CN102430383B - Preparation method of adsorbing agent simultaneously removing H2S and Hg in middle temperature coal gas - Google Patents

Preparation method of adsorbing agent simultaneously removing H2S and Hg in middle temperature coal gas Download PDF

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CN102430383B
CN102430383B CN 201110344268 CN201110344268A CN102430383B CN 102430383 B CN102430383 B CN 102430383B CN 201110344268 CN201110344268 CN 201110344268 CN 201110344268 A CN201110344268 A CN 201110344268A CN 102430383 B CN102430383 B CN 102430383B
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CN102430383A (en
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韩丽娜
鲍卫仁
王建成
吕学勇
常丽萍
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Taiyuan University of Technology
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Abstract

The invention relates to an adsorbing agent simultaneously removing H2S and Hg in middle temperature coal gas and a preparation method of the adsorbing agent as well as the application of the adsorbing agent. The adsorbing agent is metallic oxide loading gamma-Al2O3, wherein metallic oxides are Fe, Zn and/or Pd oxides; according to the total percent by weight of the adsorbing agent, the percent by weight of the Fe oxide, i.e. Fe2O3 is 0-50wt%, the percent by weight of the Zn oxide, i.e. ZnO is 0-40wt%, and the percent by weight of the Pd oxide, i.e. PdO is 0-10wt%, wherein the percent by weight of the Fe, Zn and Pd oxides is asynchronously 0, and the total percent by weight of the content of the Fe, Zn and Pd oxides is less than 100wt%, and the balance is a gamma-Al2O3 carrier. The preparation method has the advantages of simple process and easiness in operation and high removal rate of sulfur and mercury; and the prepared adsorbing agent not only can be used for separately or jointly removing H2s and H in the middle temperature coal gas, but also can be used for removing mercury from other gases.

Description

A kind of remove simultaneously in H in the warm coal gas 2The preparation of adsorbent method of S and Hg
Technical field
Warm gas purification field in the present invention relates to is specifically related to a kind of for removing H in the warm coal gas simultaneously 2Adsorbent of S and Hg and its preparation method and application.
Background technology
Coal gasification is most effective, most widely used clean coal technology at present.In raw gas, still there is H 2(wherein 90% noxious pollutant is H to noxious pollutants such as S, HCl, Hg 2S), this not only causes the corrosion of equipment, and easily makes catalyst poisoning, also serious harm environment and health.Reach low emission, oligosaprobic production requirement, raw gas must purify before using.Purposes difference after the coal gasification is to noxious pollutant content requirement difference in the gas composition.The coal gas that is used for gas turbine, H 2The content of S need reach 20～100ppm; H in the synthesis gas of use sulfur resistant catalyst 2S content then need be lower than 10ppm, and H in the general synthesis gas 2The content of S must be lower than 0.05ppm.Although it is the content of mercury is lower, because the toxicity of mercury has accumulation, very big to crowd's health threat.Mercury has hypertoxicity simultaneously, and atmospheric residence time is long, and its harm to environment can not be ignored.
The whole world is discharged into that the total amount of mercury is about 5000t in the atmosphere every year, and wherein 4000t is the artifact, and topmost source is burning row mercury.Be example with the U.S., all kinds of burnings row mercury amounts account for 87%, and wherein the coal-fired mercury emissions proportion in power station maximum reaches 35%, and the mercury pollution that visible fire coal causes is the most serious.The average mercury content of coal in China is about 0.22mg/Kg, and mercury content changes greatly in the coal of different regions.It is estimated that Chinese coal-fired atmosphere mercury emission was between 161～220t in 2000.Existing result of study shows: in the coal gasification course, and simple substance mercury (Hg in the gaseous mercury 0) and divalence mercury (Hg 2+) degree between 40%～60%, change.Along with the rising of temperature and the prolongation of the time of staying, mercuric percentage composition raises in the gas, and the percentage composition of simple substance mercury reduces.Because mercuric compound has very high water-soluble, removes relatively easily.And simple substance mercury is because its volatility height, and is insoluble in water, becomes the difficult point of gas purification.Because gasification back gas composition is reducing atmosphere, so Hg in the gas phase 0Account for the height in the ratio flue gas (oxidizing atmosphere) of total mercury; Combustion process has been owing to introduced a large amount of oxygen or air, so the concentration height of mercury in the concentration ratio flue gas of mercury in the coal gas.So may obtain better cost and environmental effect at removing of mercury in the coal gas.
