CN104812464A - Magnetic adsorbents, methods for manufacturing a magnetic adsorbent, and methods of removal of contaminants from fluid streams - Google Patents

Magnetic adsorbents, methods for manufacturing a magnetic adsorbent, and methods of removal of contaminants from fluid streams Download PDF

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Publication number
CN104812464A
CN104812464A CN201380031297.1A CN201380031297A CN104812464A CN 104812464 A CN104812464 A CN 104812464A CN 201380031297 A CN201380031297 A CN 201380031297A CN 104812464 A CN104812464 A CN 104812464A
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adsorbent
magnetic
magnetic adsorbent
active carbon
ferriferous oxide
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大卫·W·马齐克
海瑟尔·伯恩
阿米娜·可汗
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Ka Ben Koster Group Co Ltd
Carbonxt Group Ltd
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Ka Ben Koster Group Co Ltd
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    • B01D53/02—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 by adsorption, e.g. preparative gas chromatography
    • B01D53/06—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 by adsorption, e.g. preparative gas chromatography with moving adsorbents, e.g. rotating beds
    • B01D53/10—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 by adsorption, e.g. preparative gas chromatography with moving adsorbents, e.g. rotating beds with dispersed adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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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
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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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
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—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 physical properties
    • B01J20/28009—Magnetic properties
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    • 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
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3021—Milling, crushing or grinding
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    • B01D2251/108—Halogens or halogen compounds
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    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20707—Titanium
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    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/60—Heavy metals or heavy metal compounds
    • B01D2257/602—Mercury or mercury compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/80—Employing electric, magnetic, electromagnetic or wave energy, or particle radiation
    • B01D2259/814—Magnetic fields

Abstract

A magnetic adsorbent includes an adsorbent and iron oxide implanted onto a surface of the adsorbent, wherein a total surface area of the magnetic adsorbent is not substantially less than a total surface area of the adsorbent. Optionally, the adsorbent is activated carbon.

Description

Magnetic adsorbent, for the preparation of magnetic adsorbent method and from fluid stream, remove the method for pollutant
Background technology
At present by numerous harmful air pollutants (hazardous airpollutant, HAP) of EPA management and control, mercury and compound containing mercury are due to the release rate that raises and lack suitable control technology and form concern source of attaching most importance to.Although generation is in the environment usually lower, mercury can be transferred in multiple organism, is then amplified by food chain.Such as, in some fishes, the mercury concentration of accumulation can reach the level than height millions of times in water.People consume these fishes, cause mercury to accumulate in Various Tissues, can cause serious nerve and development impact, such as, lose sensation or cognitive ability, tremble, cannot walk, faint from fear and even death.Methyl mercury is the organic mercury of most common form, and it is almost absorbed in blood flow completely, and by placental metastasis to fetus institute in a organized way in, comprise in brain.Due to the health concerns relevant with edible mercury contaminated fish, as U.S.'s The Great Lakes, some areas forbid that fishing has caused sizable economic loss.
EPA estimates the burning (as in coal fired power generation field) of the artificial mercury emissions of nearly 87% from originate such as refuse (as turned at refuse in energy equipment) and fossil fuel.Recognize this point, used control technology to attempt and caught and process the mercury be present in burnt gas.At present, powdered activated carbon (Powdered Activated Carbon, PAC) is injected in flue gas stream the best control technology be proved to be for mercury removing.When the regulation for mercury removing based on Mercury and Air Toxics Standards in time implementing for 2015, estimate according to Freedonia, will reach about 260 to the demand expection of the powdered activated carbon for catching mercury, 000 ton annual.The enforcement increased causes very large financial burden by the facility by management and control.At present, shown that bromination active carbon has every pound of the highest product mercury removal rate.But these products have higher marginal cost (cost margin), therefore will increase economic impact, and may cause corrosion to shop equipment.In addition, the mercury adsorption efficiency that PAC is usually low and lack suitable regeneration techniques and evoked improvement material to reduce costs or to put forward high performance interest.
Another shortcoming using PCA injected system is the accumulation of useless PAC in flyash.Flyash, coal combustion byproduct (Coal Combustion Byproduct, CCB) (namely, noninflammability inorganic matter and the carbon do not fired) fine particle fraction, collected by from flue gas, then usually sold, for recycling valuably in the production of concrete and other materials.To replace in construction material normally used lime, cement or crushed stone material can economize energy and resource with flyash, provide the alternative of the landfill disposal to refuse simultaneously.But, when common flyash collecting device and PAC injected system in conjunction with time, due to carbon very most in ash, make the Quality Down of the flyash of collection.This flyash can not be sold again for recycling valuably, and must landfill.Current research for isolation technics does not also find the appropriate method being separated PAC from flyash.Therefore, the method that easily can be separated PAC from flyash is expected.(a) is kept for the quality of the flyash sold subsequently and recycle by such method, and (b) allows PAC is used for other mercury again catches.
