CN101553301A - Mercury adsorbents compatible as cement additives - Google Patents

Mercury adsorbents compatible as cement additives Download PDF

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Publication number
CN101553301A
CN101553301A CNA2007800452416A CN200780045241A CN101553301A CN 101553301 A CN101553301 A CN 101553301A CN A2007800452416 A CNA2007800452416 A CN A2007800452416A CN 200780045241 A CN200780045241 A CN 200780045241A CN 101553301 A CN101553301 A CN 101553301A
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compound
sorbent
mercury
catalyst
potassium
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C·朝
D·R·汤普森
J·布拉德利
S·J·蓬托尼奥
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Praxair Technology Inc
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Praxair Technology Inc
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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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

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Abstract

Solid adsorbents, following their use for mercury removal from flue gas, that do not interfere with the ability of air-entraining additives (such as surfactants) to form stable bubbles when added to fly ash containing the adsorbents. The interference is overcome by heating the materials used in the manufacture of the adsorbent so that magnesium hydroxide and/or one or more alkali compounds containing one or more silicate, aluminate, and/or phosphate moiety, added or already present in the materials, binds multivalent cations present in the materials that could otherwise interfere with the surfactant activity.

Description

Be suitable for the mercury adsorbent of making cement additire
The present invention requires the priority of the U.S. Provisional Application submitted on December 8th, 2006 number 60/873,929, and it is disclosed in this and introduces by reference.
Technical field
The present invention relates generally to can be used for from waste gas stream, removing the improvement catalyst-sorbent of mercury.The improvement of described adsorbent is that their use the existence in the flyash that the back reclaims not disturb flyash to be used as the purposes of cement additire at it from waste gas.The invention still further relates to the manufacturing and the use of this catalyst-sorbent.
Background technology
From mercury being discharged into the air-flow of atmosphere, the demand of removing mercury in the waste gas of for example in burning, discharging at present gradually widely known to.
Some are removed the trial of mercury and adopt the solid absorbent that joins in the waste gas stream from waste gas.Mercury is removed from waste exhaust gases and is attached on the adsorbent, and the adsorbent that will carry mercury by equipment separates from waste gas then, and described equipment will therefrom separate before waste gas enters atmosphere such as other solid materials of flyash equally.
The flyash that reclaims from the waste gas such as the operation of industrial combustions such as coal fired thermal power plant can be used as cement composition usually.Even desirable is once to be used for also using flyash in this way when waste gas is removed the solid absorbent of mercury when flyash contains the above.
Cement composition becomes phase-splitting to mix to form mixture with water and other, this mixture can become the thing of solid product when toppling over or form in cement solidification, often join in the cement surfactant or other air-entrainments so that form bubble in cement admixture this moment.Bubble forms the space in cured article, any water that is penetrated into thus in the solid product will expand in the space when freezing, thus the globality of entail dangers to solid product itself not.
Yet commonly known is that PAC (powder activated carbon) adsorbent that removes being used for of existing mercury in flyash from waste gas will disturb the aerating additive to form the ability of required bubble cement composition.Therefore, need find the solid absorbent that is used to remove mercury of getting rid of this interference, and manufacture method.
Summary of the invention
One aspect of the present invention is a kind of catalyst-sorbent composition of at high temperature removing mercury from waste gas stream, described catalyst-sorbent composition comprises the activated carbon that is dispersed with halogen or halogenated compound on it, such as comprising cation and anionic halogen, and described catalyst-sorbent composition is used at high temperature having blow index less than 45 at it behind waste gas stream absorption mercury.
Another aspect of the present invention is to be made the method for above-mentioned composition by the compound of carbon raw material, halogen and one or more formulas Ia and/or Ib
Mg(OH) 2 (Ia)
(Alk) a(M nO p) (Ib)
Wherein every M that occurs, it is silicon, aluminium or phosphorus, every Alk that occurs, it is sodium or potassium, and a, n and p are positive integers.Described integer is through selecting to make the compound of formula Ib not have net charge, its valence mumber according to the silicon atom of any existence is (+4), the valence mumber of the chlorine atom of any existence is, the valence mumber of the phosphorus atoms of any existence is (+5), the valence mumber of the oxygen atom of any existence is (2), and the valence mumber of the sodium atom of any existence is (+1).The preferred example of the compound of formula Ib comprises sodium orthosilicate, sodium metasilicate, sodium aluminosilicate, sodium orthophosphate and sodium metaphosphate and composition thereof.
In certain methods, described composition can form mixing mutually under the condition with required adsorbent character with the PAC adsorbent, and the gained adsorbent is heated, and the described heat energy that adds makes mixture homogenize and the combination of the polyvalent cation (such as calcium ion) that the compound promoted by one or more formulas Ia that exists and/or Ib exists in adsorbent effectively.In additive method, mix to form the desirable necessary composition of adsorbent that has less than 45 blow index, then this combination being placed to form under the condition with required adsorbent character, comprise fully and heating that wherein heating forms carbonaceous material the combination of the polyvalent cation that PAC and the compound promoted by one or more formulas Ia that exists and/or Ib exist simultaneously in adsorbent.In additive method, prepare the PAC adsorbent by carbonaceous material and halogen, and need not to add the material of more formula Ia and/or Ib, but the combination of the polyvalent cation that in adsorbent, exists of the compound promoted by one or more formulas Ia that in parent material, existed and/or Ib effectively through heating.
The invention provides catalyst-sorbent, wherein halogen or halogenated compound such as halogen is dispersed on the adsorbent that contains activated carbon.The oxidation catalytic activity of described catalyst-sorbent promotes the formation of mercury halide, and the characterization of adsorption of catalyst-sorbent has maintained the mercury halide that forms at the same time.Because it is harmless that halogen is stablized in room temperature, these doping activated carbon in waste gas stream in common high temperature and the waste gas common reactive ingredients in the presence of can form the mercury halogen compounds.These mercury halogen compounds remain on the catalyst-sorbent surface.In addition, the adsorption capacity of raising causes comparing the adsorbent that the activated carbon that do not mix that is formed by identical parent material needs less amount with the rate of adsorption faster.
Of the present invention being used for removes the catalyst-sorbent composition of mercury so comprises that (except the low foaming coefficient of being discussed in this article) it is dispersed with halogen or halid activated carbon from waste gas stream.In the embodiment that halide exists with halogen, the cation of halogen can be alkali metal, alkaline-earth metal or transition metal (for example Na, Ca, Mg, Cu and K) and related anion can be bromine or chlorine.Particularly preferred halogen includes but not limited to NaCl, CaCl 2, CuCl 2, CuBr 2, NaBr, KBr, CaBr 2And MgBr 2
Halogen is inertia in room temperature to mercury and activated carbon.At high temperature (for example, 200 °-570) and in the presence of common waste gas composite, form the mercury halogen compounds and be adsorbed the agent maintenance.Do not wish to be subject to any theory, can think following arbitrary or whole or its combination may take place.Oxidant (for example) oxidized mercury, and the counter ion of the mercury ion of the anion of alloy when oxidized dose of oxidation is provided from the oxygen of waste gas or the oxidant on the activated carbon.Replaceability ground or additivity ground, the anion in the oxidant oxidation salt, thus and oxidized anion reoxidizes mercury form the mercury halogen compounds on activated carbon.Additivity ground or alternatively, sour gas that in waste gas, exists and doping reactant salt formation hydrogen halides.The oxidized then dose oxidation of hydrogen halides also forms halogen species.Halogen species and then form the mercury halogen compounds with mercury reaction is adsorbed agent absorption thereupon.
Adsorbent of the present invention it is believed that it is because the dispersion of the compound of formula Ia that heating promotes and/or Ib and polyvalent cation mainly are calcium and the combining of the compound of above one or more formulas Ia and/or Ib at its desirable low blow index that is used for being shown behind waste gas absorption mercury.
The present invention also provides the manufacture method that so shows less than the dopped activated carbon adsorbent of 45 blow index, this method not only economy but also safety after use.Catalyst-sorbent of the present invention also can be made by several different methods, and all these methods include at a time to carve and heat combining with the compound of the dispersion of the compound that promotes formula Ia and/or Ib effectively and the polyvalent cation in the adsorbent and above-mentioned one or more formulas Ia and/or Ib fully.
Therefore, in one embodiment, can following formation catalyst-sorbent, activated carbon is put into the aqueous solution that contains halogen and contain the compound of one or more formulas Ia and/or Ib form mixture, stir described mixture until forming the homogeneous phase slurry, and dried active carbon make in the aqueous solution the water evaporation and the compound of halogen and one or more formulas Ia and/or Ib is dispersed on the surface of activated carbon.Products therefrom is then through heating to promote the polyvalent cation in the adsorbent to combine with one or more formulas Ia that exists and/or the compound of Ib effectively.
In another example fabrication method, can following manufacturing catalyst-sorbent, to soak into the mixture of the compound of also dry carbon raw material, halogen and one or more formulas Ia and/or Ib in advance, perhaps the drying composite of the compound of halogen, one or more formulas Ia and/or Ib and carbon raw material and active gas flow drop into reative cell in the lump.When (soak in advance and dry, or dry) mixture of compound that uses halogen, one or more formulas Ia and/or Ib and carbon raw material, described active gas flow can contain air and/or steam, O 2, CO 2, N 2, CO or its mixture.The compound of carbon raw material, halogen, one or more formulas Ia and/or Ib and active gases are in reative cell, its residing condition and residence time are enough to be formed on the surface of powder activated carbon and are dispersed with the powder activated carbon with cation and anionic halogen, and the combining of compound of the polyvalent cation in the generating material and described one or more formulas Ia and/or Ib wherein.In the method, reative cell can be batch reactor such as tube furnace, mixing chamber or through being designed for the reactor (for example, fluidized-bed reactor, burner etc.) of continuous mode operation.Halogenated compound is preferably cation that is selected from alkali metal, alkaline-earth metal and transition metal (for example Na, K, Mg, Ca and Cu) and the anionic salt that is selected from bromine and chlorine.In some embodiments, salt is selected from NaCl, KCl, CaCl 2, CuCl 2, CuBr 2, NaBr, KBr, CaBr 2And MgBr 2
In this embodiment, the mixture of the compound of carbonaceous material, halogenated compound and one or more formulas Ia and/or Ib can perhaps obtain by dry mixed by the salting liquid of carbonaceous material with the compound that contains described one or more formulas Ia and/or Ib soaked into.These two kinds of methods are similar, and difference is the introducing mode of alloy.Mix owing to can cut down finished cost but desirable by dry mixed.Realize the significant degree that dry type is mixed unexpectedly, mix and mix preferably on molecular level, and carbonaceous material and salt particle are usually in micron-scale scope (that is, than the high a plurality of magnitudes of molecule level).