Usually adopt the adsorbent that removes mercury mainly to comprise: acticarbon, flying dust, mineral substance adsorbent, charcoal base adsorbent, polymer chitosan adsorbent, modified activated carbon absorbent, metal oxide, metal sulfide etc.
Research is at present concentrated and the most ripe Hg the most 0The emission control mode mainly is to spray into active carbon in flue gas, but operating cost is very high, if will reach 90% mercury removal efficient, handling one pound of mercury needs 25000～70000 dollars.But because time of contact is short, adsorption efficiency is low, consumption is big etc. problem, cost is very high.Activated carbon dosage is big, is difficult to recycling.The method removal of mercury mechanism mainly is with physical absorption.In order to improve the utilization rate of active carbon, the active carbon of modification can better be used for removing mercury.Activated carbon modified main method change number of functional groups and the character of activated carbon surface, increase the quantity of oxygen-containing functional group and nitrogen-containing functional group or increase the surface-active position, the material of strengthening chemisorption or having certain metallic character at its area load by load.All be in order to strengthen the demercuration performance to its final purpose of carrying out modification, improve demercuration efficient.But acticarbon can not be kept a mercury removal efficient preferably under higher temperature.
The flying dust demercuration is because the mercury of flying dust in can enriched flue gas, forms particle mercury and is caught by cleaner and realize the demercuration purpose; Existing physical absorption also has chemisorbed.Its surperficial oxygen-containing functional group C=O is conducive to oxidation and the chemisorbed of mercury.The charcoal base adsorbent utilizes exactly with the Hg oxidation and then with it and removes.The absorption property of flying dust in common flue gas is than strong in the coal gas gasification.At present, the adsorption efficiency of flying dust is lower, wants to satisfy final demercuration requirement, also will be to the flying dust modification, to improve its adsorption efficiency.
Except the adsorbent of charcoal base, mineral substance adsorbent, polymer chitosan adsorbent reach the adsorbent after its modification also are used for the coal gas demercuration.After the modification, the sulfuric acid of interpolation and shitosan and iodine generation chemical reaction have obtained containing sulfonate radical (SO 3 2-) and the adsorbent of I active sites.Sulfuric acid content increases, and can improve its demercuration efficient significantly, but the addition of sulfuric acid is not The more the better.Along with the increase of temperature, iodine modified alta-mud and shitosan class adsorbent demercuration effect all improve a lot, and greater than 150 ℃, the removal efficiency of mercury descends rapidly in temperature.
People such as Wu [Wu, S.; Azharuddin, M.; Sasaoka, E., Characteristics of the removal of mercury vapor in coal derived fuel gas over iron oxide sorbents.Fuel 2006,85 (2), 213-218.] be application Fe 2O 3Remove the research of Hg in the coal gas, Fe 2O 3Be a kind of thick desulfurizing agent, have characteristics cheap and easy to get, that Sulfur capacity is big.Fe 2O 3Remove H 2S forms iron sulfide, forms and can reach removing of Hg with the elemental sulfur of Hg reaction at iron sulfide.But metal iron oxide can not be kept a mercury removal efficient preferably as the adsorbent that removes mercury under higher temperature.Precious metal element Pd, Pt, Au, Ir have the potentiality that remove mercury vapour in the coal gas of high temperature, Hg mainly is dissolved in the precious metal surface adsorbent with solid-state form in the metal surface only can obtain regeneration by improving temperature, thereby the mercury of catching can obtain to recycle non-secondary pollution.
Chinese patent application CN101724473A has announced the method for catalytic oxidative desulfurization heavy metal Hg in a kind of heating gas, in coal gas atmosphere, introduce minor amounts of oxygen, with active carbon as adsorbent, adopt the method for catalytic oxidation, promote simple substance mercury and hydrogen sulfide reaction in the coal gas, be converted into mercuric sulphide (Hg+H 2S+O 2→ 2HgS+2H 2O), realize removing and harmless treatment of mercury in the coal gas.Said method has been introduced oxygen in heating gas, bring difficulty for next step application of coal gas, has improved production cost, and has had certain safety problem on the technology, and its application is restricted.