U.S. Patent No. 7,879,136 teach a kind of method that magnetic active carbon by producing by the wet type precipitation method reclaims PAC from flyash.The method and United States Patent (USP) 2,479,930,6,914,034 and 8,097,185B2 is similar, and the latter also teach that the method using iron precursor to prepare magnetic active carbon.Other document produces magnetic adsorbent as follows: use adhesive to make adsorbent and magnetic material combine (U.S. Patent No. 7,429,330), adsorbent is mixed (U.S. Patent No. 4 with magnetic material, 260,523) or by magnetic material with organic material mix and then activate (United States Patent (USP) 4,260,523,4,201,831 and 7,429,330).
Although the method that referenced patent describes all can perform well in laboratory scale application, it also brings challenge to full large-scale production, includes but not limited to high-energy source cost.Therefore, dry type production method is the key that magnetic active carbon technology turns to full scale.U.S. Patent No. 8,057,576 (" ' 576 patents ") have taught and have used physical method to produce the blend product of catching for mercury.This product is sorbing material and forms complex compound with mercury or make the mixture of mercury oxidation or additive that the two all has.Described additive is not be implanted on adsorbent surface.
This point is highlighted by the following fact, and adsorbent and additive are injected in flue gas by an embodiment instruction of this patent respectively.The invention of ' 576 patents does not comprise magnetic additive, and therefore product does not reclaim from flyash by magnetic.
Summary of the invention
By being physically implanted on adsorbent by magnetic additive by dry type production method, the cost-benefit method of the adsorbent of catching for mercury can be produced on a large scale.
Disclosed herein is the method preparing magnetic adsorbent, use magnetic adsorbent from fluid stream, remove the method for pollutant and use the recovery of rear magnetic adsorbent.
More specifically, provide magnetic adsorbent, it has enough oxidizing force, affinity and surface area for catching mercury from the flue gas of coal-burning facility.This material also can be used for catching other target contaminants, such as arsenic and selenium.Then described magnetic adsorbent can be reclaimed from coal combustion flyash, and be re-introduced in flue gas and catch for other mercury.
The method preparing magnetic adsorbent comprises and selected adsorbent and magnetic additive and oxidation additive in some cases being combined.Precursor adsorption agent can be active carbon, reactivation charcoal, silica gel, zeolite, alumina clay or have other solid materials of enough surface areas of catching for mercury.The one that magnetic additive is preferably following: magnetic iron ore, bloodstone, goethite or maghemite.Oxidation additive can include but not limited to halide (that is, the NH of alkali metal, alkaline-earth metal and ammonium 4br, KBr, LiBr, NaBr, NaCl, KCl, LiCl, KI, LiI, NaI) and semiconductor (TiO 2, ZnO, SnO 2, VO 2and CdS).
Provide the method (magnetic adsorbent production method) for the preparation of magnetic adsorbent, described magnetic adsorbent removes the application of pollutant and the recovery after using thereof from fluid stream.
Prepare the method for magnetic adsorbent, it comprises the other additive combination by improving oxidability under selected adsorbent and magnetic additive and certain situation.Described additive can use multiple method to be implanted on adsorbent, includes but not limited to: adsorbent and additive are mixed together, grind or grind until material some part physical be implanted on the surface of active carbon.
In addition, the method (contaminant removal method) for removing one or more pollutants from fluid stream is provided.Described method comprises to be made fluid stream contact with magnetic adsorbent thus makes pollutant be adsorbed on magnetic adsorbent, then from fluid stream, removes the magnetic adsorbent that it is adsorbed with pollutant.
Additionally provide and the composite of collection is recycled to fluid contact for the method (composite method for recycling) further removing pollutant.
In one embodiment, magnetic adsorbent comprises adsorbent and is implanted to the ferriferous oxide on the surface of adsorbent, and wherein the total surface area of magnetic adsorbent is not less than the total surface area of adsorbent substantially.Optionally, adsorbent is active carbon.In a kind of configuration, add the additive being selected from halogen, photochemical catalyst and adhesive.In selecting at one, magnetic adsorbent does not comprise secondary deposit (secondarydeposit).Optionally, the ratio of the weight of ferriferous oxide and the gross weight of magnetic adsorbent is 1% to 20%.In one structure, the ratio of the weight of ferriferous oxide and the gross weight of magnetic adsorbent is 5% to 15%.Or the ratio of the weight of ferriferous oxide and the gross weight of magnetic adsorbent is 10%.Optionally, ferriferous oxide highly crystalline after the implantation.In one structure, the crystalline nature of ferriferous oxide keeps after the implantation.
In another embodiment, magnetic adsorbent is substantially composed of the following components: adsorbent; Be implanted to the ferriferous oxide on the surface of adsorbent, wherein the surface area of magnetic adsorbent is not less than the surface area of adsorbent substantially.In one structure, adsorbent is active carbon.