In other embodiments, powder activated carbon or other carbonaceous materials and halogen X 2Or hydrohalide HX contacts, and wherein X is Br, Cl or I.Contact being enough to make under the temperature and time that is attached to (no matter being) on the carbonaceous material surface for halogen or halid X by covalency keyed jointing, physical absorption or other modes.
Catalyst-sorbent of the present invention is applicable at high temperature from containing the air-flow of oxidant and/or sour gas, such as remove mercury in the waste gas stream of discharging from boiler or combustion process.In this process, catalyst-sorbent of the present invention injects waste gas stream and captures with the mercury that carries out offline mode.As discussed above, the halogen alloy is inertia in room temperature to mercury.Yet in the presence of EGT and activated carbon, oxidant and/or sour gas, the halogen alloy is removed mercury effectively from waste gas stream.Mercury remains on the activated carbon with the form of mercury halogen compounds, and separates from waste gas stream with flyash.
The flyash and the adsorbent that reclaim from waste gas stream can be used as cement composition, and (comparing the flyash that contains adsorbent that the combination of polyvalent cation wherein as described herein does not obtain promoting) shows the very big minimizing to the surface-active interference that joins the aerating additive in the cement composition.
The condition of the condition of burning coal generating and activating carbonaceous raw material manufacturing activated carbon is also inequality basically.For example, very high and all carbon of having sufficient dioxygen oxidation to exist of boiler temperature in the combustion chamber.Therefore halogen can be oxidized and be carried out complicated reaction and form hydrogen halides.On the contrary, the temperature range during the carbon activation is about 1200 °-2000 °F, and is low more than boiler temperature.The small amounts agent is consumed and carbon surface maintenance reproducibility fast.Therefore, halogen can experience activation process and be kept perfectly.Therefore can realize the doping of activated carbon by the doping coal.Consider that the halogen on the activated carbon can react with mercury in about 270 waste gas, the active gases that unexpected discovery contains oxidant can make halogen be kept perfectly in activation process.
Term definition
Term used herein " combination " and " carrying out combination " comprise any mechanism, by described mechanism, the mercury adsorbent composition of the compound that contains one or more formulas Ia and/or Ib heated reduced or the ability of promotion bubble formation when having prevented that the polyvalent cation in the composition from disturbing aerating additive (surfactant) to mix with the flyash that contains the described adsorbent composition that is used to remove mercury in water.A kind of such mechanism is the wherein reaction of the compound of (Alk) formula Ia of being replaced by polyvalent cation and/or Ib.Another kind of such mechanism is the formation such as the physical barriers of melten glass matter layer, has stoped the reaction of polyvalent cation and aerating the additive anionicsite of anion surfactant (especially with).
Term blow index used herein (" FI ") is to form the required amount of surfactant of lasting froth bed.The surface-active more high-compatibility of less numeric representation and aerating additive or other surfactants.As used herein, the blow index of material is measured by following steps:
Two gram flyash (obtain in the waste gas by the coal combustion generation, do not contain unburned coal substantially) are positioned over the cylindrical measuring cup of 70ml that the inside dimension that fills 25cc distilled water is 40mm * 80mm.Sample adds Portland (Portland) cement of 8gm subsequently through ultrasonic dispersion in 5 minutes.Thereby measuring cup covered and rock fully made flyash and cement complete wetting in 1 minute.
Prepare test solution by Darex II, described Darex II is that the merchant sells aerating surfactant interpolation product (being sold by W.R.Grace), and it is the sodium salt of composite organic acid and the aqueous slkali of sylvite.Water joined in the described commercial product form diluted composition, wherein the concentration of commercial product is 10 volume %.This diluted composition is test solution.
By 2cc is that buret dropwise adds test solution.After every adding number droplet,, take off lid subsequently and check liquid surface on the bottle cap and fiercely rocked 15 seconds.Before the test maximal end point, any foam that forms at liquid surface all is extremely unsettled, and is included in the bubble of several seconds implosion.When arriving maximal end point, one deck foam will keep for 45 seconds on the surface at least.Produce the blow index that the required test solution volume (ml) of this stable foam is flyash/cement admixture.
What adopt is to sell the Portland cement that provides by Quikrete merchant, class of trade model I/II and from Pleasant Prairie power plant, the flyash of Wisconsin State (" P4 ").P4 has sold for many years, and its flyash is used for the cement purposes.This flyash is with to be used for the aerating additive of cement compatible and have a low blow index.
The 8gm cement that does not contain additive is carried out the blow index that this test process obtains cement.Difference between the blow index of the mixture of flyash (containing adsorbent) and cement and the blow index of cement is the flyash blow index of (not containing adsorbent).
The 8gm cement that contains 1.98gm flyash and 0.02gm powder activated carbon (PAC) adsorbent is carried out the blow index that this test process obtains having the flyash of 1 weight % adsorbent/cement admixture.Because adding the adsorbent of 1 weight % in flyash is the reasonable target dose of effectively removing mercury, the employed blow index value of this paper has characterized the surface-active compatibility of adsorbent and aerating additive.
Description of drawings
Fig. 1 has described an embodiment of making catalyst-sorbent of the present invention.
Fig. 2 has described the using method of catalyst-sorbent of the present invention.
The specific embodiment
The invention provides and be applicable to the catalyst-sorbent of at high temperature from waste gas stream, removing mercury.Catalyst-sorbent of the present invention comprises the composition that contains activated carbon, is dispersed with halogen or halogen or other halogenated compounds on the surface of described activated carbon.The cation of described halogen alloy can be alkali metal, alkaline-earth metal or transition metal, and anion can be bromine or chlorine.Described adsorbent is used for also showing blow index less than 45 at it after waste gas absorption mercury.
The present invention also provide the sour gas in high temperature and the waste gas stream that produces by coal combustion, found usually and/or oxidizing gas in the presence of, these are used for the using method of the composition that mercury captures.
The mercury effect of capturing is the synergistic combination of composition, waste gas stream and exhaust flow temperature in the adsorbent composition.As described in U.S. publication application 2006/0204418A1, activated carbon is from 270 mercurys in the adsorption of nitrogen air-flow not.KBr doping silica gel does not adsorb the mercury of perceived amount yet, even there is waste gas completely.The graphite that KBr mixes does not absorb mercury fully.Yet, the activated carbon that Bromide mixes since can remove mercury to low-down level from but the especially effective adsorbent the waste gas.In addition, they can also go out some mercurys in the nitrogen stream.
Discuss as this paper, the halide of alkali metal, alkaline-earth metal and transition metal is harmless salt and is inertia in room temperature to mercury and activated carbon.Yet about 200 °-570 °F (for example, 270 °F), and in the presence of the sour gas and/or oxidizing gas of waste gas, these doping activated carbon compositions can be captured mercury expeditiously.Untapped halogen remains its salt form.
Catalyst-sorbent of the present invention does not disturb the use of flyash in cement in addition, also in the waste gas stream (present adsorbent can not play a role therein effectively such as Norit FGD carbon) that produces by burning subchloride coal Powder River Basin (PRB) coal of the Wyoming State (for example, from), do well.
Therefore the present invention provides (part) thereby halogen and halide has been dispersed in and made them keep its chemical inertness in room temperature on the activated carbon, but produces non-volatile mercury halide with the mercury reaction in hot waste gas.More specifically, in about 200 °-570 temperature range, in the presence of from the acidity of waste gas and/or oxidizing gas, halogen and halide and mercury reaction also help sorbent capture to be present in mercury in the waste gas stream with low-down concentration.Catalyst-sorbent of the present invention adopts at high temperature very fast dynamics to optimize physical absorption and chemisorbed.Therefore the reactive of the employed halogen of this paper be cooperative phenomenon.
Such as hereinafter discussion, can make the catalyst-sorbent of ability with absorption mercury of the present invention and 45 following low blow indexs by various parent materials.
Can make adsorbent by the powder activated carbon that comprises the PAC that contains halogenic ingredient (PAC) or by thick carbonaceous material.Be applicable to that exemplary PAC of the present invention includes but not limited to FGD (by Norit America, Inc. provides), the ashless active carbon powder that makes by the purifying petroleum coke and the carbon fiber powder that makes by the carbonization of rayon fiber.Be understandable that other activated carbon are also in the present invention available.
Catalyst-sorbent of the present invention can be made by the whole bag of tricks.In an embodiment of the invention, can followingly make adsorbent, activated carbon is immersed in the aqueous solution of the compound that contains one or more halogens and one or more formulas Ia and/or Ib, promotes the combining of compound of polyvalent cation and one or more formulas Ia and/or Ib in the adsorbent subsequently by heating.This method is the technology of economic security with respect to handle activated carbon with hydrogen halides or halogen gas for.
In this embodiment, the preferred necessary minimum water of preparation halide salt solution that adopts.The cation of halogen alloy can be alkali metal, alkaline-earth metal or transition metal.Related anion can be bromine or chlorine.Be applicable to that therefore salt of the present invention include but not limited to NaCl, CaCl 2, CuCl 2, CuBr 2, NaBr, KBr, CaBr 2And MgBr 2In some embodiments, KBr, NaBr or CaBr 2Be preferred, in some embodiments, NaBr or KBr are most preferred salt.
