiency in flying dust.
But as described above is only preferred embodiment of the present invention, when not limiting the scope of the present invention with this; Therefore all simple equivalences of doing according to the present patent application the scope of the claims and creation description change and modify, and all should still remain within the scope of the patent.

Claims (9)

1. a flying dust method of resource, is characterized in that, comprises:
A stream is washed step, that flying dust is placed in a room, a kind of remover passes into this room to carry out stream to flying dust and washes, wherein, pressure in this room is 200 ~ 350 bar, temperature in this room is 40 ~ 120 ℃, and this remover comprises supercritical carbon dioxide fluid, a kind of auxiliary solvent and a kind of metal absorbent; And
A separation by displacement step, pass into this room by a kind of displacement fluid, to replace the remover in this room, then this displacement fluid separated with flying dust.
2. flying dust method of resource as claimed in claim 1, it is characterized in that, this metal absorbent is: two-tri-fluoridize dithiocarbamate salt, diethyldithiocar bamic acid, dipropyl disulfide is for carbaminate, dibutyl dithiocaarbamate salt, diamyl dithiocarbamate salt, the dihexyl dithiocar-bamate, pyrrolidine dithiocarbamate, 2, the 4-diacetylmethane, 1, 1, 1-tri-fluoro-2, the 4-diacetylmethane, hexafluoroacetylacetone, the 2-thenoyltrifluoroacetone, 2, 2-dimethyl-6, 6, 7, 7, 8, 8, 8,-seven fluoro-3, 5-diketone octane, tributyl phosphate, tributylphosphine oxide (TBPO), trioctyl-phosphine oxide, triphenylphosphine oxide, two (2, 4, the 4-tri-methyl-amyl) phosphonic acids, 2, 4, 4-tri-methyl-amyl phosphonodithioic acid, two (2, 4, the 4-tri-methyl-amyl) phosphonothionic acid, di-(2-ethylhexyl)phosphoric acid or dicyclohexyl 18 hats 6.
3. flying dust method of resource as claimed in claim 1, is characterized in that, this auxiliary solvent is low carbon number alkanes or alcohols, and its carbon number is 1 to 6.
4. flying dust method of resource as claimed in claim 3, is characterized in that, this auxiliary solvent is methyl alcohol or normal hexane.
5. as claim 1,2,3 or 4 described flying dust method of resource, it is characterized in that, the weight percent that this auxiliary solvent accounts for this remover is 1.0 ~ 20.0%, the weight percent that this metal absorbent accounts for this remover is 0.1 ~ 3.0%, and the weight percent that this supercritical carbon dioxide fluid accounts for this remover is 79.9 ~ 98.9%.
6. one kind in order to remove the remover of dioxin homologue and leachable heavy metal in flying dust, it is characterized in that, it comprises:
The auxiliary solvent that weight percent is 1.0 ~ 20.0%;
The metal absorbent that weight percent is 0.1 ~ 3.0%; And
The supercritical carbon dioxide fluid that weight percent is 79.9 ~ 98.9%.
7. as claimed in claim 6 in order to remove the remover of dioxin homologue and leachable heavy metal in flying dust, it is characterized in that, this metal absorbent is: two-tri-fluoridize dithiocarbamate salt, diethyldithiocar bamic acid, dipropyl disulfide is for carbaminate, dibutyl dithiocaarbamate salt, diamyl dithiocarbamate salt, the dihexyl dithiocar-bamate, pyrrolidine dithiocarbamate, 2, the 4-diacetylmethane, 1, 1, 1-tri-fluoro-2, the 4-diacetylmethane, hexafluoroacetylacetone, the 2-thenoyltrifluoroacetone, 2, 2-dimethyl-6, 6, 7, 7, 8, 8, 8,-seven fluoro-3, 5-diketone octane, tributyl phosphate, tributylphosphine oxide (TBPO), trioctyl-phosphine oxide, triphenylphosphine oxide, two (2, 4, the 4-tri-methyl-amyl) phosphonic acids, 2, 4, 4-tri-methyl-amyl phosphonodithioic acid, two (2, 4, the 4-tri-methyl-amyl) phosphonothionic acid, di-(2-ethylhexyl)phosphoric acid or dicyclohexyl 18 hats 6.
8. as claimed in claim 6ly in order to remove the remover of dioxin homologue and leachable heavy metal in flying dust, it is characterized in that, this auxiliary solvent is low carbon number alkanes or alcohols, and its carbon number is 1 to 6.
9. as claimed in claim 8ly in order to remove the remover of dioxin homologue and leachable heavy metal in flying dust, it is characterized in that, this auxiliary solvent is methyl alcohol or normal hexane.
CN2012101414217A 2012-05-09 2012-05-09 Fly ash utilization method and remover for removing dioxin homologue and soluble heavy metal from fly ash Pending CN103388078A (en)

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CN111036667A (en) * 2019-11-23 2020-04-21 山东碧泉环境工程技术有限公司 Method for repairing heavy metal contaminated soil
CN113955787A (en) * 2021-08-31 2022-01-21 江西盖亚环保科技有限公司 Process for removing dioxin in fly ash

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CN111036667A (en) * 2019-11-23 2020-04-21 山东碧泉环境工程技术有限公司 Method for repairing heavy metal contaminated soil
CN113955787A (en) * 2021-08-31 2022-01-21 江西盖亚环保科技有限公司 Process for removing dioxin in fly ash
CN113955787B (en) * 2021-08-31 2023-10-13 江西盖亚环保科技有限公司 Process for removing dioxin from fly ash

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Application publication date: 20131113