In one embodiment, the method preparing magnetic adsorbent comprises use mechanical mixing equipment and adsorbent and magnetic material is combined.Optionally, adsorbent is active carbon and magnetic material is ferriferous oxide.In a replacement scheme, mechanical mixing equipment is selected from ball mill, aeropulverizer (jet mill), conical mills (conical mill).In a further alternative, the friction between mechanical mixing equipment promotion particle and collision.Optionally, described method comprises and being implanted on the surface of adsorbent by magnetic material.In a further alternative, described combination comprises grinding, and is performed until magnetic adsorbent by till 325 mesh sieves.
In one embodiment, process the method for effluent stream to comprise and process effluent stream by injecting magnetic adsorbent particle and use magnetic field to reclaim magnetic adsorbent particle.Optionally, after recovery, magnetic absorption particle is re-introduced in effluent stream together with other magnetic absorption particle.Optionally, magnetic adsorbent particle removes mercury from effluent stream.
In another embodiment, high-quality flyash is reclaimed from by the stream of magnetic adsorbent process.Described method comprises use magnetic field and from the flyash effluent stream, catches magnetic adsorbent to produce two kinds of products: (1) high-quality flyash, and the magnetic adsorbent that (2) reclaim.
In one embodiment, comprise for the system removing mercury from effluent stream: active carbon injected system, it injects activated carbon product in effluent.Described system also comprises the first electrostatic precipitator be arranged on after active carbon injected system, and it receives effluent.Optionally, after the first electrostatic precipitator is arranged on next-door neighbour's active carbon injected system, and without any intermediate treatment.In a replacement scheme, activated carbon product is magnetic.In another is selected, activated carbon product comprises photochemical catalyst.Optionally, the first electrostatic precipitator activation light catalyst.Or, before the second electrostatic precipitator next-door neighbour active carbon injected system.Optionally, activated carbon product has the ferriferous oxide be implanted on surface, and its surface area is not less than the surface area of not oxides-containing iron substantially.
In another embodiment, the magnetic part that adsorbent comprises activated carbon section and is connected with activated carbon section, wherein the magnetic activity of magnetic part is not shielded by activated carbon section.Optionally, magnetic part is implanted on the surface of activated carbon section.Or the total surface area not containing the activated carbon section of magnetic part is at least substantially identical with the total surface area of adsorbent.
Accompanying drawing is sketched
Fig. 1 shows the titanium dioxide of acticarbon and the SEM image (image) of iron signal and EDS Surface scan figure (map), proves that adsorbent surface does not exist additive;
Fig. 2 shows SEM image and the EDS Surface scan figure of the iron signal of the magnetic adsorbent prepared by the magnetic iron ore of grinding absorbent charcoal material and 10% load capacity by weight, demonstrates the distribution of the magnetic iron ore spread all on sample surfaces;
Fig. 3 represents and analyzes the some EDS of particle independent in Fig. 2, proves the obvious existence of iron on adsorbent;
Fig. 4 represents by acticarbon and the TiO being respectively 1% and 10% load capacity by weight 2the iron of magnetic adsorbent prepared by ball milling and the SEM image of titanium dioxide signal and EDS Surface scan figure is carried out with magnetic iron ore.This figure demonstrates the extensive distribution of magnetic iron ore on adsorbent surface, and the existence of titanium dioxide;
Fig. 5 represents and analyzes the some EDS of particle independent in Fig. 4, proves the obvious existence of iron on adsorbent;
Fig. 6 represents and analyzes the some EDS of particle independent in Fig. 4, proves the obvious existence of titanium dioxide on adsorbent;
Fig. 7 represents SEM image and the EDS Surface scan figure of the iron signal of the magnetic adsorbent prepared by the magnetic iron ore of 10% load capacity by weight by mechanical fusion.This figure demonstrates the distribution of magnetic iron ore on whole sample surfaces;
Fig. 8 represents the schematic diagram of the laboratory scale for collecting fixed bed data provided herein;
Fig. 9 represents the mercury removing curve in the fixed bed evaluation procedure using multiple magnetic absorption agent material, proves the benefit that additive removes for mercury;
Figure 10 represents at the mercury removing curve of magnetic adsorbent under true flue gas conditions using Basal activity charcoal and produce, and demonstrates the benefit for mercury removing;
Figure 11 a and 11b shows the embodiment of the active carbon injected system of electrostatic precipitator (ESP) upstream;
Figure 12 shows for existing commercially available industrial PAC (industrial charcoal), is coated with 10%Fe by weight 3o 4mPAC (MPAC), be coated with 10%Fe by weight 3o 4and 1%TiO 2mPAC (MPAC-TiO 2) and be coated with 10%Fe by weight 3o 4the mercury removing curve of the active carbon in 5MW slip-stream (slip stream) flue gas is injected into the another kind (MPAC-Na-Br) of 2.5%NaBr.