Summary of the invention
In order to overcome the defective that exists in the prior art, the object of the present invention is to provide in a kind of can the removing simultaneously H in the warm coal gas 2The adsorbent of S and Hg.
Adsorbent provided by the present invention is metal oxide-loaded γ-Al 2O 3, metal oxide evenly distributes on its surface.Described metal oxide is the oxide of Fe, Zn and/or Pd, and in the total amount of adsorbent, the oxide of described Fe is with Fe 2O 3Meter, its quality percentage composition is 0～50wt%, is preferably 1～30wt%; The oxide of Zn is in ZnO, and its quality percentage composition is 0～40wt%, is preferably 1～30wt%; The oxide of Pd is in PdO, and its quality percentage composition is 0～10wt%, is preferably 0.1～5wt%, and wherein the oxide content of Fe, Zn and Pd is not 0 simultaneously, and the summation＜100wt% of the oxide content of Fe, Zn and Pd, and surplus is γ-Al 2O 3Carrier.
The present invention also provide a kind of remove simultaneously in H in the warm coal gas 2The preparation of adsorbent method of S and Hg, its step comprises:
A. with γ-Al 2O 3Carrier granular carries out dry preliminary treatment, places drier standby;
B. according to the load capacity of each metal oxide component in adsorbent, the soluble metallic salt of Fe, Zn and/or Pd is configured to certain density precursor solution;
C. the precursor solution of above-mentioned configuration evenly is added drop-wise to the described pretreated γ-Al of step a is housed 2O 3In the container of carrier granular, saturated to carrier suction till, place the ventilation to dry, place baking oven to dry then, place Muffle furnace again, be warming up to 400 ℃-600 ℃, and stop heating after being incubated 1.5～3h, make adsorbent.
Described γ-Al 2O 3The granularity of carrier granular is 1-5mm.
Described γ-Al 2O 3The dry preliminary treatment of carrier granular is to dry 3h down at 120 ℃.
The soluble metallic salt of described Fe, Zn and/or Pd is nitrate, sulfate, chloride or the oxalates of Fe, Zn and/or Pd, and the soluble metallic salt of wherein said Fe is preferably Fe (NO 3) 39H 2O, the soluble metallic salt of Zn is preferably Zn (NO 3) 26H 2O, the soluble metallic salt of Pd is preferably Pd (NO 3) 32H 2O.
Oven dry among the step c is to dry 12h down at 100 ℃.
But the dip operation among the repeating step c is 2～3 times as required.
The present invention also provides described adsorbent to be used for removing simultaneously H in the warm coal gas 2The application of S and Hg.
The representative condition of described application gas purification is: coal gas is formed 0.01-0.3vol%H 2S, 30-80 μ g/m 3Hg, 5～35vol%H 2, 5～30vol%CO, 5～10vol%CO 2, 1～15vol%H 2O, balance gas N 2Reaction temperature is 100～350 ℃.The reaction volume air speed is 1000～10000h -1
Among the above-mentioned preparation method, Fe, Zn, Pd salt among the step b can select a kind of also optional 2～3 kinds.
Among the above-mentioned preparation method, precursor solution Fe (NO among the step b 3) 39H 2O, Zn (NO 3) 26H 2The concentration of O is respectively 0.1～1g/ml, Pd (NO 3) 32H 2The concentration of O is 0.05～0.3g/ml.
Among the above-mentioned preparation method, the temperature of Muffle furnace rises to 500 ℃ among the step c, and stops heating behind the insulation 2h.
Compared to existing technology, the present invention has advantage as described below: (1) is of the present invention remove simultaneously in H in the warm coal gas 2The adsorbent of S and Hg can keep good desulfuration demercuration ability in higher temperature.(2) according to the inventive method, the H in the coal gas 2S is 100% remove almost, and the best removal efficiency of mercury can reach more than 60.0%.(3) the present invention adopts metal oxide-loaded γ-Al 2O 3As adsorbent, promote that the simple substance mercury in the coal gas is converted into mercuric sulphide, mercury efficiently removes and harmless treatment in the realization coal gas.(4) with the H in the middle temperature coal gas 2S and Hg remove simultaneously, can play synergy, have also reduced removing cost, simplify technology.