The compound of PAC (being preferably powder type) and one or more formulas Ia and/or Ib is placed in the halogen aqueous solution, mixture becomes the homogeneous phase slurry through stirring until it, so has between salting liquid and the PAC and make sufficient time of contact salting liquid (compound that comprises one or more formulas Ia and/or Ib) be dispersed on the PAC.The compound that those skilled in the art have porous so solution and halogen and one or more formulas Ia and/or an Ib with the accessible PAC of being will be distributed among the PAC.
In the method, the necessary salt amount of the aqueous solution is determined (that is, salt dopping thing level determines the concentration of salting liquid in required PAC) according to the amount of PAC and the required salt of concrete adsorbent with the ratio of PAC.In some embodiments, the halogen dopant levels is 1: 10 with the ratio of PAC, 000 to 30: 100.In preferred embodiment, alloy is 1: 4000 to 10: 100 with the ratio of PAC, and in most preferred embodiments, alloy is 0.1: 100 to 7: 100 with the ratio of PAC.
The salting liquid that contains the compound of PAC and one or more formulas Ia and/or Ib soaked into and subsequently fully drying make PAC to flow freely.After the PAC drying, it is a powder type.Should heat combining then with the compound that promotes polyvalent cation and one or more formulas Ia and/or Ib in the sorbent material.
The material that makes in this ad hoc approach can be through being ground to any suitable required size.In this way, PAC can be used for the mercury removal to be less than or equal to 200 order materials.It will be understood by those skilled in the art that can handle adsorbent according to the desired use of adsorbent obtains suitable dimensions.For example, in some purposes, need littler particle diameter (for example, 400 orders).
Can think that as long as salt is dispersed on the PAC surface catalyst-sorbent of the present invention can at high temperature be removed mercury from waste gas stream.Do not wish to be subject to any theory, it is believed that described salt is inertia to element mercury under room temperature and high temperature (being burner interval).Yet, at the high temperature (for example, about 270-300F) of about 200-570F, and in waste gas oxidisability and/or sour gas and doping activated carbon in the presence of, the mercury in the waste gas stream can be oxidized and effectively from wherein removing.
The another kind of method that PAC is immersed in the aforesaid aqueous solution is to contain the water droplet of required halogen and the compound of one or more formulas Ia and/or Ib so that the dispersed as described above mode of compound of halogen and one or more formulas Ia and/or Ib is sprayed on the PAC.Such method can with the open U.S. Patent application 11/078 according to the Bool that submits on March 14th, 2005 etc., 517, the open U.S. Patent application 11/224 of publication number 2006/0204429A1 and Bool etc., 590, the activated charcoal of publication number 2006/0204430A1 manufacturing is united use, the two title is " Production of Activated Char Using Hot Gas ", introduces by reference at this.
The another kind of manufacture method that is applicable to catalyst-sorbent of the present invention is presented among Fig. 1.In this embodiment, can make catalyst-sorbent by various parent materials arbitrarily, pulverize in advance such as the carbon raw material in the aqueous solution that will be immersed in the compound that contains alkali metal, alkaline-earth metal or transition metal halogen and one or more formulas Ia and/or Ib in advance.Another kind of mode, the carbon raw material of Fen Suiing can be immersed in alcohol (for example ethanol) solution of the compound that contains alkali metal, alkaline-earth metal or transition metal halogen and one or more formulas Ia and/or Ib in advance.The raw material of Jin Paoing is exposed to oxidation gas mixture such as air and steam then under the high temperature in reative cell in advance, thereby makes catalyst-sorbent and waste gas.High temperature also promotes the combination of the compound of polyvalent cation and one or more formulas Ia in the adsorbent and/or Ib.
With respect at first making activated carbon, thereby the activated carbon that mixes is then made the method for catalyst-sorbent, and directly the catalyst-sorbent by the carbon raw material preparation can provide significant composition to save.Therefore, substitute and soak in advance, thus the carbon raw material manufacturing catalyst-sorbent that also can pass through the compound of dry mixed alkali metal, alkaline-earth metal or transition metal halogen powder and one or more formulas Ia and/or Ib and pulverize in advance.Married operation is wished for completely, promptly as much as possible near molecular mixing.For example, can use blender such as the multidirectional amount fluidisation technology of NLI Alfr.Andersoen a.s. or the plough formula blender of Scott Equipment Co. etc. to realize sufficient mixing with shearing force effect.In the testing stand level,, can finish mixing by the grinding of using mortar and pestle with very little amount.
Dry mixed principle in reative cell, under such as 1200-2000 high temperature, is exposed to and contains such as air, steam, O subsequently 2, N 2, H 2O, CO 2, CO or its mixture activating gas mixt in to make catalyst-sorbent and waste gas.Activating gas mixt can be the oxidisability hyperoxia voltinism or high reproducibility or any level between the two or reproducibility intensity.The chemical composition of carbonaceous material has determined the requirement to the oxidability of activating gas mixt, and this has determined the composition of activated gas mixt again thereupon.For example, high-grade (high-carbon content) coal can need the high oxidative capacity mixture so that active surface to be provided.For brown coal or other elevated oxygen level carbonaceous materials, need suboxides ability gas so that the activated carbon products of high yield to be provided.
Dry type is mixed also can further simplify the manufacture method of catalyst-sorbent of the present invention.Owing to removed activation, be preferred therefore with the drying steps in the preparation of doping carbon raw material.
The ultimate density of the compound of halogen and one or more formulas Ia and/or Ib is determined (promptly as said method in the preparation catalyst-sorbent, thereby the ratio of halogen and activated carbon pre-determines the concentration of determining salting liquid, thereby the amount of the compound of one or more formulas Ia and/or Ib then is no longer to disturb the surface-active of aerating additive according to the amount of the combined polyvalent cation of the needs that exist in material), the difference in the present embodiment is in reative cell owing to the carbonaceous material weight of losing of burning must be taken into account.Thereby therefore can determine the loss in weight that the concentration explanation causes because of activation according to the productive rate of final products.
Although halogen is necessary for fully removing mercury, thereby do not need excessive halogen to cause extra manufacturing cost.Found that extremely excellent catalyst-sorbent of the present invention can be prepared according to the halogen coal ratio of about 1: 1000 (weight ratio).
Describe as Fig. 1, carbon raw material 16 injects reative cell 10.Carbon raw material 16 is not activated and can be selected from various types of raw materials such as coal or biological material.Should not be construed as under the situation about limiting, be applicable to that coal of the present invention includes but not limited to brown coal, ub-bituminous coal, bituminous coal or anthracite.Raw material can be pulverized in advance is suitable dimensions, for example about 5-200 micron.
Before injecting reative cell 10, carbon raw material 16 can carry out premixed by dry mixed, perhaps soak in advance with containing the solution of required halogen with the compound of one or more formulas Ia and/or Ib as mentioned above, perhaps carbon raw material 16 injects reative cell with the solution of the compound that contains required halogen and one or more formulas Ia and/or Ib.In the embodiment that soaks in advance, solution can be formed by water or ethanol, but water is preferred.
Activated gas 12 and 14 (for example air 12 and steam 14) is with 16 whiles of carbon raw material or near injecting reative cell 10 simultaneously.Be preferably, steam injects through preheating and with about 1800 temperature.Some raw materials (such as brown coal) are easier to react with oxygen, thereby improves activated carbon output, and activated gas also can only be steam and/or nitrogen.Under very high temperature, such as 2000 °F, water can react and become the oxygen source of activated carbon surface with carbon.Activated gas also can comprise O 2, N 2, H 2O, CO 2, CO mixture, the composition of described mixture can be used for the redox ability of adjustments of gas mixture to satisfy the requirement of raw material.Here too, the temperature that realizes of activated gas must provide combining of the enough heat compound to promote polyvalent cation and one or more formulas Ia and/or Ib in the sorbent material.
Reative cell 10 can be selected from various reactors, such as batch reactor, wherein material flowization or stratification (such as being suspended on the filter medium) and reacting gas flows through raw material (for example tube furnace), perhaps such as flow reactor, wherein gas temperature, composition and raw material residence time can be controlled to be optimum condition (for example fluidized-bed reactor).Raw material can activated gas or fluidizer carry out fluidisation (being used for continuous processing) such as the plough formula blender that provides by Scott Equipment Company.
Reative cell 10 heating can be provided by multiple source.For example, but reative cell electrical heating or pass through flame heat.Substitute or be additional to these heating, reative cell can be heated by the reaction between raw material and the air.Those skilled in the art are accessible to be that temperature required in reative cell depended on and multiple factor comprise the stoichiometric ratio of oxygen or oxidizing gas and raw material, the time of contact and the reactivity of raw material.As long as can being provided by any source, heating is enough to produce waste gas 18 and adsorbent 19.Usually, the temperature in the stove will be about 1450-2700 °F, and most preferably be about 1650-2200 °F.When the stoichiometric ratio of oxygen and raw material greater than one, will more important time of contact between oxidizing gas and the raw material, this is because how potential raw material need be consumed and therefore influence product yield.When stoichiometric ratio less than one, then do not have time of contact so crucial.
Carbon raw material 16 and reactive activated gas (such as air 12 and steam 14) thus the residence time long enough in reative cell 10 make in reative cell 10 and to produce waste gas 18 and adsorbent 19.The residence time of carbon and gas are irrelevant also can be controlled independently.This is very important, because need the sufficient time to remove volatile ingredient and partial oxidation in the raw material.When residence time more in short-term, importantly long enough is with activated carbon fully.In some embodiments, residence time can be the magnitude of dividing, but also may be as little to several milliseconds.Should be understood that the adsorbent productive rate will be subjected to negative effect if residence time is oversize or too many oxygen or steam are arranged.