Detailed description of the invention
In an embodiment of magnetic adsorbent production method, prepare magnetic adsorbent composite, made magnetic material physically be implanted on the exposed surface of adsorbent whereby.Implant by adsorbent and ferriferous oxide being grouped together and using mechanical mixing equipment such as ball mill, aeropulverizer, conical mills etc. to realize simultaneously.This hybird environment is conducive to friction between particle and collision, thus promotes to implant.Power for implanting can comprise Van der Waals force, capillary force, electrical force (electrical force) and statcoulomb power.These power can be improved in mixed process.
Compared with some the prior art adsorbents being implanted to absorbent interior with magnetic material, surface implantation is the key character of produced magnetic adsorbent.Implantation on surface do not shield or barrier effect in the magnetic force of magnetic material.Owing to can it be caught again by using magnetic force after the treatment, which feature provides catching again and recycling magnetic adsorbent.This greatly improves the cost benefit of methods described herein and material.The implantation of magnetic material is discussed in this paper many places.The amount of magnetic material implanted and the marked change of kind should be considered, and it may use with the implanted prosthetics discussed relevant with herein institute.
Sorbing material for generation of magnetic adsorbent will have the porous of estimable surface area and exploitation.It can be: active carbon, reactivation charcoal, zeolite, alumina clay, silica gel etc.For many application, adsorbent is active carbon.Term used herein " active carbon " refers to powdery or graininess charcoal for being carried out purifying by absorption.In many structures, the surface area of the active carbon used is 200m 2/ g to 1,000m 2/ g, more preferably 300m 2/ g to 700m 2/ g, most preferably 400m 2/ g to 600m 2/ g.In some are selected, use powdered activated carbon (PAC).For this application, term " powdered activated carbon " refers to that 90% can by the active carbon of 352 mesh sieves (45 μm) (that is, at least 90% by 352 mesh sieves).In addition, following abbreviation may be used herein: active carbon: AC; Powdered activated carbon: PAC; And magnetic powder shaped activated carbon: MPAC.
Magnetic material can be following at least one: magnetic iron ore (Fe 3o 4), maghemite (γ-Fe 2o 3), bloodstone (α-Fe 2o 3) and goethite (FeO (OH)), in many embodiments, be magnetic iron ore.In composite, the amount of magnetic material is preferably gross weight based on final composite by weight at least 1% to being less than 20%; More preferably, based on the gross weight by weight 5% to 15% of final composite; Most preferably, based on the gross weight by weight 5% of final composite.
Fig. 1-3 shows the result of the composite of preparation as mentioned above.Fig. 1 shows the titanium dioxide of acticarbon and the SEM image of iron signal and EDS Surface scan figure under 500 x magnifications according to an embodiment, proves that adsorbent surface does not exist additive.In FIG, SEM image and EDS (energy dispersion X-ray spectrometer) Surface scan figure show to have occurred iron signal on the activated carbon.Fig. 2 shows the sample produced by grinding above-mentioned active carbon.Fig. 2 shows SEM image and the EDS Surface scan figure of the iron signal of magnetic adsorbent under 500 x magnifications prepared by the magnetic iron ore of grinding absorbent charcoal material and 10% load capacity by weight, demonstrates the distribution of the magnetic iron ore spreading all over sample surfaces.In figure 3, the chart of the appearance of the main Fe 330 shown on active carbon compared with other pollutants is shown.Fig. 3 represents that the some EDS of independent particle on Fe particle in milled sample (FeOx) analyzes, and demonstrates the obvious existence of iron on adsorbent.The graph show counting 310 and in contrast to energy (keV) 320.Fig. 1 shows the titanium dioxide of acticarbon and the SEM image of iron signal and EDS Surface scan figure under 500 x magnifications according to an embodiment, proves that adsorbent surface does not exist additive.
In addition, other additives can be used, such as oxidant, photochemical catalyst and adhesive.Oxidation additive can be selected from halide (that is, the NH of alkali metal, alkaline-earth metal and ammonium 4br, KBr, LiBr, NaBr, NaCl, KCl, LiCI, KI, LiI, NaI) and photochemical catalyst (that is, TiO 2, ZnO, VO 2, SnO 2and CdS).Some oxidation additives and photochemical catalyst also can be used as adhesive, promote that magnetic additive adhesion is to adsorbent surface.Also other independently adhesives (that is, adhesive) can be used.In many embodiments described herein, adsorbent is active carbon, and magnetic material is magnetic iron ore, and oxidant and/or adhesion additive are NaBr and/or TiO 2.The amount of additive material additional in composite is preferably gross weight based on final composite by weight at least 0.1% to being less than 10%; More preferably based on the gross weight by weight 0.5% to 5% of final composite.
