CN105289665B - Pd‑CuCl2/γ‑Al2O3The preparation method and applications of demercuration composite catalyst - Google Patents
Pd‑CuCl2/γ‑Al2O3The preparation method and applications of demercuration composite catalyst Download PDFInfo
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Abstract
The invention discloses a kind of Pd CuCl2/γ‑Al2O3The preparation method and applications of demercuration composite catalyst, the preparation method of composite catalyst is：Dichloride's palladium and copper chloride are supported on γ Al by infusion process2O3After on carrier, high-temperature activation is produced；This method process is simple and environmentally-friendly, and obtained composite catalyst can be applied to the catalysis oxidation of Elemental Mercury, (can contain SO under the conditions of realizing high-sulfur in the range of 100~200 DEG C2>=2000ppm) nonvalent mercury Efficient Conversion, conversion ratio is up to 90%.Composite catalyst tolerance sulfur dioxide performance is good, is difficult poisoning.
Description
Technical field
The present invention relates to a kind of Pd-CuCl2/γ-Al2O3The preparation method of demercuration composite catalyst, and composite catalyst
Application in catalysis oxidation Elemental Mercury generates bivalent mercury technique, belongs to mercury pollution emission control field.
Background technology
Mercury In The Air has the characteristics of persistence, bioaccumulation, neuron excitotoxicity effect and long range are transmitted because of it, at present
Extensive concern is caused.Based on the harm of air mercury pollution, Mercury In The Air contamination control is just included early in 1990s
International agreement.From 2002, the United Nations's Intergovernmental Conference " global environment minister forum " every two years once is just by global mercury
Pollution problem is used as the main themes.However, though China is non-ferrous metal metallurgy big country, related mercury pollution study on prevention phase
To delayed, most of smelting enterprises do not carry out flue gas mercury removal.Because mercury is global contaminant, with 2010《The whole world
Mercury vacancy pact》Proposition and progressively set up, China's non-ferrous metal metallurgy to air arrange mercury the problem of caused the world
Dispute, also makes the Chinese government increasingly pay close attention to the pollution problem of mercury.2011,《Heavy metal pollution integrated control " 12 " is advised
Draw》In explicitly point out, mercury is included in emphasis prevention and control object, starts China's mercury pollution source discharge investigation, and by non-ferrous metal smelting
Refining is classified as emphasis prevention and control industry.
In mercury fume, the removal difficulty of the mercury of three kinds of different shapes is different：For converting and being formed is adsorbed by flue dust in part
Grain state mercury Hg(p)With part gaseous active mercury Hg2+Property relatively stablize, can by dust collection device (such as cyclone dust collection, bag collection and
Electricity gathers dust) trapped；Fail the fine smoke and Hg trapped by link of being gathered dust2+It is soluble in water, it is washed in wet dedusting
Journey can enter waste acid and be removed；Fraction Hg2+With the Hg for being insoluble in water0With of a relatively high inertia, it is difficult to be captured and
It is discharged into air.Non-ferrous metal metallurgy has turned into China after another main artificial mercury emissions source behind coal-burning power plant, mercury mainly with
Gaseous elemental form is discharged, it is difficult to removed by existing smoke eliminator, and in most of flue gas during smelting (such as zinc abstraction)
Sulfur dioxide concentration is high, and this also increases the difficulty of the removing of Elemental Mercury.It can be seen that, the difficulty or ease journey that mercury pollution is controlled in flue gas during smelting
Degree, mainly depends on the fractions distribution of mercury, therefore, and the conversion ratio for improving Elemental Mercury to other form mercury is the main side studied at present
To the cardinal principle of exploitation smoke mercury emission control technology is to utilize the synchronous demercuration of existing flue gas polution control device, therefore
Its core is the catalysis oxidation of Elemental Mercury, i.e., aoxidize Hg using catalyst after fume dust remover0, improve Elemental Mercury
The speed of oxidation, aoxidizes the bivalent mercury formed, it is removed in flue washing device or desulfurizer.
At present, domestic relevant flue gas during smelting demercuration catalyst patent is less, because metallurgical sulphur dioxide concentration is very
Height, is easily caused catalyst poisoning and loses activity.Therefore, a kind of environmentally friendly, efficient, cheap, anti-sulfur dioxide of exploitation is high answers
Alloy metal catalyst is extremely urgent.
The content of the invention
It is difficult to for demercuration catalyst in the prior art due to sulfur resistance difference suitable for flue gas during smelting hydrargyrum-removing technology
Problem, it is an object of the invention to provide a kind of demercuration performance is good, non-secondary pollution, is resistant to answering for high sulfur dioxide concentration environment
The preparation method of catalyst is closed, this method is simple to operate, environmental protection, meets demand of industrial production.