Adsorbent 19 takes out from reative cell 10, in order to being used as the adsorbent of removing mercury at high temperature from waste gas stream.Waste gas 18 comprises burning gases usually such as CO 2, CO, N 2And H 2O.Unreacted, partially combusted in the air-flow 18 then (for example CO) or escaping gas can further burn.
The another kind of substituting manufacture method that is used for catalyst-sorbent of the present invention can be at the open U.S. Patent application 11/078 of Bool etc., 517, the open U.S. Patent application 11/224 of publication number 2006/0204429A1 and Bool etc., 590, find among the publication number 2006/0204430A1, the two title is " Production of Activated Char Using Hot Gas ", introduces by reference at this.In this embodiment, raw material soaks in advance with the aqueous solution or the alcoholic solution of the compound that contains halogen and one or more formulas Ia and/or Ib as mentioned above.Handle the raw material that soaks in advance then and disclose disclosed activated charcoal in the application to make as those.The heating of parent material has been promoted the combining of compound of polyvalent cation and one or more formulas Ia and/or Ib in the desirable material.
Catalyst-sorbent of the present invention also can be by starting from thick carbonaceous material that dry mixed pulverizes in advance and halogen powder and one or more formulas Ia and/or Ib the step of compound form.In this embodiment, the compound of thick carbonaceous material, halogen powder and one or more formulas Ia and/or Ib mixes with dried forms.By disclosed method in above-mentioned publication application mixture is heat-treated then.Thereby the temperature in the reaction zone will equal or be higher than the fusing point of halogen makes halogen melt the also surface of wetting carbonaceous material, and halogen begins to be dispersed in the carbonaceous material thus.Heating also promotes the combining of compound of polyvalent cation and one or more formulas Ia and/or Ib in the material.
Utilize it and put into practice adsorbent of the present invention also can be by for X 2Or the preparation of the halogen of HX form, wherein X is bromine, chlorine or iodine, and is preferably bromine.By X 2Or the methods availalbe that HX prepares adsorbent is described in the United States Patent (USP) 6,953,494 of Nelson Jr..With the method for Nelson or additive method by X 2Or the product made of HX can mix mutually with the compound of one or more formulas Ia and/or Ib and with after heat treatment makes it compatible with the surface-active of AEA compound.Carbonaceous material and gas X such as PAC 2Or HX is in contact with one another to form absorbent composition apace.Can use the mixed method of any routine and equipment so that gas X 2Or HX contacts with carbonaceous material.The mixing that is preferably halogen-containing gas and carbonaceous material is at high temperature carried out.This will keep halogen-containing gas such as bromine is gas form, and makes the amount of any halogen of only physical absorption on carbon reduce to minimum.Only physical absorption and to be not chemical bond will handle, preserve especially and be emitted when injecting hot waste gas at the halogen on the carbon lattice.
The carbonaceous material of any kind described herein can with halogen X 2Thereby or HX reaction preparation adsorbent composition.
Preferred carbonaceous parent material is an activated carbon.If manufacture method of the present invention is incorporated in the manufacturing of activated carbon active carbon material self, carbonaceous matrix can be the material with carbon element that has for example carried out the steam activation process at it.Another mode, activated carbon can be any existing commercial product such as above-mentioned those.Be preferably, activated carbon is very fine state, makes it obtaining more uniform halogenation in the method subsequently.An example is powder activated carbon (PAC).
If carbonaceous material starts from normal temperature, be preferably it is preheated to and be higher than about 100 ℃ temperature from carbonaceous matrix, to disperse the moisture of any physical absorption, described moisture will block the hole of material and disturb halogenation step.Halogen is as X 2Or HX provides with 100% pure air-flow or mix mutually with other materials that for halogenation are inertia and to provide.Be preferably this gas and comprise Br 2And/or HBr.Halogen-containing gas can be finished under any favourable pressure with contacting of carbon solid, comprises atmospheric pressure.
Carbonaceous material is that the physical absorption halogen species also carries out chemical reaction with it.Be preferably and reduce to the halogen quantity of faint physical absorption on carbonaceous material minimum.When only the halogen of physical absorption is easy to for example be injected into when condition changes in the hotter air-flow from the composition desorption.Desirable is to make halogen stable as much as possible on carbon, but the form for reacting with mercury still.By at high temperature carbon being exposed to bromine or other halogens, halogen species still less transportation, when preserving or being injected in the hot waste gas stream from the adsorbent composition volatilization and go out.
As if the halogenation of any level of carbonaceous material all improve mercury and remove performance.For example ought report the Br that surpasses 30 weight % 2When being adsorbed onto in some powder activated carbons, compare the Br of the 1 weight % that only has an appointment among the PAC 2, report the reactive significantly increase of observed mercury.The bromination of the higher degree maximum mercury capacity with bigger concrete carbonaceous matrix really is relevant.Carry out in a large amount of possible reactor that halogenation step can be known in the art, as Nelson, Jr. is described.Randomly but for preferably, the halogen species that adsorbent is handled faint maintenance removes from adsorbent subsequently.This can finish by several different methods, comprises by reducing pressure and bleed filling container of material, and is paramount in the temperature of halogenation temperature by adding heat-adsorbent by blast air or inert gas to container, perhaps the combination by these methods.
Comprise in all methods of adsorbent of the compound that adds one or more formulas Ia and/or Ib in manufacturing, the compound of described one or more formulas Ia and/or Ib should be added into and make amount (formula Ia that will exist and the amount of Ib are taken into account) be enough to be combined in the polyvalent cation that exists in the adsorbent, otherwise described polyvalent cation joins interference the surface-active of the aerating additive in the cement composition that contains flyash, and described flyash reclaims from waste gas and contains the adsorbent that is used for removing from waste gas mercury.Usually the compound of described one or more formulas Ia and/or Ib should exist with 0.001 weight % to 20 weight % of activated carbon weight then.Equally, thus be preferably and the compound of formula Ia and/or Ib is disperseed to spread all over composition promote combining of compound and polyvalent cation greatly.
Usually, combination for the compound of one or more formulas Ia that realizes polyvalent cation in the desirable sorbent material and existence and/or Ib, in these methods of any manufacturing adsorbent, material should be heated to 40 ℃ of temperature to 1300 ℃ of magnitudes and reach 0.001sec to 1hr.Suitable temperature changed with different parent materials with the duration of heat, but can easily determine suitable level by experiment.
No matter the heat treatment of carrying out in these adsorbent manufacture methods is carried out suitable, all promote in the material polyvalent cation be present in material in one or more formulas Ia and/or the combining of the compound of Ib.This combination comprises that reaction forms compound, and wherein multivalence example such as calcium replaces (Alk) among the formula Ib.In fact a spot of polyvalent cation can capture in the material that is added and can not react with surfactant molecule more thus.The combination of the polyvalent cation in adsorbent also can comprise the physical encapsulation of the compound that has polyvalent cation in the sorbent material, thereby makes the polyvalent cation in these compounds not react with surfactant and other aerating additives.
In some cases, solid absorbent of the present invention also can not add the compound of the Ia of any additional amount and/or Ib and provide.These are that wherein adsorbent has been had the situation of the compound of one or more formulas Ia of enough high-loads and/or Ib by its carbon raw material that is prepared (such as some coal), thus under the condition that effectively promotes combination by the heating carbon raw material can realize polyvalent cation and one or more formulas Ia and/or Ib in the sorbent material compound combine reduce or eliminating to the surface-active interference of aerating additive.In these situations, can carry out above-described any method preparation and on carbonaceous material, be dispersed with the adsorbent of halogen or other forms of halogen, but not add one or more formulas Ia and/or the Ib of any amount.The heating of being carried out in aforesaid every kind of method is carried out equally, perhaps carries out before halogen or other forms of halogen are acted on carbon raw material or carries out in the process of preparation adsorbent, decides with situation.
Heating must promote adsorbent combining by the compound of the polyvalent cation in its prepared material and one or more formulas Ia and/or Ib effectively, in these situations, the compound of described one or more formulas Ia and/or Ib is (usually, they exist with a large amount of relatively silicic acid (orthosilicic acid) sodium) in the material Already in.Yet, in these situations, thereby must provide heating both to promote modestly in conjunction with also making adsorbent by the carbonaceous parent material.Instruction is handled parent material simply and is made and be dispersed with halogen on it or halid adsorbent can not promote desirable hungry combination described herein effectively as described above, and vice versa.Realize that simultaneously the heating condition of two targets can easily determine according to the parent material of any particular combinations, but be not to be not take into account or do not consider the purpose that the polyvalent cation in the sorbent material is combined with the compound of formula Ia and/or formula Ib and use existing open guidance to carry out the condition of using in the manufacturing of adsorbent.
With reference now to Fig. 2,, shown the example system of using catalyst-sorbent of the present invention.The result of burning forms waste gas 22 in stove or the boiler 20.Waste gas 22 forms and temperature can change, and the model group compound can comprise: 6%O 2, 12%CO 2, 8%H 2O, 1600ppm SO 2, 400ppm NO, 50ppm HCl, 20ppm NO 2With 12 μ g/m 3Element Hg by after the various heat exchangers, is discharged into before the air, and temperature can be about 200-570 °F.The catalyst-sorbent 30a that is formed by above-described any means can be injected into the upstream of particle collection device (PCD) 24.Particle collection device 24 is dust storage chamber or electrostatic precipitator (ESP) normally.Adsorbent 30a is injected in the waste gas stream 22 of PCD24 upstream, thereby makes catalyst-sorbent have sufficient residence time to capture and remove mercury from waste gas 22.
From PCD24, remove degranulation and the adsorbent that contains mercury by air-flow 28.Therefore waste gas 26 contain than waste gas 22 mercury still less, and can deliver to chimney.In some embodiments, desirable is that catalyst-sorbent is injected in the waste gas in PCD downstream.
As discussed above, can think that as long as salt is dispersed on the PAC surface catalyst-sorbent of the present invention can at high temperature be removed mercury well from waste gas stream.