The other feature of the embodiment of the magnetic adsorbent produced comprises: unique ferriferous oxide concentration, the crystalline nature of the ferriferous oxide comprised, there is not secondary deposit or accessory substance on the surface, on the impact of the physical characteristic of magnetic adsorbent, and the additive that may add.In some embodiments, the ferriferous oxide concentration of the magnetic adsorbent produced is by weight 1% to 20%, more preferably by weight 5% to 15%, most preferably by weight 10%.By using the magnetic additive of native crystal, such as (maghemite (γ-Fe 2o 3), bloodstone (α-Fe 2o 3) and magnetic iron ore (Fe 3o 4)), magnetic adsorbent production method produces the adsorbent of the crystal structure that remain magnetic material.This degree of crystallinity is probably greater than the degree of crystallinity of the material produced by wet chemical process.In addition, owing to not needing heat treatment in magnetic adsorbent production method, so crystalline nature is not destroyed.
By magnetic adsorbent production method, also reduce or eliminate secondary sedimental generation.By contrast, wet chemical process can comprise leave accessory substance and with adsorbent or the interactional reactant of ferrous oxide.Magnetic adsorbent production method does not also corrode pore volume or the aperture of magnetic adsorbent, and due on activated carbon surface adhered particles produce clearance space add in useable surface area, total surface area can be caused to increase a little with measuring.In many wet chemical process, the deposition of ferriferous oxide may reduce surface area, aperture and pore volume.Halide, photochemical catalyst or adhesive can be utilized to produce magnetic adsorbent to improve the oxidation to mercury further, thus absorption and removing from contaminated stream.
Controlled and be deposited on the known magnetic material on the surface of adsorbent by adding magnetic intensity.The surface deposition of magnetic material can make the magnetic force for reclaiming maximize.In addition, form and the degree of crystallinity of magnetic material do not change because of production, thus protect its magnetic property.This is with by magnetic material, those methods be deposited in adsorbent define contrast, and the sorbent material of the latter itself may be sheltered magnetic field and hinder recovery.In addition, instruct and magnetic-doped those methods then activated are carried out to adsorbent precursors may run into the problem being difficult to control form and degree of crystallinity, be therefore difficult to the magnetic property controlling magnetic compound.
Once produce, material can be used for remove the pollutant in fluid stream.Although the known pollutant mercury to flue gas and fluid stream are effectively, described material is effective potentially to the multiple pollutant in much fluid stream.In this expression, by Typical particle gathering-device, (the such as operation of electrostatic precipitator, sack cleaner, cyclone dust collectors (cyclone) and even scrubbing tower (scrubber) removes described material from flue gas.Although it will be understood by those skilled in the art that and describe the embodiment relevant with removing mercury from flue gas, embodiment is not limited to remove mercury from flue gas, and it can be used for removing other heavy metals, includes but not limited to arsenic, selenium and boron.
After composite is separated and collects from fluid stream, recyclable and recycle.Recycle the magnetic property of material.For such scheme, magnetic material is collected in electrostatic precipitator together with other flue gas particles (flyash).After electrostatic precipitator is collected, use magnetic recovery system that magnetic material is separated with flyash.Then magnetic material is stored and be used for recycling.In addition, before recycling, can by materials'use chemistry or thermal technology regeneration.Then material can be applied to again and further from fluid stream, remove pollutant.This technology is used to make save considerably the cost of user and decrease the amount of waste material.
In one embodiment, it is known for being oxidized Hg with halogen process composite.In this regard, halo composite can be formed as follows: (i) mechanically mixes halogen compounds, magnetic material and adsorbent; (ii) composite of adsorbent and magnetic material is exposed to halogen gas; Or (iii) makes magnetic material and halogen react, and then gains and adsorbent is ground altogether.
In another embodiment, in magnetic adsorbent, comprise photochemical catalyst, such as titanium dioxide (TiO 2).Excitation state TiO 2surface can produce hydroxyl radical free radical, these strong oxidizers improve mercury catch by element Hg oxidation are formed such as HgO.Oxidized mercury (such as, HgO) subsequently as the additional adsorption site of element mercury, can improve mercury and catches on the whole.In addition, to be caught for mercury because adsorbent reinjects, the HgO that adsorbent builds up can improve the picked-up of injection cycle mercury.Carry out, in those schemes of particle capture, exciting TiO in use electrostatic precipitator (ESP) 2electronics provided by ESP itself with the energy produced needed for hydroxyl radical free radical form.For bag house (bag house) equipment, will generation be needed lower than the UV lamp of about 365nm wavelength to provide TiO 2excite required energy.As skilled in the art will be aware of, UV radiation comprises the invisible ray of about 4 nanometers (on border, X-ray district) to about 380 nanometers (purple light just beyond in visible spectrum) wavelength.
