CN103285805A - Mercury removal agent and preparation method thereof - Google Patents

Mercury removal agent and preparation method thereof Download PDF

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Publication number
CN103285805A
CN103285805A CN2013102421354A CN201310242135A CN103285805A CN 103285805 A CN103285805 A CN 103285805A CN 2013102421354 A CN2013102421354 A CN 2013102421354A CN 201310242135 A CN201310242135 A CN 201310242135A CN 103285805 A CN103285805 A CN 103285805A
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China
Prior art keywords
removal agent
carrier
mercury removal
mercury
oxide
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CN2013102421354A
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CN103285805B (en
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肖天存
黄瑜
陈浩逸
张钢
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GUANGZHOU BOXENERGY TECHNOLOGY Ltd
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GUANGZHOU BOXENERGY TECHNOLOGY Ltd
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Priority to CN201310242135.4A priority Critical patent/CN103285805B/en
Publication of CN103285805A publication Critical patent/CN103285805A/en
Priority to PCT/CN2013/084801 priority patent/WO2014201782A1/en
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    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
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    • B01D53/34—Chemical or biological purification of waste gases
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Abstract

The invention discloses a mercury removal agent and a preparation method thereof. The mercury removal agent comprises the following components in percentage by weight: 40wt%-90wt% of carriers, 1wt%-40wt% of active ingredients and 0-30wt% of modifying agent, wherein the modifying agent is halogen or halide; and the active ingredients are a mixture of oxides of at least two oxidizing metals. The preparation method of the mercury removal agent comprises the following steps of: placing the carriers into one or more soluble oxidizing metal salt solutions, soaking and drying, roasting and placing in one or more soluble metal salt solutions except from the aforementioned soluble metal salts, soaking, drying and roasting to obtain the mercury removal agent. The mercury removal agent disclosed by the invention is unnecessary to vulcanize, capable of using the oxidizing metal oxides as the active ingredient and using the halogen or the halide as the modifying agent, and provided with the beneficial effects of having mercury capacity bigger than 10wt% and the mercury removing efficiency higher than 99.9%. Moreover, the mercury removal agent further can be extensively applied to the removing process of the mercury metal in smoke gas, synthesis gas, natural gas as well as a mercury-containing gas source in liquid substance.

Description

Mercury removal agent and preparation method thereof
Technical field
The present invention relates to aerochemistry adsorption cleaning field, particularly relate to a kind of mercury removal agent that removes for flue gas, synthesis gas and natural gas and liquid mercury metal and preparation method thereof.
Background technology
At present, discharge mercury in the process because coal burning, vaporizing system synthesis gas and natural gas extraction etc. utilize, wherein, this mercury mainly exists with three kinds of forms, element mercury (Hg 0), oxidation state mercury (Hg 2+) and particle mercury (Hg P).Hg 0Because its fusing point is low, volatility is high and be insoluble in characteristics such as water, be difficult to be caught by cleaner, be discharged in the atmosphere, form is relatively stable, present coal-fired mercury emissions has become maximum artificial mercury pollution emission source, the energy resource consumption of China is based on coal, and controlling coal-fired mercury emissions is the environmental problem that solution is badly in need of in China.Therefore, develop promising mercury control technology and effectively remove mercury, particularly Hg in coal gas, synthesis gas and the natural gas 0It is one of environmental pollution improvement's urgent problem.
And disclosed mercury removal agent in the present prior art, its demercuration performance is undesirable, because the mercury of this kind mercury removal agent holds and demercuration efficient is all less, and a lot of mercury removal agents all needs sulfuration just can work, this makes not only all may exist the secondary pollution problem in preparation of adsorbent also is to use. in addition, the oxidability of currently used monometallic mercury removal agent is low, be difficult to the mercury of metallic state is converted into the mercury of the oxidation state that steam forces down, so press for a kind of high-performance and don't produce many metal actives mercury removal agent of secondary pollution.
Summary of the invention
Based on this, the invention provides a kind of mercury removal agent and preparation method thereof.
The concrete technical scheme that solves the problems of the technologies described above is as follows:
A kind of mercury removal agent, described mercury removal agent comprise the carrier of 40-90wt%, the active component of 1-40wt% and the modifier of 0-30wt%; Described modifier is halogen or halide; Described active component is the mixture of at least two kinds oxidisability metal oxide; Described modifier can have been strengthened the ability of oxidation simple substance mercury by chemical reaction, also with regard to the corresponding amount that has increased oxidized and fixing mercury, is conducive to the raising that demercuration efficient and mercury hold.