It is a further object to provide application of the composite catalyst in oxidizing simple substance mercury, particularly in smelting
Refine the application in flue gas demercuration technique, with demercuration efficiency at low temperature is high, anti-sulfur dioxide poisoning the characteristics of.
In order to realize the technical purpose of the present invention, the invention provides a kind of Pd-CuCl2/γ-Al2O3Demercuration composite catalyzing
The preparation method of agent, this method is that by infusion process dichloride's palladium and copper chloride are supported on into γ-Al2O3After on carrier, it is placed in
Activated in 200~400 DEG C of temperature environments, produce Pd-CuCl2/γ-Al2O3Demercuration composite catalyst.
The Pd-CuCl of the present invention2/γ-Al2O3The preparation method of demercuration composite catalyst also includes following preferred scheme：
It is preferred that scheme in, the mol ratio of dichloride's palladium and copper chloride is (0.01~0.2):1.
It is preferred that scheme in, Pd-CuCl2/γ-Al2O3In demercuration composite catalyst the gross mass of palladium and copper chloride be γ-
Al2O3The 2%~20% of carrier quality.
It is preferred that scheme in, described activation is progressively heating treatment process, i.e., successively in 200~230 DEG C of insulations 0.5
~1.5h, 0.5~1.5h is incubated at 280~320 DEG C, and 3~5h is incubated at 370~400 DEG C.Most preferred progressively heating treatment
Journey is to be incubated 1h at 200 DEG C, and 1h is incubated at 300 DEG C, and 4h is incubated at 400 DEG C.
It is preferred that scheme in, comprise the following steps：(1) dichloride's palladium solution is first impregnated into γ-Al2O3On, at ultrasound
After reason, dry, obtain sample A；(2) copper chloride solution is impregnated on sample A again, it is ultrasonically treated, dry, obtain sample B；
(3) sample B is placed under air atmosphere, successively 200~230 DEG C be incubated 0.5~1.5h, 280~320 DEG C be incubated 0.5~
1.5h, 3~5h is incubated at 370~400 DEG C；Produce.
Present invention also offers Pd-CuCl2/γ-Al2O3The application of demercuration composite catalyst, composite catalyst is applied to
Catalysis oxidation Elemental Mercury.
It is preferred that application process in, the catalysis oxidation applied to Elemental Mercury during flue gas during smelting hydrargyrum-removing technology.
The Pd-CuCl of the present invention2/γ-Al2O3Demercuration composite catalyst can be not only used for removing the Hg in coal-fired flue-gas0,
It can be applied under the conditions of removing high-sulfur (contain SO2>=2000ppm) Hg in flue gas during smelting0.The present invention passes through a large amount of simulated flue gas
(air, HCl, SO2And Hg0) under atmosphere to composite catalyst catalysis oxidation Elemental Mercury Hg0Catalysis oxidation ability, summing up can
The mechanism that can exist is as follows：
CuCl2+Hg0→HgCl2+Cu2Cl2 (1)
CuCl2+0.5O2→CuO·CuCl2 (2)
PdCl2+Cu2Cl2→Pd0+CuCl2 (3)
Pd0+2HCl+0.5O2→PdCl2+H2O (4)
CuO·CuCl2+2HCl→2CuCl2+H2O (5)
Compared with the prior art, the advantageous effects that the present patent application technical scheme is brought：
1st, the preparation technology of catalyst is simple, environmental protection, meets demand of industrial production；
2nd, the high catalytic efficiency (Elemental Mercury conversion ratio more than 90%) of catalyst, adaptable, at low temperature (100~
200 DEG C of scopes) it can also keep catalysis oxidation high efficiency；
3rd, catalyst has excellent resistance to SO_2, containing the higher (SO of sulfur dioxide2>=2000ppm) flue gas during smelting in,
Also can efficiently catalyzing and oxidizing Hg0。
Embodiment
Technical scheme is further elaborated below by way of specific embodiment, rather than limits right of the present invention
It is required that protection domain.
Comparative example 1
Take 0.6696g copper chlorides CuCl2·2H2Copper chloride impregnating solution is made in O, the deionized water for being dissolved in 25mL；Utilize
A diameter of 1.5~2mm γ-Al2O3Bead, using equi-volume impregnating, weighs 2g γ-Al as catalyst carrier2O3Leaching
Enter above-mentioned copper chloride solution 2.3mL；Ultrasound 10min is impregnated, air-dries and dries 2h after 6h under the conditions of 60 DEG C, obtain catalyst
CuCl2(3.1%)/γ-Al2O3(leaching).