Fig. 4-6 illustrates and uses TiO as mentioned above 2/ FeO xprepare the result of milled sample.Fig. 4 represents by acticarbon and the TiO being respectively 1% and 10% load capacity by weight 2the iron of magnetic adsorbent prepared by ball-milling treatment and SEM (SEM) figure and EDS Surface scan figure (500 x magnification) of titanium dioxide signal is carried out with magnetic iron ore, demonstrate the extensive distribution of adsorbent surface magnetic iron ore, and the existence of titanium dioxide.Fig. 5 represents milled sample (TiO 2/ FeO x) in the some EDS of independent particle on Fe particle analyze, prove the obvious existence of iron on adsorbent.Fig. 5 proves to exist the iron with peak 530.Figure indicates counting 510 and in contrast to energy (keV) 520.Fig. 6 represents milled sample (TiO 2/ FeO x) on Ti particle separately the some EDS of particle analyze, prove the obvious existence of titanium dioxide on adsorbent.Fig. 6 proves to exist the Ti with peak 630.The graph show counting 610 and in contrast to energy (keV) 620.Fig. 7 represents SEM image and the EDS Surface scan figure (500 x magnification) of the iron signal of the magnetic adsorbent that the magnetic iron ore being utilized as 10% load capacity is by weight prepared by mechanical fusion, demonstrates the distribution of the magnetic iron ore spreading all over sample surfaces.
According to manufacturing technology, magnetic adsorbent has the specific part of magnetized particles.In some embodiments, this part can reclaim from other non-magnetic particles of flyash or fluid stream (as air and water).Magnetic recovery is realized by magnetic recovery device by making the grain flow of mixing.An example uses the design being similar to the electrostatic precipitator (ESP) with electromagnet to collect magnetic adsorbent, allows other particles to pass through gathering-device simultaneously.Then according to application, the magnetic adsorbent reclaimed can be regenerated or recycling.For in the flue gas treatment of mercury, magnetic adsorbent is separated with other particles (flyash) in flue gas stream.The used magnetic adsorbent reclaimed mixes with new magnetic adsorbent, and then injects for catching aerial mercury.This has raising flyash quality and makes potential additional benefit salable.Before Figure 11 a and 11b shows and is arranged on ESP and between two embodiments of active carbon injected system.Boiler 1110 is supplied to selective catalytic reduction system operating 1115.Then effluent stream is to air heater 1120.At this moment, active carbon injects from ACI 1125.Active carbon is then by producing the ESP 1130 of electrostatic charge, and in some embodiments, described electrostatic charge can the performance of stimulating activity charcoal, causes the enhancing that mercury removes.Finally, flue gas to be discharged from exhaust chimney 1140 by stack gas desulflrization facility 1135.In Figure 11 b, an ESP 1130 is before injection active carbon, and the 2nd ESP 1132 is afterwards.Inject and also can carry out before two ESP.Eliminating is used selective catalytic reduction system operating 1115 or stack gas desulflrization facility 1135 by other examples.In many of these cases, as mentioned above, active carbon comprises photochemical catalyst.The advantage of this system to obtain result similar compared with the activated carbon system with sack cleaner, but there is not the same pressure drop experienced in sack cleaner.In some cases, the ESP system of ACI system and interpolation can be used to improve existing shop equipment.As mentioned above, the synergy that this system can provide magnetic adsorbent mercury to remove, but there is the cost lower than the improved equipment (such as the sack cleaner equipment of ACI) that other are well set up well known by persons skilled in the art, and can be readily integrated in existing system.In some constructions, with compared with the system injecting comparatively earlier active carbon of system, the activity that ESP can improve active carbon is set in a typical system.As shown in Figure 11 a and 11, ESP system is arranged near the end of effluent cleaning systems usually.Therefore, active carbon can inject before next-door neighbour ESP, and effectively cooled, so active carbon can have higher effect when arriving this of system due to effluent.In addition, before next-door neighbour ESP, other less compositions in effluent, may be there are, therefore make active carbon be mainly used in removing mercury.The particular configuration of system will determine accurate operational factor and removing ability.In some embodiments, available halogen substiuted photochemical catalyst.
Embodiment 1
the preparation of active carbon/iron composite material
Following preparation has the magnetic iron ore (Fe of by weight 10% 3o 4) the magnetic active carbon sample of concentration: simultaneous grinding 9g active carbon and 1g magnetic iron ore in ball mill.Continue to be ground to the end product of 90% by 325 mesh sieves.Also identical active carbon (but not adding additive) is used to be ground to same size to prepare primary products (virgin product).
de-Hg
Fig. 8 represents the bench scale pilot platform of the adsorption capacity for quantizing MPAC of the present invention.