Among some embodiment, described halogen is bromine therein, and described halide is soluble bromine salt.
Among some embodiment, described bromine salt is ammonium bromide, KBr or sodium bromide therein.
Among some embodiment, described oxidisability metal oxide is manganese dioxide, cobalt oxide, cerium oxide, iron oxide, tungsten oxide, molybdenum oxide, cupric oxide or nickel oxide therein.
Therein among some embodiment, described carrier is at least a in activated alumina, modified active aluminium oxide, silica, kaolin, diatomite, active carbon, aluminium hydroxide or the molecular sieve; Preferred activated alumina, modified active aluminium oxide or active carbon.
Among some embodiment, the percentage by weight of described modifier is 0-25wt% therein; Preferably, the percentage by weight of modifier is 5-21wt%.
Among some embodiment, the percentage by weight of described active component is 5-35wt% therein; The percentage by weight of described carrier is 50-80wt%; The specific area of described carrier is 20-500m 2/ g, pore volume are 0.1-1.0cm 3/ g; Preferably, the percentage by weight of described active component is 10-35wt%; The percentage by weight of described carrier is 55-75wt%; Described carrier can improve dispersion degree of active components in the mercury removal agent, and with the absorption area that contacts of mercury, and the adsorbance of mercury, thus improved the demercuration efficient of mercury removal agent.
Among some embodiment, the specific area of described carrier is 50-450m therein 2/ g, pore volume are 0.2-0.7cm 3/ g; The mercury that the specific area of described carrier and pore volume more help to improve mercury removal agent holds and demercuration efficient.
The preparation method of above-mentioned mercury removal agent comprises the steps:
(1) carrier is placed a kind of solution of soluble metallic salt, dipping 1-24h gets load salt carrier;
(2) after the load salt carrier drying or roasting with step (1) gained, place one or more the soluble metal salting liquid except the described soluble metallic salt of step (1), dry behind the dipping 1-24h, at aerobic (with active carbon during as carrier, anaerobic) under the condition, in 350-600 ℃ of following calcining 2-10h, get the metal oxide-loaded carrier after the calcining;
(3) the metal oxide-loaded carrier after the calcining of step (2) gained is placed modifier solution, dry behind the dipping 1-24h, in 100-300 ℃ of following roasting 1-6h, get final product again.Sometimes hold in order to increase mercury, can place modifier solution dipping, dry, roasting to above metal oxide-loaded carrier again.
Among some embodiment, described soluble metallic salt is nitrate, sulfate, acylate or the halide salt of oxidisability metal oxide therein; Described oxidisability metal oxide is that soluble oxidized metal salt is prepared from through calcining;
The above acylate comprises: formates, acetate, citrate, oxalates etc.Certainly be not limited to above several salt, the stable acylate that forms solution of various energy and solvent for use is all included.
Among some embodiment, temperature dry described in step (2) and the step (3) is 50-200 ℃ therein, and the time is 1-8h; Preferred temperature is 100-120 ℃.
A kind of mercury removal agent of the present invention and preparation method thereof has the following advantages and beneficial effect:
(1) mercury removal agent of the present invention sulfur-bearing not, as active component, halogen or halide are as modifier with the oxidisability metal oxide for it, and the mercury that the mercury removal agent that makes has greater than 10wt% holds, and demercuration efficient reaches more than 99.9%.
(2) mercury removal agent of the present invention can be widely used in flue gas, synthesis gas and natural gas and the liquid in the mercurous source of the gas in the removing process of mercury metal.
(3) preparation method's preferred aqueous solutions infusion process of the present invention, active component is the metal oxide of oxidation state, preparation process does not need to need to vulcanize just and can work as a lot of existing mercury removal agents, comparatively flexible aspect the carrier selection, as required, can prepare flexibly and be applicable to that different occasions possess the mercury removal agent of different performance.