Comparative example 2
Take 0.6696g copper chlorides CuCl2·2H2Copper chloride impregnating solution is made in O, the deionized water for being dissolved in 25mL；Utilize
A diameter of 1.5~2mm γ-Al2O3Bead, using equi-volume impregnating, weighs 2g γ-Al as catalyst carrier2O3Leaching
Enter above-mentioned copper chloride solution 2.3mL；Ultrasound 10min is impregnated, air-dries and dries 2h after 6h under the conditions of 60 DEG C, then catalyst is existed
In 200~400 DEG C of temperature programming activation process 6 hours (200 DEG C of 1h, 300 DEG C of 1h, 400 DEG C of 4h) in air atmosphere, that is, obtain
Catalyst CuCl2(3.1%)/γ-Al2O3(roasting).
Comparative example 3
Take 0.0957g dichloride palladium Pd (NH3)4Cl2, dipping solution is made in the deionized water that 25mL is dissolved in respectively；Profit
With a diameter of 1.5~2mm γ-Al2O3Bead, using equi-volume impregnating, weighs 2g γ-Al as catalyst carrier2O3
The above-mentioned 3mL of dipping solution containing palladium of immersion；Ultrasound 10min is impregnated, the drying 2h under the conditions of 60 DEG C is air-dried after 6h, then by catalyst
In 200~400 DEG C of temperature programming activation process 6 hours (200 DEG C of 1h, 300 DEG C of 1h, 400 DEG C of 4h) in air atmosphere, produce
To catalyst Pd (0.4%)/γ-Al2O3(roasting).
Embodiment 1
Take 0.6696g copper chlorides CuCl2·2H2O and 0.0957g dichloride palladium Pd (NH3)4Cl2, it is dissolved in 25mL's respectively
Dipping solution is made in deionized water；Utilize a diameter of 1.5~2mm γ-Al2O3Bead as catalyst carrier, using etc. body
Product infusion process, weighs 2g γ-Al2O3The above-mentioned 3mL of dipping solution containing palladium of immersion；Ultrasound 10min is impregnated, is air-dried after 6h at 60 DEG C
Under the conditions of dry 2h；Take above-mentioned copper chloride solution 2.3mL to be impregnated into above-mentioned catalyst again, impregnate ultrasound 10min, air-dry
2h is dried after 6h under the conditions of 60 DEG C, obtained catalyst is in air atmosphere in 200~400 DEG C of activation process 6 of temperature programming
Hour (200 DEG C of 1h, 300 DEG C of 1h, 400 DEG C of 4h), that is, obtain catalyst Pd (0.4%)-CuCl2(3.1%)/γ-Al2O3
(roasting).
Embodiment 2
Take 2.1739g copper chlorides CuCl2·2H2O and 0.3107g dichloride palladium Pd (NH3)4Cl2, it is dissolved in 25mL's respectively
Dipping solution is made in deionized water；Utilize a diameter of 1.5~2mm γ-Al2O3Bead as catalyst carrier, using etc. body
Product infusion process, weighs 2g γ-Al2O3The above-mentioned 3mL of dipping solution containing palladium of immersion；Ultrasound 10min is impregnated, is air-dried after 6h in 60 DEG C of bars
2h is dried under part；Take above-mentioned copper chloride solution 2.3mL to be impregnated into above-mentioned catalyst again, impregnate ultrasound 10min, air-dry 6h
2h is dried under the conditions of 60 DEG C afterwards, obtained catalyst is small in 200~400 DEG C of activation process 6 of temperature programming in air atmosphere
When (200 DEG C of 1h, 300 DEG C of 1h, 400 DEG C of 4h), that is, obtain catalyst Pd (1.4%)-CuCl2(10%)/γ-Al2O3(roasting).
Embodiment 3
Take 0.6696g copper chlorides CuCl2·2H2O and 0.00479g dichloride palladium Pd (NH3)4Cl2, 25mL is dissolved in respectively
Deionized water in dipping solution is made；Utilize a diameter of 1.5~2mm γ-Al2O3Bead as catalyst carrier, using etc.
Volume impregnation method, weighs 2g γ-Al2O3The above-mentioned 3mL of dipping solution containing palladium of immersion；Ultrasound 10min is impregnated, is air-dried after 6h at 60 DEG C
Under the conditions of dry 2h；Take above-mentioned copper chloride solution 2.3mL to be impregnated into above-mentioned catalyst again, impregnate ultrasound 10min, air-dry
2h is dried after 6h under the conditions of 60 DEG C, obtained catalyst is in air atmosphere in 200~400 DEG C of activation process 6 of temperature programming
Hour (200 DEG C of 1h, 300 DEG C of 1h, 400 DEG C of 4h), that is, obtain catalyst Pd (0.2%)-CuCl2(3.1%)/γ-Al2O3(roasting).