Embodiment
Present invention is described as parent material from the coal in three geographical position.They are: from the ub-bituminous coal (" PRB ") of Wyoming State Powder River Basin, from the brown coal (" NDL ") of North Dakota State Antelope Valley with from the bituminous coal (" Utah ") of the outer Deer Creek of Utah State Huntington.The Si of these coals and Ca content are listed in (former state when receiving is before any burning or other heat treated) in the table 1.
The silicon of table 1 coal and calcium content
Sample name Si Ca Si/Ca
mmol/g mmol/g
m m
Wyoming State Powder River
0.13 0.25 0.51
Basin coal (PRB)
North Dakota State Antelope
0.16 0.28 0.57
Valley brown coal (NDL)
Utah State Deer Creek (Utah) 0.47 0.21 2.27
Adsorbent by the two kinds of different formulations of each manufacturing in these coals.In a kind of prescription, in the manufacturing of adsorbent, add NaBr as additive (give mercury and remove ability), but do not add the compound of formula Ia and/or Ib.In another prescription, in the manufacturing of adsorbent, add NaBr and silica or aluminate.The amount of additive, the additive that adds in the manufacturing of adsorbent and the activation condition that uses in the manufacturing of adsorbent all are listed in the table 3,4 and 5.Avoid very harsh coal activation condition to avoid the disintegration of activated carbon.For PRB and NDL coal, add the obvious difference (blow index (FI) by measured gained adsorbent is determined) that 0.2 weight % sodium metasilicate causes the AEA compatibility.For example, the sodium metasilicate that adds 0.2 weight % has reduced by 2 or 3 factors with FI.The gained result is even more important for the PRB coal, and this is because it has Si/Ca ratio (1.4) minimum in the material of being tested.These results show that having good mercury removes the compatible adsorbent of AEA of ability and can make by before activation silicate or clay being joined in the coal.The NDL brown coal are also benefited from the manufacturing of adsorbent and are added silicate, but less to its dependence.The Utah coal to the dependence minimum of silicate, obviously has natural silicate content the highest in the material of being tested because of it aspect the excellent compatibility of AEA.
Thereby tested another embodiment of the present invention does not add formula Ia and/or Ib to determine brown coal that activation condition can be applied to medium paramount Si/Ca ratio and make AEA compatible adsorbent additive.
The result has confirmed to utilize the activation temperature of gentle activation condition such as appropriateness and the adsorbent that short soak time can realize having good mercury adsorption capacity and gratifying AEA compatibility (promptly low blow index), yet, if in overactivity temperature and long-term job time or be rich under the condition of steam, will lose the AEA compatibility.For example, can make the compatible adsorbent of AEA, but carry out then destroying in 20 minutes the AEA compatibility at 1000 ℃ 900 ℃ of activation processs of carrying out 10 minutes.The restriction of these activation conditions sometimes to the quality of activated carbon for example surface area have a negative impact.In these cases, the adding of the compound of formula Ia and/or Ib can provide the bigger flexibility of activation process condition.
The result shows that Utah bituminous coal contains enough silicate under its native state so thereby it does not need to add more silicate has gratifying mercury adsorbent and AEA compatibility (promptly hanging down blow index) with this material manufacturing of heat treatment the adsorbent of starving to it.
By following method, the coal sample described in this paper and table 1 prepares adsorbent.Be crushed to the degree that convention in the power plant uses (70% by 200 orders and be less than 1% greater than 50 orders) coal soak with the sodium metasilicate of minimal volumes and the mixed aqueous solution of sodium bromide, dry then and pulverize once more or (wherein dry mixed is indicated in following table) grinds solid mixture or mix until the acquisition homogeneous mixture.In each situation, sodium metasilicate: NaBr: the ratio of coal is 0.02-10: 0.02-10: 100.Pack in the ceramic boat by the 12 gram mixtures that these methods obtain, and described boat put into 2 " the diameter tube furnace, described tube furnace remains on activation temperature (900 ℃ to 1200 ℃) and blasts constantly with 100 ℃ of saturated air and flows (or as shown).Coal activates the time of different length, then drying nitrogen is replaced by in the rapid cooling zone territory of hot sample immigration tube furnace and the air-flow that blasts.The activated carbon adsorbent of Zhi Zaoing is broken for powder and is measured its blow index thus.
In order to contrast, (blow index of self of Quikrete Business Registration type i/II) is measured as 5, and (5 10%DarexII, 53/ml), this cement is 9 with blow index from the compound of the flyash of P4 to cement.Cement is measured as 120 with the blow index of the mixture of the flyash that contains 16% residual carbon.
For being replicated in the amount of practical commercial scale in using, wherein in flyash, need the mercury adsorbent of 1-3% usually, use 1.98gm flyash from P-4 to dilute the 0.02gm activated carbon adsorbent of preparation as described herein and measure blow index.Also measured the blow index of commercial PAC (DARCOHg, DARCO LH, Norit FGD, carbon source ACF1300/200 (activated carbon fiber) and pitch class BAC).These contrast blow index values are listed in the table 2.Carbon fiber has 1400m 2The surface area of/gm.Darco Hg-LH has 429m 2The surface area of/gm, but the blow index of Darco Hg-LH is higher by 100% than the blow index of carbon fiber.Darco Hg-LH, Darco Hg and FGD are coal class activated carbon and ash content with 25% magnitude.
Use the test condition and the result of the test of PRB coal to be summarised in the table 3.Embodiment 1-4 shows or by activation temperature is reduced to 900 ℃ or soak time was foreshortened to 10 minutes energy by 20 minutes blow index is reduced to 43 (37) by 88 by 1000 ℃.These improvement are useful, through also off-peak.Embodiment 5-6 shows with the sodium metasilicate activated carbon that simply mixes to be provided unacceptable high blow index and has therefore thought and almost be no advantage to improving the concrete compatibility.Embodiment 7-12 shows with sodium metasilicate, Cab-O-Sil, boehmite or bentonite doping and mixes under suitable activation condition and can reduce the blow index of gained activated carbon adsorbent to 23-24.
The blow index of table 2 comparative sample
FI test mixing thing mean F I mean F I, cc
Cement 5 0.09 is only arranged
Cement+P4 ash 9 0.17
Cement+high C ash 120 2.26
Cement+P4+FGD 58 1.10
Cement+P4+DarcoHg-LH 49 0.92
Cement+P4+DarcoHg 38 0.72
Cement+P4+ carbon fiber 25 0.47
Cement+P4+ is ashless carbon 27 0.51
Table 3PRB sample
Embodiment F I
Prescription coal activation condition FI
# ml
1000 ℃ of air
PRB: NaBr=100: 2 liters of/minute steam, 100
1 88 1.66
0.2 ℃, 20 minutes
900 ℃ of air
PRB∶NaBr＝100∶
22 liters of/minute steam, 100 43 0.81
0.2 ℃, 20 minutes
1070 ℃ of air
PRB∶NaBr＝
32 liters of/minute steam, 37 0.70
100∶0.2
10 minutes
1070 ℃ of air
PRB∶NaBr＝
44 liters of/minute steam 43 0.81
100∶0.1
10 minutes
1000℃N 2
PRB∶NaBr＝100∶
100 ℃ of 52 liters of/minute steam, 82 1.55
0.2
30 minutes
17390-93H+1％
The air drying; No high temperature
6 Nasilicate wet methods mix 70 1.32
Handle
Assorted
PRB: NaBr: 1070 ℃ of air of silicic acid
7 23 0.43
Sodium=100: 0.2: 52 liters of/minute steam
1070 ℃ of air
PRB: NaBr: silicic acid
82 liters of/minute steam 24 0.45
Sodium=100: 0.2: 1
10 minutes
1070 ℃ of air
PRB: NaBr: silicic acid
92 liters of/minute steam 23 0.43
Sodium=100: 0.2: 0.1
10 minutes
PRB: NaBr: 1070 ℃ of furnace temperature;
10 Cab-O-Sil=100: 4 liters of/minute air, logical 24 0.45
0.2: 2 cross boiling water, 10 minutes
1070 ℃ of air
PRB: NaBr: Bo Mu
11 2 liters of/minute steam, 10 minutes 28 0.53
Stone=100: 0.2: 0.2
Clock
PRB: NaBr: 1070 ℃ of furnace temperature;
2 liters of/minute air of 12 Wyo-ben=, logical 23 0.43
Cross boiling water, 10 minutes at 100: 0.2: 2
Use the test condition and the result of NDL coal to be summarised in the table 4.Embodiment 13-14 shows that the sodium metasilicate doping can improve FI.Yet brown coal have higher oxygen content, and with such as one group of different chemical property of the ub-bituminous coal of PRB.The AEA compatibility performance that derives from the adsorbent of NDL is controlled relatively simply by adjusting activation condition.Embodiment 15 shows by remove steam from the activation air-flow can realize better that FI improves.Embodiment 16-17 shows by reducing activation temperature simultaneously and shortening soak time and can realize extraordinary 15 FI.
Yet in making the mercury adsorbent, target comprises having the high-adsorption-capacity and the mercury rate of adsorption fast, and have and the compatibility of AEA additive (promptly low blow index), realize that arbitrary these target calls depend on the different activation conditions of the chemistry of certain enzyme.Thereby the result that this paper obtains points out to add silicate and gives the more leeway of manufacture method to select the ability of all targets of activation condition raising realization to gratifying degree.