Description of drawings
Fig. 1 is the made adsorbent 1wt%PdO3wt%Fe of embodiment 3 2O 3/ γ-Al 2O 3Demercuration performance evaluation result.Coal gas is formed: 0.10vol%H 2S, 35 μ g/m 3Hg, 20vol%H 2, 30vol%CO, 15vol%CO 2, balance gas is N 2, the reaction volume air speed is 2000h -1
Fig. 2 is adsorbent 4wt%PdO15wt%ZnO/ γ-Al that embodiment 5 makes 2O 3The demercuration evaluation result.Coal gas is formed: 0.30vol%H 2S, 80 μ g/m 3Hg, 35vol%H 2, 30vol%CO, 10vol%CO 2, 15vol%H 2O, balance gas are N 2, the reaction volume air speed is 7000h -1
The specific embodiment
Provided by the invention for removing coal gas H 2The preparation of adsorbent method of S and Hg, its specific embodiment are to get 10g γ-Al 2O 3Carrier carries out titration with the buret that is added with distilled water in crucible, saturated to the carrier suction till, being measured as saturated water adsorptive value is 13.00ml.Measure a certain amount of Pd (NO 3) 22H 2O, Fe (NO 3) 39H 2O and/or Zn (NO 3) 26H 2O stirs with distilled water diluting.Join uniformly γ-Al is housed 2O 3In the crucible of carrier.Dry oven dry, roasting.Obtain adsorbent.
Of the present invention for removing coal gas H 2The activity rating of the adsorbent of S and Hg is to carry out in tube furnace fixed bed evaluating apparatus.This device is made up of gas circuit and flow control system thereof, generation systems, tube furnace fixed-bed quartz reactor and the temperature-controlling system thereof of Hg, detection system five parts.With bottled gas simulation coal gas, by the flow of flowmeter control gas.Each sorbent used quality is 1.0～5.0g, and reacting gas consists of: 0.01-0.3vol%H 2S, 30-80 μ g/m 3Hg, 5～35vol%H 2, 5～30vol%CO, 5～10vol%CO 2, 1～15vol%H 2O, balance gas N 2Reaction temperature is 100～350 ℃.The reaction volume air speed is 1000～10000h -1Hg concentration detects with the coal-fired flue-gas mercury vapourmeter in the gas before and after the reaction.H 2S gas is measured with gas chromatograph GC950.
Describe in further detail with specific embodiment below and of the present inventionly a kind ofly remove H simultaneously for coal gas 2S and Hg preparation of adsorbent method and activity rating result.
Embodiment 1
A: carrier preliminary treatment
At first with the Al of certain particle diameter 2O 3Carrier is dried 3h down at 120 ℃, places drier standby.
B: the preparation of precursor solution
Fe (the NO of preparation 0.4g/ml 3) 39H 2O solution.
C: preparation adsorbent
Take by weighing the pretreated γ-Al of 10g 2O 3Carrier is measured 1.90ml Fe (NO in crucible 3) 39H 2O stirs with the distilled water diluting of 11.10ml.Evenly join γ-Al is housed 2O 3In the crucible of carrier.Dry 10h, dry 12h down at 100 ℃, at 500 ℃ of following roasting 2h, make adsorbent 3wt%Fe 2O 3/ γ-Al 2O 3
With the adsorbent 3wt%Fe that makes 2O 3/ γ-Al 2O 3Place fixed bed reactors, reacting gas is formed: 0.03vol%H 2S, 60 μ g/m 3Hg, 5vol%H 2, 5vol%CO, 5vol%CO 2, balance gas N 2, the reaction volume air speed is 5000h -1, carry out activity rating at 100 ℃, 150 ℃, 200 ℃ respectively.When reaction temperature was 100 ℃, the demercuration rate was 80% during 390min, and it is 4.50mg/g that mercury holds, and desulfurization degree is 85%, and Sulfur capacity is 17.78mg/g.When reaction temperature was 300 ℃, desulfurization degree was 99.90% when the mercury appearance was almost 0,400min during 60min, and Sulfur capacity is 19.44mg/g.