Air 815 and high-level nitrogen 815, by flow controller 820, flow to into system with the air controlling to represent effluent.Nitrogen 815 from container has 10ug/m by element mercury osmos tube 825 to produce 3the mercury vapour load air of Hg.Then mercury vapour is transported to fixed bed reaction post by heating tube 830.MPAC 835 monitored upstream Hg gas temperature and remain on 150 DEG C.Make adsorbent be dispersed in the Medium Culture of silica sand, and be supported on quartz glass material.Monitor the temperature of adsorbent bed and use heating tape to maintain 110 DEG C.Use a series of rams 840,845 cooling in water-bath from the effluent gas of adsorbent bed, afterwards by connecting RA-915 ZeemanMercury Spectrometer (Ohio Lumex) the 855 monitoring elements mercury of machine.The effluent mercury concentration recorded from testing stand is used for comparing with composite PAC sample.Carbon catches all the other refuses collected with gas extraction system 860 from system.
The Hg adsorption capacity of the composite that service test platform is quantitative and original homologue is shown in Figure 8.Table 1 summarizes test result.As shown, add ferriferous oxide and create the adsorbent with higher de-Hg ability.
Table 1: the de-Hg result of original AC and MPAC product
Table 2: the characteristic of original AC and MPAC product
By table 1 it is clear that ferriferous oxide coating improves the ability that Hg caught by adsorbent from air stream.This probably makes because element Hg is oxidized to the Hg (II) be more easily tightly held by activated carbon by iron.
Embodiment 2
the preparation of active carbon/iron composite material
Following preparation has the magnetic iron ore (Fe of by weight 10% 3o 4) the magnetic active carbon sample of concentration: simultaneous grinding 18 pounds of active carbons and 2 pounds of magnetic iron ores in ball mill.Continue to be ground to the end product of 95% by 325 mesh sieves.Also by adding extra oxidant to prepare two kinds of other adsorbents.The first by ball mill by 18 pounds of active carbons and 2 pounds of magnetic iron ores and 0.2 pound of TiO 2simultaneous grinding to start most that identical size specification and prepare.The second by ball mill by 18 pounds of active carbons and 2 pounds of magnetic iron ores and 0.5 pound of NaBr simultaneous grinding to start most that identical dimensions and prepare.4th kind of charcoal, available from commercial activated carbons supplier, is designed for mercury removing from flue gas application.
After above-described embodiment, Fig. 9 represents with the mercury removing curve in multiple magnetic adsorbent material evaluation fixed bed process, proves the benefit that additive removes for mercury.Y-axis 910 represents normalized mercury concentration C/Co.X-axis 920 represent by minute in units of time.Show the result of multiple additives, comprise the PAC 920 according to multiple embodiment described herein, MPAC 930, PAC-Br935, MPAC-Br 940 and MPAC-TiO 2945.
Figure 10 represents with the mercury removing curve of Basal activity charcoal (injecting basic AC (PAC) 1030 and the MPAC 1040 being coated with 5%Fe3O4 by weight in 5MW slip-stream flue gas) under actual flue gas conditions, the benefit that the magnetic adsorbent demonstrating production removes for mercury.Y-axis 1010 represents that the percent of total that mercury removes, x-axis represent that with pound/MMacf be the charge velocity of unit.
mercury removes
This 4 kinds of products are tested at Mercury Research Center (MRC).MRC removing is from constant, about 20,500acfm the flue gas stream (representing 5 5MW boilers) of Southern Company Plant Christ Boiler (78MW).Boiler combustion is from the low-sulfur bituminous coal mixture in multiple source.Although the SO3 concentration that fuel mixture before produces usually is less than the SO3 of 1ppm, current coal mixtures causes the SO3 concentration in air heater (AH) downstream to be 2 to 3ppm.Product is pneumatically injected into electrostatic precipitator (ESP) upstream with the charge velocity of 3,5 and 7 pounds/MMacf.The removing to particulate is realized by ESP.In MRC entrance and the monitored down mercury concentration being close to ESP, the concentration adjustment of observation is used for standardization to 3% oxygen concentration and compares.By entrance mercury concentration (unit ug/m 3, at STP and 3%O 2under) deduct outlet mercury concentration (unit ug/m 3, at STP and 3%O 2under) calculate mercury removal rate divided by entrance mercury concentration, and describe in fig. 12.With commercially available active carbon ratio, MPAC charcoal 1241,1242,1243,1251,1252,1253,1261,1262,263 shows the remarkable advantage of higher mercury removing percentage.Showing the figure of active carbon injection 5MW slip-stream flue gas, the post illustrated is as follows: existing industrial PAC (industrial charcoal) 1231,1232,1233 on market, and is coated with 10%Fe by weight 3o 4mPAC (MPAC) 1241,1242,1243, there is 10%Fe 3o 4and 1%TiO 2mPAC (MPAC-TiO 2) 1251,152,1253, and there is 10%Fe 3o 4with the another kind of MPAC (MPAC-Na-Br) 1261,1262,1263 of 2.5%NaBr.
Describe in detail before just for implementing the sub-fraction embodiment of the Compounds and methods for relevant to magnetic adsorbent (such as magnetic active carbon), it is not intended to limited field.Claims forth more particularly some embodiments of the Compounds and methods for relevant to disclosed magnetic adsorbent (such as magnetic active carbon).