The specific embodiment
The present invention adopts active constituent loading on carrier, and can select for use modifier to carry out modification in order to realize its removing mercury; Wherein carrier comprises activated alumina, modified active aluminium oxide, kaolin, diatomite, active carbon, aluminium hydroxide, molecular sieve etc., active component is selected manganese dioxide, cobalt oxide, cerium oxide, iron oxide, tungsten oxide, molybdenum oxide for use, the compound of transition metal such as cupric oxide and nickel oxide, modifier is halogen and halide, by oxidation mechanism mercury vapour is converted into mercury oxide.
Halide of the present invention refers to chloride, bromide or iodide;
Described halogen refers to fluorine, chlorine, bromine or iodine;
Described halide salt refers to ammonium chloride, potassium chloride, ammonium bromide, sodium bromide or KBr etc.;
Described molecular sieve refers to the molecular sieve of series such as A series, X series, Y. series, ZSM;
Activated alumina is available from Qingdao connection letter chemical company and Chalco Zibo Aluminium Factory among the following embodiment;
The modified active aluminium oxide is for to use titanium oxide, alkali metal such as potassium or sodium, and alkaline-earth metal such as calcium, magnesium or barium etc. carry out modification to activated alumina, as: the titaniferous activated alumina is available from Qingdao connection letter chemical company.
The present invention will be further described below with reference to specific embodiment.
Embodiment 1
A kind of mercury removal agent comprises the active aluminum oxide carrier of 90wt%, the manganese dioxide of 5wt% and the cobalt oxide active component of 5wt%; The preparation method of this kind mercury removal agent comprises the steps:
(1) choose the 40-60 order, specific surface is 80m 2/ g, pore volume are 0.1cm 3The active aluminum oxide carrier 40g of/g puts into 20ml and contains 7.0gCoCl 26H 2In the solution of O, flooded 1 hour, treat that above-mentioned maceration extract immerses carrier fully after, carrier is taken out;
(2) under 110 ℃ with the carrier drying of step (1) gained 8 hours, remove moisture in the carrier, will have the active aluminum oxide carrier of cobalt chloride to put into through dried load again and contain 5.1gMnCl 24H 2In the solution of O, flooded 24 hours, carrier is taken out, in 120 ℃ of dryings 1 hour, under aerobic conditions, in 400 ℃ of following calcination activations 2 hours, make chlorate decompose, and and then obtain the active aluminum oxide carrier that load has manganese dioxide and cobalt oxide active component, namely obtain mercury removal agent, be designated as A.
Embodiment 2
A kind of mercury removal agent comprises the absorbent charcoal carrier of 56wt%, the cupric oxide of 14wt% and the manganese dioxide active component of 18wt%, the NH of 12wt% 4Cl modifier; The preparation method of this kind mercury removal agent comprises the steps:
(1) get the 40-60 order, specific surface is 400m 2/ g, pore volume are 1.0cm 3The absorbent charcoal carrier 40g of/g puts into 15ml and contains 30.5gCu (NO 3) 23H 2In the solution of O, flooded 12 hours, treat that above-mentioned maceration extract immerses carrier fully after, carrier is taken out;
(2) under 100 ℃ with the carrier drying of step (1) gained 5 hours, remove moisture in the carrier, will have the absorbent charcoal carrier of copper nitrate to put into 12ml through dried load again and contain 29.1gMnCl 24H 2In the solution of O, flooded 12 hours, this carrier taken out, in 120 ℃ of dryings 6 hours, under oxygen free condition, in 450 ℃ of following calcination activations 3 hours, make chlorate decompose, and and then obtain the absorbent charcoal carrier that load has cupric oxide and manganese dioxide active component;
(3) there is the carrier of active component to put into 10ml above-mentioned load and contains 8.7gNH 4In the solution of Cl, flooded 10 hours, carrier is taken out, in 100 ℃ of dryings 3 hours, afterwards under oxygen free condition, in 200 ℃ of following calcination activations 3 hours, namely obtain mercury removal agent, be designated as B.