Embodiment 2
A: carrier preliminary treatment
With embodiment 1.
B: the preparation of precursor solution
Pd (the NO of preparation 0.1g/ml 3) 32H 2O solution.
C: preparation adsorbent
Take by weighing the pretreated γ-Al of 10g 2O 3Carrier is measured 2.00mlPd (NO in crucible 3) 22H 2O stirs with the 11.00ml distilled water diluting.Evenly join γ-Al is housed 2O 3In the crucible of carrier.Dry 10h, dry 12h down at 100 ℃, at 500 ℃ of following roasting 2h.Make adsorbent 1wt%PdO/ γ-Al 2O 3With the adsorbent 1wt%PdO/ γ-Al that makes 2O 3Place fixed bed reactors, reacting gas is formed: 0.07vol%H 2S, 80 μ g/m 3Hg, 10vol%H 2, 20vol%CO, 5vol%CO 2, balance gas N 2, the reaction volume air speed is 5000h -1, carried out activity rating at 100 ℃, 200 ℃, 300 ℃ respectively.When reaction temperature was 300 ℃, the demercuration rate was 50% when the reaction time was 400min, and it is 2.78mg/g that mercury holds; Desulfurization degree is 69%, and Sulfur capacity is 30.68mg/g.
Embodiment 3
A: carrier preliminary treatment
With embodiment 1
B: the preparation of precursor solution
Prepare the Fe (NO of 0.4g/ml respectively 3) 39H 2Pd (the NO of O solution and 0.1g/ml 3) 32H 2O solution.
C: preparation adsorbent
Take by weighing the pretreated γ-Al of 10g 2O 3Carrier is measured 1.90ml Fe (NO in crucible 3) 39H 2O stirs with the distilled water diluting of 11.10ml.Evenly join γ-Al is housed 2O 3In the crucible of carrier.Dry 10h, dry 12h down at 100 ℃, at 500 ℃ of following roasting 2h.Make 3wt%Fe 2O 3/ γ-Al 2O 3Adsorbent.Measure 2.00ml Pd (NO again 3) 22H 2O stirs with the 11.00ml distilled water diluting.Join uniformly the above-mentioned 3wt%Fe that makes is housed 2O 3/ γ-Al 2O 3In the adsorbent, dry 10h, dry 12h down at 100 ℃, at 500 ℃ of following roasting 2h.Make adsorbent 1wt%PdO3wt%Fe 2O 3/ γ-Al 2O 3The above-mentioned adsorbent that makes is placed fixed bed reactors, and reacting gas is formed: 0.10vol%H 2S, 35 μ g/m 3Hg, 20vol%H 2, 30vol%CO, 15vol%CO 2, balance gas N 2, the reaction volume air speed is 2000h -1, carried out activity rating at 100 ℃, 200 ℃, 300 ℃ respectively, as shown in Figure 1.When reaction temperature was 300 ℃, the demercuration rate was 50% when the reaction time was 390min, and it is 3.49mg/g that mercury holds; Desulfurization degree is 90.80%, and Sulfur capacity is 44.4mg/g.
Embodiment 4
A: carrier preliminary treatment
With embodiment 1
B: the preparation of precursor solution
Prepare the Fe (NO of 0.8g/ml respectively 3) 39H 2Pd (the NO of O solution and 0.1g/ml 3) 32H 2O solution.