Application example 1
The catalyst of preparation, the key step that it is used for flue gas demercuration is as follows：Weigh the above-mentioned catalyst of 25mg (comparative example 1,
2nd, 3, and embodiment 1), it is placed in tubular type fixed reactor, is passed through containing the μ g/m of Elemental Mercury 230~2603, oxidant
HCl concentration is 10ppm, oxygen O2(carrier gas of gaseous mixture and nonvalent mercury is N to the simulated flue gas that concentration is 6%2).It is in temperature
Under conditions of 150 DEG C, when catalyst reaches the stably catalyzed stage, oxygenation efficiency of the catalyst to Elemental Mercury in flue gas is investigated.Its
As a result it is as shown in the table：
The catalyst oxidation susceptibility of table 1 is contrasted
| Catalyst | Elemental mercury oxidation rate |
| Comparative example 1：CuCl2(3.1%)/γ-Al2O3(leaching) | 40% |
| Comparative example 2：CuCl2(3.1%)/γ-Al2O3(roasting) | 87% |
| Comparative example 3：Pd (0.4%)/γ-Al2O3(roasting) | 5% |
| Embodiment 1：Pd (0.4%)-CuCl2(3.1%)/γ-Al2O3(roasting) | 90% |
* reaction condition：[HCl]=10ppm, [O2]=6%, residual air is N2。
Application example 2
The catalyst of preparation, the key step that it is used for flue gas demercuration is as follows：Weigh 25mg above-mentioned catalyst (comparative examples 2
And embodiment 1~3), it is placed in tubular type fixed reactor, is passed through containing the μ g/m of Elemental Mercury 230~2603, oxidant HCl
Concentration is 10ppm, oxygen O2Concentration is 6% and sulfur dioxide SO2Concentration is 2000ppm simulated flue gas (gaseous mixture and nonvalent mercury
Carrier gas be N2).Under conditions of temperature is 150 DEG C, when catalyst reaches the stably catalyzed stage, catalyst is investigated to cigarette
The oxygenation efficiency of Elemental Mercury in gas.Its result is as shown in the table：
The catalyst oxidation susceptibility of table 2 and sulfur resistance contrast
| Catalyst | Elemental mercury oxidation rate |
| Comparative example 2：CuCl2(3.1%)/γ-Al2O3(roasting) | 6% |
| Embodiment 1：Pd (0.4%)-CuCl2(3.1%)/γ-Al2O3(roasting) | 90% |
| Embodiment 2：Pd (1.4%)-CuCl2(10%)/γ-Al2O3(roasting) | 99% |
| Embodiment 3：Pd (0.2%)-CuCl2(3.1%)/γ-Al2O3(roasting) | 90% |
* reaction condition：[HCl]=10ppm, [O2]=6%, [SO2]=2000ppm, residual air is N2。
Claims (7)
1.Pd-CuCl2/γ-Al2O3The preparation method of demercuration composite catalyst, it is characterised in that：By dichloride's palladium and chlorination
Copper is supported on γ-Al by infusion process2O3After on carrier, it is placed in 200~400 DEG C of temperature environments and activates, produce.
2. Pd-CuCl according to claim 12/γ-Al2O3The preparation method of demercuration composite catalyst, it is characterised in that：
The mol ratio of dichloride's palladium and copper chloride is (0.01~0.2):1.
3. Pd-CuCl according to claim 12/γ-Al2O3The preparation method of demercuration composite catalyst, it is characterised in that：
Described Pd-CuCl2/γ-Al2O3The gross mass of palladium and copper chloride is γ-Al in demercuration composite catalyst2O3Carrier quality
2%~20%.
4. Pd-CuCl according to claim 12/γ-Al2O3The preparation method of demercuration composite catalyst, it is characterised in that：
Described activation is progressively heating treatment process, i.e., be incubated 0.5~1.5h at 200~230 DEG C successively, in 280~320 DEG C of insulations
0.5~1.5h, 3~5h is incubated at 370~400 DEG C.
5. Pd-CuCl according to claim 12/γ-Al2O3The preparation method of demercuration composite catalyst, it is characterised in that：
Comprise the following steps：(1) dichloride's palladium solution is first impregnated into γ-Al2O3On, it is ultrasonically treated after, dry, obtain sample A；
(2) copper chloride solution is impregnated on sample A again, it is ultrasonically treated, dry, obtain sample B；(3) sample B is placed in air atmosphere
Under, 0.5~1.5h is incubated at 200~230 DEG C successively, 0.5~1.5h is incubated at 280~320 DEG C, 3 are incubated at 370~400 DEG C
~5h；Produce.
6. Pd-CuCl made from any one of Claims 1 to 5 preparation method2/γ-Al2O3Demercuration composite catalyst should
With, it is characterised in that：Applied to catalysis oxidation Elemental Mercury.
7. the Pd-CuCl according to right 62/γ-Al2O3The application of demercuration composite catalyst, it is characterised in that：Applied to smelting
Refine the catalysis oxidation of Elemental Mercury in flue gas demercuration technical process.
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