Table 4 uses the sample of NDL coal
Embodiment F I
Prescription coal activation condition FI
#
ml
1000 ℃ of air
Dry mixed NaBr:
13 2 liters/minute 100 ℃ are steamed 63 1.19
NDL＝0.25∶100
Vapour, 15 minutes
1000 ℃ of air
NDL: NaBr: silicic acid
14 2 liters of/minute steam 35 0.66
Sodium=100: 0.25: 1
15 minutes
1000 ℃ of air
NDL∶NaBr＝
15 2 liters/minute 25 0.47
100∶0.25
No steam, 15 minutes
900 ℃ of air
NDL∶NaBr＝
16 2 liters of/minute steam 42 0.79
100∶0.2
20 minutes
900 ℃ of air
NDL∶NaBr＝
17 2 liters of/minute steam 15 0.28
100∶0.2
10 minutes
Use test condition and the result of the embodiment of Utah bituminous coal to be summarised in the table 6.The result shows because the natural silicate height of employed " Utah " coal does not need to add extra silicate.
Table 6 uses the embodiment of Utah bituminous coal
FI
Embodiment # prescription coal activation condition FI
ml
1070 ℃ of furnace temperature; 2 liters/
Dry mixed Utah coal:
18 fens steam; 23 0.43
NaBr＝100∶0.5
20 minutes
1000 ℃ of air
Utah∶NaBr＝
19 2 liters of/minute steam 24 0.45
100∶0.2
20 minutes
900 ℃ of air
Utah∶NaBr＝ 17 0.32
20 2 liters of/minute steam
100∶0.2
20 minutes

Claims (117)

1. catalyst-sorbent composition of at high temperature from waste gas stream, removing mercury, described catalyst-sorbent composition comprises the activated carbon that is dispersed with halogen on it, described halogen comprises cation and anion, and described catalyst-sorbent composition has the blow index less than 45 after it is used at high temperature flowing absorption mercury from waste gas.
2. composition as claimed in claim 1, wherein said cation is selected from alkali metal, alkaline-earth metal, transition metal and combination thereof.
3. composition as claimed in claim 2, wherein said cation is selected from Na, Mg, Ca, Cu, K and combination thereof.
4. composition as claimed in claim 1, wherein said anion is selected from bromine, chlorine and combination thereof.
5. composition as claimed in claim 1, wherein said halogen is selected from NaCl, KCl, CaCl 2, CuCl 2, CuBr 2, NaBr, KBr, CaBr 2, MgBr 2And composition thereof.
6. composition as claimed in claim 5, wherein said halogen are NaBr, KBr or its mixture.
7. be used at high temperature flowing from waste gas the manufacture method of the composition of matter of removing mercury, described method comprises that (a) forms the mixture of the compound of carbon raw material, halogen and one or more formulas Ia and/or Ib
Mg(OH) 2 (Ia)
(Alk) a(M nO p) (Ib)
Even every M that occurs in a part wherein, it is a silicon, aluminium or phosphorus, even every Alk that occurs in a part, it is sodium or potassium, and a, n and p are through selecting to make the compound of formula Ib not with the positive integer of net charge, (b) mixture that will form in step (a) places and can effectively form under the condition of adsorbent composition, described adsorbent composition comprises the activated carbon that is dispersed with halogen on its surface, described condition comprises heating with the combining of the compound that promotes polyvalent cation and described one or more formulas Ia and/or Ib in the described adsorbent composition effectively, thereby makes described composition of matter be used at high temperature having blow index less than 45 at it behind waste gas stream absorption mercury.
8. method as claimed in claim 7, the compound of wherein said one or more formulas Ia and/or Ib comprise sodium orthosilicate or potassium, sodium metasilicate or potassium, sodium aluminosilicate or potassium, sodium orthophosphate or potassium or sodium metaphosphate or potassium.
9. method as claimed in claim 7, the compound of wherein said one or more formulas Ia and/or Ib comprise a kind of in sodium orthosilicate and the sodium metasilicate or include.
10. be used at high temperature flowing the manufacture method of the composition of matter of removing mercury from waste gas, described method comprises that (a) forms the mixture of carbon raw material and halogen, (b) mixture that will form in step (a) places and can effectively form under the condition of adsorbent, described adsorbent composition comprises the activated carbon that is dispersed with halogen on its surface, (c) product that forms in the step (b) is mixed mutually with the compound of one or more formulas Ia and/or Ib
Mg(OH) 2 (Ia)
(Alk) a(M nO p) (Ib)
Even every M that occurs in a part wherein, it is a silicon, aluminium or phosphorus, even every Alk that occurs in a part, it is sodium or potassium, and a, n and p are through selecting to make the compound of formula Ib not with the positive integer of net charge, (d) mixture that will form in step (c) places under the certain condition, described condition comprises heating with the combining of the compound that promotes polyvalent cation and described one or more formulas Ia and/or Ib in the described adsorbent composition effectively, thereby makes described composition of matter be used at high temperature having blow index less than 45 at it behind waste gas stream absorption mercury.
11. method as claimed in claim 10, the compound of wherein said one or more formulas Ia and/or Ib comprise sodium orthosilicate or potassium, sodium metasilicate or potassium, sodium aluminosilicate or potassium, sodium orthophosphate or potassium or sodium metaphosphate or potassium.
12. method as claimed in claim 10, the compound of wherein said one or more formulas Ia and/or Ib comprise a kind of in sodium orthosilicate and the sodium metasilicate or include.
13. be used at high temperature flowing from waste gas the manufacture method of the composition of matter of removing mercury, described method comprises that (a) forms the mixture of carbon raw material and halogen, wherein said carbon raw material contains the compound of one or more formulas Ia and/or Ib
Mg(OH) 2 (Ia)
(Alk) a(M nO p) (Ib)
Even every M that occurs in a part wherein, it is a silicon, aluminium or phosphorus, even every Alk that occurs in a part, it is sodium or potassium, and a, n and p are through selecting to make the compound of formula Ib not with the positive integer of net charge, (b) mixture that will form in step (a) places and can effectively form under the condition of adsorbent composition, described adsorbent composition comprises the activated carbon that is dispersed with halogen on its surface, described condition comprises heating combining with the compound that promotes polyvalent cation and described one or more formulas Ia and/or Ib in the described adsorbent composition effectively, thereby make described composition of matter be used at high temperature behind waste gas stream absorption mercury, having blow index, wherein do not add the compound of any formula Ia of any more volume or Ib and carry out described method less than 45 at it.
14. method as claimed in claim 13, the compound of wherein said one or more formulas Ia and/or Ib comprise sodium orthosilicate or potassium, sodium metasilicate or potassium, sodium aluminosilicate or potassium, sodium orthophosphate or potassium or sodium metaphosphate or potassium.
15. method as claimed in claim 13, the compound of wherein said one or more formulas Ia and/or Ib comprise a kind of in sodium orthosilicate and the sodium metasilicate or include.
16. be used at high temperature flowing from waste gas the manufacture method of the catalyst-sorbent of absorption mercury, described method comprises:
Powder activated carbon is put into the aqueous solution that contains halogen and contain the compound of one or more formulas Ia and/or Ib form mixture
Mg(OH) 2 (Ia)
(Alk) a(M nO p) (Ib)
Even every M that occurs in a part wherein, it is silicon, aluminium or phosphorus, though in a part every Alk that occurs, it is sodium or potassium, and a, n and p are through selecting to make the compound of formula Ib not with the positive integer of net charge; Stir described mixture until forming the homogeneous phase slurry;
Dry described powder activated carbon make in the aqueous solution the water evaporation and the compound of halogen and one or more formulas Ia and/or Ib is dispersed on the surface of powder activated carbon, by heating combining with the compound that promotes polyvalent cation and described one or more formulas Ia and/or Ib in the described adsorbent composition effectively, thereby make described composition of matter be used at high temperature behind waste gas stream absorption mercury, having blow index, wherein do not add the compound of any formula Ia of any more volume or Ib and carry out described method less than 45 at it.
17. method as claimed in claim 16, wherein said cation is selected from Na, Mg, Ca, Cu, K and combination thereof.
18. method as claimed in claim 16, wherein said anion is selected from bromine, chlorine and combination thereof.
19. method as claimed in claim 16, wherein said halogen is selected from NaCl, KCl, CaCl 2, CuCl 2, CuBr 2, NaBr, KBr, CaBr 2, MgBr 2And composition thereof.
20. method as claimed in claim 16, wherein said halogen are one or both among NaBr and the KBr.
21. method as claimed in claim 16, the compound of wherein said one or more formulas Ia and/or Ib comprise sodium orthosilicate or potassium, sodium metasilicate or potassium, sodium aluminosilicate or potassium, sodium orthophosphate or potassium or sodium metaphosphate or potassium.
22. method as claimed in claim 16, the compound of wherein said one or more formulas Ia and/or Ib comprise a kind of in sodium orthosilicate and the sodium metasilicate or include.
23. be used at high temperature flowing from waste gas the manufacture method of the catalyst-sorbent of absorption mercury, described method comprises: will inject reative cell with the carbon raw material that the compound with cation and anionic halogen and one or more formulas Ia and/or Ib soaks in advance
Mg(OH) 2 (Ia)
(Alk) a(M nO p) (Ib)
Even every M that occurs in a part wherein, it is silicon, aluminium or phosphorus, though in a part every Alk that occurs, it is sodium or potassium, and a, n and p are through selecting to make the compound of formula Ib not with the positive integer of net charge; At least a oxidizing gas is injected reative cell; Steam is injected reative cell, the wherein said carbon raw material that soaks in advance, air and steam inject reative cell, its residing condition and residence time are enough to be formed on the surface of activated carbon and are dispersed with the activated carbon with cation and anionic halogen, and promote the combining of compound of polyvalent cation and described one or more formulas Ia and/or Ib in the described adsorbent composition, thereby make described composition of matter be used at high temperature behind waste gas stream absorption mercury, having blow index less than 45 at it.
24. method as claimed in claim 23, wherein said oxidizing gas comprise air, oxygen, steam, nitrogen or its combination.
25. method as claimed in claim 23, wherein said cation is selected from Na, Ca, Cu, K and combination thereof.
26. method as claimed in claim 23, wherein said anion is selected from bromine, chlorine and combination thereof.