Embodiment 3
A kind of mercury removal agent comprises the titaniferous active aluminum oxide carrier of 60wt%, the cupric oxide of 22wt% and manganese dioxide active component, the 6wt%NH of 12wt% 4Br modifier; The preparation method of this kind mercury removal agent comprises the steps:
(1) get the 40-60 order, specific surface is 240m 2/ g, pore volume are 0.4cm 3The titaniferous activated alumina 40g of/g puts into 20ml and contains 36.2g (CH 3COO) 2CuH 2In the solution of O, flooded 10 hours, treat that above-mentioned maceration extract immerses carrier fully after, carrier is taken out;
(2) in 110 ℃ times dry 6 hours, remove moisture in the carrier, will have the titaniferous active aluminum oxide carrier of Schweinfurt green to put into 15ml through dried load again and contain 19.1gMnCl 24H 2In the solution of O, flooded 10 hours, carrier is taken out, in 120 ℃ of dryings 6 hours, afterwards under aerobic conditions, in 400 ℃ of following calcination activations 4 hours, make acetate and chlorate decompose, and and then obtain the titaniferous active aluminum oxide carrier that load has cupric oxide and manganese dioxide active component;
(3) there is the carrier of active component to put into 12ml above-mentioned load and contains 3.9gNH 4In the solution of Br, flooded 10 hours, carrier is taken out, in 120 ℃ of dryings 3 hours, afterwards under aerobic conditions, in 250 ℃ of following calcination activations 1 hour, namely obtain mercury removal agent, be designated as C.
Embodiment 4
A kind of mercury removal agent comprises the titaniferous active aluminum oxide carrier of 70wt%, the cupric oxide of 21wt% and the manganese dioxide active component of 9wt%; The preparation method of this kind mercury removal agent comprises the steps:
(1) get the 40-60 order, specific surface is 280m 2/ g, pore volume are 0.6cm 3The titaniferous activated alumina 40g of/g puts into 25ml and contains 26.5gCuCl 22H 2In the solution of O, flooded 12 hours, treat that above-mentioned maceration extract immerses carrier fully after, carrier is taken out;
(2) in 110 ℃ times dry 6 hours, remove moisture in the carrier, will have the titaniferous active aluminum oxide carrier of Schweinfurt green to put into 18ml through dried load more afterwards and contain 12.4gMnCl 24H 2In the solution of O, flooded 10 hours, this carrier is taken out, in 110 ℃ of dryings 5 hours, afterwards under aerobic conditions, in 350 ℃ of following calcination activations 3 hours, make acetate and chlorate decompose, and and then obtain the titaniferous active aluminum oxide carrier that load has cupric oxide and manganese dioxide active component, namely obtain mercury removal agent, be designated as D.
Embodiment 5
A kind of mercury removal agent comprises the active aluminum oxide carrier of 75wt%, the cobalt oxide of 14wt% and the molybdenum oxide active component of 11wt%; The preparation method of this kind mercury removal agent comprises the steps:
(1) get the 40-60 order, specific surface is 200m 2/ g, pore volume are 0.8cm 3The activated alumina 40g of/g puts into 25ml and contains 38.6gCo (NO 3) 2.6H 2In the solution of O, flooded 12 hours, treat that above-mentioned maceration extract immerses carrier fully after, carrier is taken out;
(2) in 100 ℃ times dry 5 hours, remove moisture in the carrier, will have the active aluminum oxide carrier of cobalt nitrate to put into 15ml through dried load more afterwards and contain 7.2g (NH 4) 6Mo 7O 244H 2In the solution of O, flooded 12 hours, this carrier is taken out, in 120 ℃ of dryings 6 hours, afterwards under aerobic conditions, in 400 ℃ of following calcination activations 4 hours, make cobalt nitrate and ammonium molybdate decompose, and and then obtain the active aluminum oxide carrier that load has cobalt oxide and molybdenum oxide active component, namely obtain mercury removal agent, be designated as E.
Embodiment 6
A kind of mercury removal agent comprises the titaniferous active aluminum oxide carrier of 60wt%, molybdenum oxide and the 10wt% manganese dioxide active component of 10wt%, and 20wt%Br 2Modifier; The preparation method of this kind mercury removal agent comprises the steps:
(1) get the 40-60 order, specific surface is 80m 2/ g, pore volume are 0.75cm 3The titaniferous activated alumina 6.5g of/g puts into 25ml and contains (NH 4) 6Mo 7O 244H 2In the solution of O, flooded 24 hours, treat that above-mentioned maceration extract immerses carrier fully after, this carrier is taken out, in 110 ℃ of dryings 6 hours, 400 ℃ of roastings 3 hours in air again obtained the carrier of load molybdenum oxide;
(2) carrier of the above-mentioned load molybdenum oxide that obtains is put into 15ml and contain 12.2gMnCl 24H 2In the solution of O, flooded 12 hours, this carrier is taken out, in 120 ℃ of dry 6h, afterwards under aerobic conditions, in 450 ℃ of following calcination activations 5 hours, make manganese chloride decompose, and and then obtain the titaniferous active aluminum oxide carrier that load has molybdenum oxide and manganese dioxide active component;
(3) there is the carrier of active component to put into 12ml above-mentioned load and contains 13.3gBr 2Solution in, flooded 10 hours, carrier is taken out, in 120 ℃ of dryings 3 hours, afterwards under aerobic conditions, in 250 ℃ of following calcination activations 1 hour, namely obtain mercury removal agent, be designated as F.