Take by weighing the pretreated γ-Al of 10g 2O 3Carrier is measured 12.70ml Fe (NO in crucible 3) 39H 2O joins uniformly γ-Al is housed 2O 3In the crucible of carrier.Dry 10h, dry 12h down at 100 ℃, at 500 ℃ of following roasting 2h.Make 20wt%Fe 2O 3/ γ-Al 2O 3Adsorbent.Measure 6.00ml Pd (NO again 3) 22H 2O stirs with the 7.00ml distilled water diluting.Join uniformly the above-mentioned 20wt%Fe that makes is housed 2O 3/ γ-Al 2O 3In the adsorbent, dry 10h, dry 12h down at 100 ℃, at 500 ℃ of following roasting 2h.Make adsorbent 3wt%PdO20wt%Fe 2O 3/ γ-Al 2O 3The above-mentioned adsorbent that makes is placed fixed bed reactors, form at reacting gas: 0.20vol%H 2S, 80 μ g/m 3Hg, 20vol%H 2, 30vol%CO, 15vol%CO 2, balance gas N 2, the reaction volume air speed is 3000h -1, carried out activity rating at 100 ℃, 200 ℃, 300 ℃ respectively.When reaction temperature was 300 ℃, the demercuration rate was 65% when the reaction time was 400min, and it is 5.49mg/g that mercury holds; Desulfurization degree is 90.90%, and Sulfur capacity is 64.44mg/g.
Embodiment 5
A: carrier preliminary treatment
With embodiment 1
B: the preparation of precursor solution
Prepare the Zn (NO of 0.8g/ml respectively 3) 36H 2Pd (the NO of O solution and 0.1g/ml 3) 32H 2O solution.
Take by weighing the pretreated γ-Al of 10g 2O 3Carrier is measured 6.87ml Zn (NO in crucible 3) 39H 2O stirs with the distilled water diluting of 5.87ml.Join uniformly γ-Al is housed 2O 3In the crucible of carrier.Dry 10h, dry 12h down at 100 ℃, at 500 ℃ of following roasting 2h.Make single load 15wt%ZnO/ γ-Al 2O 3Adsorbent.Measure 8.0ml Pd (NO 3) 22H 2O stirs with the 5.0ml distilled water diluting.Join uniformly the above-mentioned 15wt%ZnO/ γ-Al that makes is housed 2O 3In the adsorbent, dry 10h, dry 12h down at 100 ℃, at 500 ℃ of following roasting 2h.Make 4wt%PdO15wt%ZnO/ γ-Al 2O 3Compound adsorbent.The above-mentioned adsorbent that makes is placed in the fixed bed reactors, and reacting gas consists of: 0.30vol%H 2S, 80 μ g/m 3Hg, 35vol%H 2, 30vol%CO, 10vol%CO 2, 15vol%H 2O, balance gas N 2The reaction volume air speed is 7000h -1, carried out activity rating at 100 ℃, 200 ℃, 300 ℃ respectively, as shown in Figure 2.When reaction temperature was 300 ℃, the demercuration rate was 56% when the reaction time was 380min, and it is 3.5mg/g that mercury holds; Desulfurization degree is 80.92%, Sulfur capacity 34.85mg/g.
Embodiment 6
A: carrier preliminary treatment
With embodiment 1
B: the preparation of precursor solution
Prepare the Pd (NO of 0.1g/ml respectively 3) 32H 2O solution, the Fe (NO of 0.8g/ml 3) 39H 2Zn (the NO of O solution and 0.8g/ml 3) 36H 2O.
Take by weighing the pretreated γ-Al of 10g 2O 3Carrier is measured 9.53ml Fe (NO in crucible 3) 39H 2O stirs with the 3.47ml distilled water diluting.Join uniformly γ-Al is housed 2O 3In the crucible of carrier.Dry 10h, dry 12h down at 100 ℃, at 500 ℃ of following roasting 2h.Make single load 10wt%Fe 2O 3/ γ-Al 2O 3Adsorbent.Measure 2.29mlZn (NO again 3) 36H 2O stirs with the 10.71ml distilled water diluting.Join uniformly the above-mentioned 10wt%Fe that makes is housed 2O 3/ γ-Al 2O 3In the adsorbent, dry 10h, dry 12h down at 100 ℃, at 500 ℃ of following roasting 2h.Make 10wt%Fe 2O 35wt%ZnO/ γ-Al 2O 3Compound adsorbent.Measure 6.00ml Pd (NO again 3) 32H 2O stirs with the distilled water diluting of 7.00ml.Join uniformly 10wt%Fe is housed 2O 35wt%ZnO/ γ-Al 2O 3In the crucible of compound adsorbent, dry 10h, dry 12h down at 100 ℃, at 500 ℃ of following roasting 2h.Make 3wt%PdO10wt%Fe 2O 35wt%ZnO/ γ-Al 2O 3Three metal composite adsorbents.The above-mentioned three metal composite adsorbents that make are placed in the fixed bed reactors, and reacting gas consists of: 0.20vol%H 2S, 80 μ g/m 3Hg, 35vol%H 2, 30vol%CO, 10vol%CO 2, 15vol%H 2O, balance gas N 2The reaction volume air speed is 9000h -1, carried out activity rating at 200 ℃ and 300 ℃ respectively.The demercuration rate was respectively 65.65% and 55.68% when 200 ℃ and 300 ℃ of reaction time were 400min, and mercury holds and is respectively 5.13mg/g and 4.96mg/g.Desulfurization degree is respectively 89.97% and 95.99%.Sulfur capacity is respectively 44.86mg/g and 49.89mg/g.