27. method as claimed in claim 23, wherein said halogen is selected from NaCl, KCl, CaCl 2, CuCl 2, CuBr 2, NaBr, KBr, CaBr 2, MgBr 2And composition thereof.
28. method as claimed in claim 23, wherein said halogen are one or both among NaBr and the KBr.
29. method as claimed in claim 23, the compound of wherein said one or more formulas Ia and/or Ib comprise sodium orthosilicate or potassium, sodium metasilicate or potassium, sodium aluminosilicate or potassium, sodium orthophosphate or potassium or sodium metaphosphate or potassium.
30. method as claimed in claim 23, the compound of wherein said one or more formulas Ia and/or Ib comprise a kind of in sodium orthosilicate and the sodium metasilicate or include.
31. be used at high temperature flowing from waste gas the manufacture method of the catalyst-sorbent of absorption mercury, described method comprises: the compound of dry mixed carbon raw material and halogen and one or more formulas Ia and/or Ib
Mg(OH) 2 (Ia)
(Alk) a(M nO p) (Ib)
Even every M that occurs in a part wherein, it is silicon, aluminium or phosphorus, though in a part every Alk that occurs, it is sodium or potassium, and a, n and p are through selecting to make the compound of formula Ib not with the positive integer of net charge; The carbon raw material that mixes is injected reative cell; At least a activated gas is injected reative cell; Wherein said carbon raw material and at least a activated gas inject reative cell, its residing condition and stay the time to be enough to be formed on the surface of activated carbon and be dispersed with activated carbon with cation and anionic halogen, described condition comprises heating with the combining of the compound of the polyvalent cation in the described adsorbent composition of effective promotion and described one or more formulas Ia and/or Ib, thereby makes described composition of matter be used at high temperature having blow index less than 45 at it behind waste gas stream absorption mercury.
32. method as claimed in claim 31, wherein said at least a activated gas comprises air, oxygen, steam, nitrogen, CO 2, CO or its combination.
33. method as claimed in claim 31, wherein said cation is selected from alkali metal, alkaline-earth metal, transition metal and combination thereof.
34. method as claimed in claim 31, wherein said cation is selected from Na, Ca, Mg, Cu, K and combination thereof.
35. method as claimed in claim 31, wherein said anion is selected from bromine, chlorine and combination thereof.
36. method as claimed in claim 31, wherein said halogen is selected from NaCl, KCl, CaCl 2, CuCl 2, CuBr 2, NaBr, KBr, CaBr 2, MgBr 2And composition thereof.
37. method as claimed in claim 31, wherein said halogen are one or both among NaBr and the KBr.
38. method as claimed in claim 31, the compound of wherein said one or more formulas Ia and/or Ib comprise sodium orthosilicate or potassium, sodium metasilicate or potassium, sodium aluminosilicate or potassium, sodium orthophosphate or potassium or sodium metaphosphate or potassium.
39. method as claimed in claim 31, the compound of wherein said one or more formulas Ia and/or Ib comprise a kind of in sodium orthosilicate and the sodium metasilicate or include.
40. method as claimed in claim 31, wherein said carbon raw material comprises coal.
41. method as claimed in claim 40, wherein said coal comprises ub-bituminous coal.
42. method as claimed in claim 40, wherein said coal comprises bituminous coal.
43. method as claimed in claim 40, wherein said coal comprises brown coal.
44. be used at high temperature flowing from waste gas the manufacture method of the catalyst-sorbent of absorption mercury, described method comprises: the compound of wet-mixing carbon raw material and halogen and one or more formulas Ia and/or Ib
Mg(OH) 2 (Ia)
(Alk) a(M nO p) (Ib)
Even every M that occurs in a part wherein, it is silicon, aluminium or phosphorus, though in a part every Alk that occurs, it is sodium or potassium, and a, n and p are through selecting to make the compound of formula Ib not with the positive integer of net charge; Dry described mixture; The mixture of drying is injected reative cell; At least a activated gas is injected reative cell; Wherein said carbon raw material and at least a activated gas inject reative cell, its residing condition and residence time are enough to be formed on the surface of activated carbon and are dispersed with the activated carbon with cation and anionic halogen, described condition comprises heating with the combining of the compound of the polyvalent cation in the described adsorbent composition of effective promotion and described one or more formulas Ia and/or Ib, thereby makes described composition of matter be used at high temperature having blow index less than 45 at it behind waste gas stream absorption mercury.
45. method as claimed in claim 44, wherein, wherein said at least a activated gas comprises air, oxygen, steam, nitrogen, CO 2, CO or its combination.
46. method as claimed in claim 44, wherein said cation is selected from alkali metal, alkaline-earth metal, transition metal and combination thereof.
47. method as claimed in claim 44, wherein said cation is selected from Na, Ca, Mg, Cu, K and combination thereof.
48. method as claimed in claim 44, wherein said anion is selected from bromine, chlorine and combination thereof.
49. method as claimed in claim 44, wherein said halogen is selected from NaCl, KCl, CaCl 2, CuCl 2, CuBr 2, NaBr, KBr, CaBr 2, MgBr2 and composition thereof.
50. method as claimed in claim 44, wherein said halogen are one or both among NaBr and the KBr.
51. method as claimed in claim 44, the compound of wherein said one or more formulas Ia and/or Ib comprise sodium orthosilicate or potassium, sodium metasilicate or potassium, sodium aluminosilicate or potassium, sodium orthophosphate or potassium or sodium metaphosphate or potassium.
52. method as claimed in claim 44, the compound of wherein said one or more formulas Ia and/or Ib comprise a kind of in sodium orthosilicate and the sodium metasilicate or include.
53. method as claimed in claim 44, wherein said carbon raw material comprises coal.
54. method as claimed in claim 53, wherein said coal comprises ub-bituminous coal.
55. method as claimed in claim 53, wherein said coal comprises bituminous coal.
56. method as claimed in claim 53, wherein said coal comprises brown coal.
57. be used at high temperature flowing the manufacture method of the catalyst-sorbent of absorption mercury from waste gas, described method comprises: will be with having the coal injection reative cell that cation and anionic halogen soak in advance, and wherein said coal contains the compound of one or more formulas Ia and/or Ib
Mg(OH) 2 (Ia)
(Alk) a(M nO p) (Ib)
Even every M that occurs in a part wherein, it is silicon, aluminium or phosphorus, though in a part every Alk that occurs, it is sodium or potassium, and a, n and p are through selecting to make the compound of formula Ib not with the positive integer of net charge; At least a oxidizing gas is injected reative cell; Steam is injected reative cell, the wherein said coal that soaks in advance, air and steam inject reative cell, its residing condition and residence time are enough to be formed on the surface of activated carbon and are dispersed with the activated carbon with cation and anionic halogen, described condition comprises heating combining with the compound of the polyvalent cation in the described adsorbent composition of effective promotion and described one or more formulas Ia and/or Ib, thereby make described composition of matter be used at high temperature behind waste gas stream absorption mercury, having blow index, wherein do not add the compound of any formula Ia of any more volume or Ib and carry out described method less than 45 at it.
58. method as claimed in claim 57, wherein said oxidizing gas comprise air, oxygen, steam, nitrogen or its combination.
59. method as claimed in claim 57, wherein said cation is selected from Na, Ca, Cu, K and combination thereof.
60. method as claimed in claim 57, wherein said anion is selected from bromine, chlorine and combination thereof.
61. method as claimed in claim 57, wherein said halogen is selected from NaCl, KCl, CaCl 2, CuCl 2, CuBr 2, NaBr, KBr, CaBr 2, MgBr2 and composition thereof.
62. method as claimed in claim 57, wherein said halogen are one or both among NaBr and the KBr.
63. method as claimed in claim 57, the compound of wherein said one or more formulas Ia and/or Ib comprise sodium orthosilicate or potassium, sodium metasilicate or potassium, sodium aluminosilicate or potassium, sodium orthophosphate or potassium or sodium metaphosphate or potassium.
64. method as claimed in claim 57, the compound of wherein said one or more formulas Ia and/or Ib comprise a kind of in sodium orthosilicate and the sodium metasilicate or include.
65. be used at high temperature from the manufacture method of the catalyst-sorbent of waste gas stream absorption mercury, described method comprises: dry mixed coal and have cation and anionic halogen, wherein said coal contains the compound of one or more formulas Ia and/or Ib
Mg(OH) 2 (Ia)
(Alk) a(M nO p) (Ib)
Even every M that occurs in a part wherein, it is silicon, aluminium or phosphorus, though in a part every Alk that occurs, it is sodium or potassium, and a, n and p are through selecting to make the compound of formula Ib not with the positive integer of net charge; The mixture of coal cinder halogen such as reative cell, and is injected reative cell with at least a activated gas; At least a activated gas of wherein said coal cinder places reative cell, its residing condition and residence time are enough to be formed on the surface of activated carbon and are dispersed with the activated carbon with cation and anionic halogen, described condition comprises heating combining with the compound of the polyvalent cation in the described adsorbent composition of effective promotion and described one or more formulas Ia and/or Ib, thereby make described composition of matter be used at high temperature behind waste gas stream absorption mercury, having blow index, wherein do not add the compound of any formula Ia of any more volume or Ib and carry out described method less than 45 at it.
66. as the described method of claim 65, wherein said at least a activated gas comprises air, oxygen, steam, nitrogen, CO 2, CO or its combination.
67. as the described method of claim 65, wherein said cation is selected from alkali metal, alkaline-earth metal, transition metal and combination thereof.
68. as the described method of claim 65, wherein said cation is selected from Na, Ca, Mg, Cu, K and combination thereof.
69. as the described method of claim 65, wherein said anion is selected from bromine, chlorine and combination thereof.
70. as the described method of claim 65, wherein said halogen is selected from NaCl, KCl, CaCl 2, CuCl 2, CuBr 2, NaBr, KBr, CaBr 2, MgBr2 and composition thereof.
71. as the described method of claim 65, wherein said halogen is one or both among NaBr and the KBr.