Embodiment 7 activity ratings
One, evaluation method
The mercury removal agent that above-described embodiment 1～6 is prepared is particles filled to be in the 1.5ml demercuration clean-up bed of 6mm to internal diameter.Be 8000h at normal temperature, normal pressure, volume space velocity -1Condition under, be 10500 μ g/m to contain hydrogen sulfide 70ppm and mercury concentration 3The methane of (± 2%) is estimated resulting result such as table 1 through this clean-up bed to the demercuration effect of mercury removal agent.
Two, evaluation result
Demercuration effect comparing result before and after table 1 purifies
As known from Table 1, the mercury removal agent demercuration effect that the present invention prepares is very remarkable, and the mercury appearance can reach more than the 10wt%, and the demercuration rate ranges up to 99.999%.Described demercuration rate refers to the percentage of the amount of mercury in the amount of the mercury that removes and the former source of the gas.As seen, use mercury removal agent of the present invention to have higher demercuration activity, namely mercury holds high and demercuration efficient height.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to claim of the present invention.Should be pointed out that for the person of ordinary skill of the art without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.

Claims (10)

1. a mercury removal agent is characterized in that, described mercury removal agent comprises the carrier of 40-90wt%, the active component of 1-40wt% and the modifier of 0-30wt%; Described modifier is halogen or halide; Described active component is the mixture of at least two kinds oxidisability metal oxide.
2. mercury removal agent according to claim 1 is characterized in that, described halogen is bromine, and described halide is soluble bromine salt.
3. mercury removal agent according to claim 2 is characterized in that, described bromine salt is ammonium bromide, KBr or sodium bromide.
4. mercury removal agent according to claim 1 is characterized in that, described oxidisability metal oxide is manganese oxide, cobalt oxide, iron oxide, tungsten oxide, cerium oxide, molybdenum oxide, cupric oxide or nickel oxide; Described carrier is at least a in activated alumina, modified active aluminium oxide, silica, kaolin, diatomite, active carbon, aluminium hydroxide or the molecular sieve.
5. mercury removal agent according to claim 1 is characterized in that, the percentage by weight of described active component is 5-35wt%; The percentage by weight of described carrier is 50-80wt%; The percentage by weight of modifier is 0-25wt%.
6. mercury removal agent according to claim 5 is characterized in that, the specific area of described carrier is 20-500m 2/ g, pore volume are 0.1-1.0cm 3/ g.
7. mercury removal agent according to claim 6 is characterized in that, the specific area of described carrier is 50-450m 2/ g, pore volume are 0.2-0.7cm 3/ g.
8. according to the preparation method of each described mercury removal agent of claim 1-7, it is characterized in that, comprise the steps:
(1) carrier is placed the solution of one or more soluble metallic salts, dipping 1-24h gets load salt carrier;
(2) after the load salt carrier drying or roasting with step (1) gained, place one or more the soluble metal salting liquid except the described soluble metallic salt of step (1), dry behind the dipping 1-24h, in 350-600 ℃ of calcining 2-10h, get the carrier of the load oxidisability metal oxide after the calcining;
(3) carrier with the load oxidisability metal oxide after the calcining of step (2) gained places modifier solution, and is dry behind the dipping 1-24h, in 100-300 ℃ of following roasting 1-6h, gets final product again.
9. the preparation method of mercury removal agent according to claim 8 is characterized in that, described soluble metallic salt is nitrate, sulfate, acylate or the halide salt of oxidisability metal oxide.
10. according to the preparation method of the described mercury removal agent of claim 9, it is characterized in that temperature dry described in step (2) and the step (3) is 50-200 ℃, the time is 1-8h.
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