Claims (34)

1. a magnetic adsorbent, it comprises: adsorbent; With the ferriferous oxide be implanted on the surface of described adsorbent, the total surface area of wherein said magnetic adsorbent is not less than the total surface area of described adsorbent substantially.
2. magnetic adsorbent according to claim 1, wherein said adsorbent is active carbon.
3. magnetic adsorbent according to claim 1, it also comprises the additive being selected from halogen, photochemical catalyst and adhesive.
4. magnetic adsorbent according to claim 1, wherein said magnetic adsorbent does not comprise secondary deposit.
5. magnetic adsorbent according to claim 1, the ratio of the weight of wherein said ferriferous oxide and the gross weight of described magnetic adsorbent is 1% to 20%.
6. magnetic adsorbent according to claim 1, the ratio of the weight of wherein said ferriferous oxide and the gross weight of described magnetic adsorbent is 5% to 15%.
7. magnetic adsorbent according to claim 1, the ratio of the weight of wherein said ferriferous oxide and the gross weight of described magnetic adsorbent is 10%.
8. magnetic adsorbent according to claim 1, wherein said ferriferous oxide highly crystalline after the implantation.
9. magnetic adsorbent according to claim 1, wherein keeps the crystalline nature of described ferriferous oxide after the implantation.
10. a magnetic adsorbent, it is substantially composed of the following components: adsorbent; With the ferriferous oxide be implanted on the surface of described adsorbent, the total surface area of wherein said magnetic adsorbent is not less than the total surface area of described adsorbent substantially.
11. magnetic adsorbents according to claim 10, wherein said adsorbent is active carbon.
12. 1 kinds of methods preparing magnetic adsorbent, it comprises:
Use mechanical mixing equipment by adsorbent and magnetic material combination.
13. methods according to claim 12, wherein said adsorbent is active carbon, and described magnetic material is ferriferous oxide.
14. methods according to claim 12, wherein said mechanical mixing equipment is selected from ball mill, aeropulverizer, classification grinding system etc.
15. methods according to claim 12, the friction between wherein said mechanical mixing equipment promotion particle and collision.
16. methods according to claim 12, it also comprises and being implanted on the surface of described adsorbent by described magnetic material.
17. methods according to claim 12, wherein said combination comprises grinding, and continues until that described magnetic adsorbent can by till 325 mesh sieves.
18. 1 kinds of methods for the treatment of effluent stream, it comprises: process described effluent stream by injecting magnetic adsorbent particle; Magnetic field is used to reclaim described magnetic adsorbent particle.
19. methods according to claim 18, wherein said magnetic adsorbent particle is re-introduced in described effluent stream after recovery together with other magnetic adsorbent particle.
20. methods according to claim 18, wherein said absorbent particles has the ferriferous oxide be implanted on surface.
21. methods according to claim 18, wherein said magnetic adsorbent particle removes mercury from described effluent stream.
22. 1 kinds of methods reclaiming high-quality flyash from the effluent through powdered activated carbon process, it comprises: be injected into by magnetic adsorbent in effluent stream to remove pollutant from described effluent stream; Magnet is used to catch described magnetic adsorbent; Recycling powder coal ash from described effluent stream, described flyash is not containing described magnetic adsorbent.
23. methods according to claim 22, wherein said magnetic adsorbent produces by being ground together with ferriferous oxide by active carbon.
24. 1 kinds for removing the system of mercury from effluent system, described system comprises:
Active carbon injected system, it injects activated carbon product in effluent;
First electrostatic precipitator, it receives described effluent after being arranged on described active carbon injected system.
25. systems according to claim 24, after wherein said first electrostatic precipitator is arranged on the described active carbon injected system of next-door neighbour, and without any intermediate treatment.
26. systems according to claim 24, wherein said activated carbon product is magnetic.
27. systems according to claim 26, wherein said activated carbon product comprises photochemical catalyst.
28. systems according to claim 27, wherein said first electrostatic precipitator activates described photochemical catalyst.
29. systems according to claim 22, before wherein the second electrostatic precipitator is arranged on the described active carbon injected system of next-door neighbour.
30. systems according to claim 26, wherein said activated carbon product has the ferriferous oxide be implanted on surface, and total surface area is not less than substantially not containing total surface area during described ferriferous oxide.
31. systems according to claim 25, after wherein said active carbon injected system is positioned at selective catalytic reduction system operating and air heater.
32. 1 kinds of adsorbents, it comprises:
Activated carbon section;
The magnetic part be connected with described activated carbon section, the magnetic activity of wherein said magnetic part is not shielded by described activated carbon section.
33. adsorbents according to claim 32, wherein said magnetic part is implanted on the surface of described activated carbon section.
34. adsorbents according to claim 32, the total surface area wherein not containing the described activated carbon section of described magnetic part is at least substantially identical with the total surface area of described adsorbent.
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