Claims (9)

  1. One kind remove simultaneously in H in the warm coal gas 2The adsorbent of S and Hg is characterized in that described adsorbent is metal oxide-loaded γ-Al 2O 3, described metal oxide is the oxide of Fe, Zn and Pd, in the total amount of adsorbent, the oxide of described Fe is with Fe 2O 3The quality percentage composition of meter is 1～30wt%, and the oxide of Zn is 1～30wt% in the quality percentage composition of ZnO, and the oxide of Pd is 0.1～5wt% in the quality percentage composition of PdO, and surplus is γ-Al 2O 3Carrier, described metal oxide is at carrier γ-Al 2O 3The surface evenly distributes.
  2. According to claim 1 remove simultaneously in H in the warm coal gas 2The adsorbent of S and Hg is characterized in that described γ-Al 2O 3The granularity of carrier is 1-5mm.
  3. A claim 1 or 2 described remove simultaneously in H in the warm coal gas 2The preparation of adsorbent method of S and Hg may further comprise the steps:
    A. with γ-Al 2O 3Carrier granular carries out dry preliminary treatment, inserts in the drier standby;
    B. according to the load capacity of each metal oxide component in adsorbent, the soluble metallic salt of Fe, Zn and Pd is configured to certain density precursor solution;
    C. the precursor solution of above-mentioned configuration evenly is added drop-wise to the described pretreated γ-Al of step a is housed 2O 3In the container of carrier granular, saturated to carrier suction till, place the ventilation to dry, place baking oven to dry then, place Muffle furnace again, be warming up to 400 ℃-600 ℃, and stop heating after being incubated 1.5～3h, make adsorbent.
  4. 4. preparation method according to claim 3, the soluble metallic salt that it is characterized in that described Fe, Zn and Pd is nitrate, sulfate, chloride or the oxalates of Fe, Zn and Pd.
  5. 5. preparation method according to claim 3, the soluble metallic salt that it is characterized in that described Fe is Fe (NO 3) 39H 2O, the soluble metallic salt of Zn are Zn (NO 3) 26H 2O, the soluble metallic salt of Pd are Pd (NO 3) 32H 2O.
  6. 6. preparation method according to claim 3 is characterized in that precursor solution Fe (NO 3) 39H 2O or Zn (NO 3) 26H 2The concentration of O is 0.1～1g/ml, precursor solution Pd (NO 3) 32H 2The concentration of O is 0.05～0.3g/ml.
  7. 7. preparation method according to claim 3 is characterized in that dip operation 2-3 time among the repeating step c.
  8. 8. the application of the adsorbent of each described preparation method's preparation of claim 1 or 2 described adsorbents or claim 3-7 is used for removing simultaneously the H in the warm coal gas 2S and Hg.
  9. 9. the described application of claim 8, the representative condition of gas purification is: reaction gas consists of 0.01-0.3vol%H 2S, 30-80 μ g/m 3Hg, 5～35vol%H 2, 5～30vol%CO, 5～10vol%CO 2, 1～15vol%H 2O, balance gas N 2Reaction temperature is 100～350 ℃, and the reaction volume air speed is 1000～10000h -1
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CN104338435B (en) * 2014-07-01 2017-03-22 太原理工大学 Method for removing mercury in flue gas by use of waste desulfurizer after being used for recycling elemental sulfur
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