72. as the described method of claim 65, the compound of wherein said one or more formulas Ia and/or Ib comprises sodium orthosilicate or potassium, sodium metasilicate or potassium, sodium aluminosilicate or potassium, sodium orthophosphate or potassium or sodium metaphosphate or potassium.
73. as the described method of claim 65, the compound of wherein said one or more formulas Ia and/or Ib comprises a kind of in sodium orthosilicate and the sodium metasilicate or includes.
74. be used at high temperature flowing from waste gas the manufacture method of the catalyst-sorbent of absorption mercury, described method comprises: wet-mixing coal and halogen, wherein said coal contains the compound of one or more formulas Ia and/or Ib
Mg(OH) 2 (Ia)
(Alk) a(M nO p) (Ib)
Even every M that occurs in a part wherein, it is silicon, aluminium or phosphorus, though in a part every Alk that occurs, it is sodium or potassium, and a, n and p are through selecting to make the compound of formula Ib not with the positive integer of net charge; Dry described mixture; The mixture of drying is injected reative cell; At least a activated gas is injected reative cell; Wherein said carbon raw material and at least a activated gas inject reative cell, its residing condition and residence time are enough to be formed on the surface of activated carbon and are dispersed with the activated carbon with cation and anionic halogen, described condition comprises heating combining with the compound of the polyvalent cation in the described adsorbent composition of effective promotion and described one or more formulas Ia and/or Ib, thereby make described composition of matter be used at high temperature behind waste gas stream absorption mercury, having blow index, wherein do not add the compound of any formula Ia of any more volume or Ib and carry out described method less than 45 at it.
75. as the described method of claim 74, wherein said at least a activated gas comprises air, oxygen, steam, nitrogen, CO 2, CO or its combination.
76. as the described method of claim 74, wherein said cation is selected from alkali metal, alkaline-earth metal, transition metal and combination thereof.
77. as the described method of claim 74, wherein said cation is selected from Na, Ca, Mg, Cu, K and combination thereof.
78. as the described method of claim 74, wherein said anion is selected from bromine, chlorine and combination thereof.
79. as the described method of claim 74, wherein said halogen is selected from NaCl, KCl, CaCl 2, CuCl 2, CuBr 2, NaBr, KBr, CaBr 2, MgBr2 and composition thereof.
80. as the described method of claim 74, wherein said halogen is one or both among NaBr and the KBr.
81. as the described method of claim 74, the compound of wherein said one or more formulas Ia and/or Ib comprises sodium orthosilicate or potassium, sodium metasilicate or potassium, sodium aluminosilicate or potassium, sodium orthophosphate or potassium or sodium metaphosphate or potassium.
82. as the described method of claim 74, the compound of wherein said one or more formulas Ia and/or Ib comprises a kind of in sodium orthosilicate and the sodium metasilicate or includes.
83. pass through the catalyst-sorbent composition of the method preparation of claim 7.
84. pass through the catalyst-sorbent composition of the method preparation of claim 10.
85. pass through the catalyst-sorbent composition of the method preparation of claim 13.
86. pass through the catalyst-sorbent composition of the method preparation of claim 16.
87. pass through the catalyst-sorbent composition of the method preparation of claim 23.
88. pass through the catalyst-sorbent composition of the method preparation of claim 31.
89. pass through the catalyst-sorbent composition of the method preparation of claim 44.
90. pass through the catalyst-sorbent composition of the method preparation of claim 57.
91. pass through the catalyst-sorbent composition of the method preparation of claim 65.
92. pass through the catalyst-sorbent composition of the method preparation of claim 74.
93. a method of at high temperature removing mercury from air-flow, described method comprises: catalyst-sorbent as claimed in claim 1 is injected air-flow; Mercury is adsorbed onto on the catalyst-sorbent; From air-flow, remove the catalyst-sorbent that contains mercury.
94. as the described method of claim 93, wherein said air-flow contains oxidizing gas, sour gas or its combination.
95. as the described method of claim 93, wherein said air-flow contains inert gas.
96. as the described method of claim 95, wherein said inert gas contains nitrogen.
97. a method of at high temperature removing mercury from air-flow, described method comprises: will inject air-flow as the described catalyst-sorbent of claim 83; Mercury is adsorbed onto on the catalyst-sorbent; From air-flow, remove the catalyst-sorbent that contains mercury.
98. a method of at high temperature removing mercury from air-flow, described method comprises: will inject air-flow as the described catalyst-sorbent of claim 84; Mercury is adsorbed onto on the catalyst-sorbent; From air-flow, remove the catalyst-sorbent that contains mercury.
99. a method of at high temperature removing mercury from air-flow, described method comprises: will inject air-flow as the described catalyst-sorbent of claim 85; Mercury is adsorbed onto on the catalyst-sorbent; From air-flow, remove the catalyst-sorbent that contains mercury.
100. a method of at high temperature removing mercury from air-flow, described method comprises: will inject air-flow as the described catalyst-sorbent of claim 86; Mercury is adsorbed onto on the catalyst-sorbent; From air-flow, remove the catalyst-sorbent that contains mercury.
101. a method of at high temperature removing mercury from air-flow, described method comprises: will inject air-flow as the described catalyst-sorbent of claim 87; Mercury is adsorbed onto on the catalyst-sorbent; From air-flow, remove the catalyst-sorbent that contains mercury.
102. a method of at high temperature removing mercury from air-flow, described method comprises: will inject air-flow as the described catalyst-sorbent of claim 88; Mercury is adsorbed onto on the catalyst-sorbent; From air-flow, remove the catalyst-sorbent that contains mercury.
103. a method of at high temperature removing mercury from air-flow, described method comprises: will inject air-flow as the described catalyst-sorbent of claim 89; Mercury is adsorbed onto on the catalyst-sorbent; From air-flow, remove the catalyst-sorbent that contains mercury.
104. a method of at high temperature removing mercury from air-flow, described method comprises: will inject air-flow as the described catalyst-sorbent of claim 90; Mercury is adsorbed onto on the catalyst-sorbent; From air-flow, remove the catalyst-sorbent that contains mercury.
105. a method of at high temperature removing mercury from air-flow, described method comprises: will inject air-flow as the described catalyst-sorbent of claim 91; Mercury is adsorbed onto on the catalyst-sorbent; From air-flow, remove the catalyst-sorbent that contains mercury.
106. a method of at high temperature removing mercury from air-flow, described method comprises: will inject air-flow as the described catalyst-sorbent of claim 92; Mercury is adsorbed onto on the catalyst-sorbent; From air-flow, remove the catalyst-sorbent that contains mercury.
107. an adsorbent that comprises activated carbon, described adsorbent have the blow index less than 45 after it is used at high temperature flowing absorption mercury from waste gas, described activated carbon is by its surface and be selected from formula X 2Or thereby one or more reagent of the molecule of HX contact and have halide from the teeth outwards and comprise having halide or halogen in its surface, and wherein X is bromine, chlorine or iodine.
108. as the described adsorbent of claim 107, wherein X is Br.
109. be used at high temperature flowing from waste gas the manufacture method of the composition of matter of removing mercury, described method comprises
(a) can be effectively with the atom keyed jointing of X or be adsorbed onto under the condition on the activated carbon surface, with activated carbon and formula X 2Or the compound of HX contacts, and wherein X is bromine, chlorine or iodine,
(b) product that will form in step (a) mixes mutually with the compound of one or more formulas Ia and/or Ib
Mg(OH) 2 (Ia)
(Alk) a(M nO p) (Ib)
Even every M that occurs in a part wherein, it is silicon, aluminium or phosphorus, though in a part every Alk that occurs, it is sodium or potassium, and a, n and p be through selecting to make the compound of formula Ib not with the positive integer of net charge, and
(c) mixture that will form in step (b) places and can effectively form under the condition of adsorbent composition, described adsorbent composition comprises the activated carbon that is dispersed with halogen on its surface, described condition comprises heating with the combining of the compound that promotes polyvalent cation and described one or more formulas Ia and/or Ib in the described adsorbent composition effectively, thereby makes described composition of matter be used at high temperature having blow index less than 45 at it behind waste gas stream absorption mercury
110. as the described method of claim 109, wherein X is Br.
111. as the described method of claim 109, the compound of its Chinese style Ib is a sodium metasilicate.
112. pass through the adsorbent product that the method for claim 109 is made.
113. pass through the adsorbent product that the method for claim 110 is made.
114. pass through the adsorbent product that the method for claim 111 is made.
115. a method of at high temperature removing mercury from air-flow, described method comprises: will inject air-flow as the described adsorbent product of claim 112; Mercury is adsorbed onto on the catalyst-sorbent; From air-flow, remove the catalyst-sorbent that contains mercury.
116. a method of at high temperature removing mercury from air-flow, described method comprises: will inject air-flow as the described adsorbent product of claim 113; Mercury is adsorbed onto on the catalyst-sorbent; From air-flow, remove the catalyst-sorbent that contains mercury.
117. a method of at high temperature removing mercury from air-flow, described method comprises: will inject air-flow as the described adsorbent product of claim 114; Mercury is adsorbed onto on the catalyst-sorbent; From air-flow, remove the catalyst-sorbent that contains mercury.
CNA2007800452416A 2006-12-08 2007-12-10 Mercury adsorbents compatible as cement additives Pending CN101553301A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103338831A (en) * 2010-11-22 2013-10-02 阿尔比马尔公司 Brominated inorganic sorbents for reduction of mercury emissions
CN103608086A (en) * 2011-03-25 2014-02-26 阿尔比马尔公司 Compositions and methods to sequester flue gas mercury in concrete

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103338831A (en) * 2010-11-22 2013-10-02 阿尔比马尔公司 Brominated inorganic sorbents for reduction of mercury emissions
CN103608086A (en) * 2011-03-25 2014-02-26 阿尔比马尔公司 Compositions and methods to sequester flue gas mercury in concrete

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