CN100493702C - Micro-carbon monoxide normal temperature eliminating catalyst and preparing method thereof - Google Patents
Micro-carbon monoxide normal temperature eliminating catalyst and preparing method thereof Download PDFInfo
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- CN100493702C CN100493702C CNB2004100132793A CN200410013279A CN100493702C CN 100493702 C CN100493702 C CN 100493702C CN B2004100132793 A CNB2004100132793 A CN B2004100132793A CN 200410013279 A CN200410013279 A CN 200410013279A CN 100493702 C CN100493702 C CN 100493702C
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- 239000003054 catalyst Substances 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims description 17
- 229910002091 carbon monoxide Inorganic materials 0.000 title description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000002253 acid Substances 0.000 claims abstract description 20
- 229910052802 copper Inorganic materials 0.000 claims abstract description 11
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 50
- 238000007598 dipping method Methods 0.000 claims description 35
- 229910052799 carbon Inorganic materials 0.000 claims description 29
- 230000009467 reduction Effects 0.000 claims description 16
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 239000012752 auxiliary agent Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical group [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 15
- 238000006424 Flood reaction Methods 0.000 claims 2
- 229910000510 noble metal Inorganic materials 0.000 claims 1
- 239000012279 sodium borohydride Substances 0.000 claims 1
- 229910000033 sodium borohydride Inorganic materials 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 20
- 238000005406 washing Methods 0.000 abstract description 4
- 238000001914 filtration Methods 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 39
- 238000003756 stirring Methods 0.000 description 28
- 239000008367 deionised water Substances 0.000 description 25
- 230000008030 elimination Effects 0.000 description 21
- 238000003379 elimination reaction Methods 0.000 description 21
- 229910021641 deionized water Inorganic materials 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 14
- 101150003085 Pdcl gene Proteins 0.000 description 13
- 239000002250 absorbent Substances 0.000 description 12
- 230000002745 absorbent Effects 0.000 description 12
- 239000003610 charcoal Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 238000005303 weighing Methods 0.000 description 6
- 229920004482 WACKER® Polymers 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 230000001147 anti-toxic effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- -1 salt compounds Chemical class 0.000 description 2
- 238000009938 salting Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Classifications
-
- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A catalyst for eliminating small quantity of CO (5-30 ppm) is composed of Pd, assistant chosen from Li, K, P, Cu and V, and activated carbon. It is prepared through boilig activated carbon in acid, water washing, immersing for adsorbing said Pd and assistant, wet reducing, filtering and baking.
Description
Technical field
The invention relates to micro CO normal temperature and eliminate Catalysts and its preparation method.
Background technology
All the time, the elimination of micro CO (ppm level) all is essential in the closed system surrounding airs such as space station, submarine cabin, powerhouse of hydropower station and underground antiaircraft facility.Along with the raising that people require habitation environment quality, the micro CO pollution problem in the room air in recent years also receives publicity gradually.Micro CO (CO) normal temperature null method has absorption process, absorption method and catalytic oxidation etc., and the successful CosorB method (absorption process) of the U.S. Tenneco chemical company research seventies in 20th century can effectively be eliminated CO under low pressure, room temperature condition.Cosor B solution has under the normal temperature has high the selection to absorb to CO, and viscosity is low, and good stability absorbs characteristics such as load is big.But because essential complex apparatus and technological process are not suitable for the elimination of trace amounts of CO under the environment such as family room, space station, greenhouse, submarine cabin.
Absorption method is that contaminated air is contacted with the porous solid absorbent.CO adsorbent commonly used has active carbon, Immesion active carbon, molecular sieve etc.The occasion that active carbon commonly used is made adsorbent comprises: food storage warehouse, greenhouse, dwelling house, submarine and space closed cabin etc.Charcoal absorption CO mainly is physical absorption, is characterized in existing adsorption equilibrium.Therefore under certain condition, it adsorbable CO total amount be limited.Unless use a large amount of sorbing materials, and need frequent the replacing, this is a very thing of trouble.
Is CO by active catalyst with the CO complete oxidation
2Be catalytic oxidation with the method for eliminating CO in the contaminated air.In indoor or other closed system air, aspect the elimination of trace amounts of CO, by catalytic oxidation CO is carried out the catalytic oxidation elimination under the room temperature and have crucial meaning.From appliance arrangement and the easy difficult angle of operation, it is good that absorption process and absorption method can not show a candle to catalytic oxidation.
There is the catalyst of greater activity to mainly contain Wacker catalyst, Hopcalite catalyst and improved catalyst thereof to the CO catalytic oxidation under the normal temperature, though the Wacker catalyst is eliminated catalyst as CO normal temperature certain activity is arranged, but along with the growth in reaction time, the heat that the CO oxidizing process discharges makes the HCl of the generation disengaging reaction system of volatilizing gradually.The volatilization of HCl is run off and not only can be shortened the service life of catalyst, also becomes new pollution sources in indoor air purification.With PdCl
2-CuCl
2Solution impregnation is adsorbed on active A l
2O
3On the carrier, make the PdCl that contains 0.29wt%Pd and 4.13wt%Cu
2-CuCl
2/ Al
2O
3Support type Wacker catalyst, it is 50000hr with air speed that this catalyst is 60 ℃ in temperature
-1Condition under, after 180 hours, the CO elimination factor reduces to 40% by initial 85%.The support type Wacker catalyst (Pd content is 1.0wt%) that with PAN carbon felt is carrier is at 40 ℃ of reaction temperatures and air speed 10000hr
-1Under react 230 hours after, the CO conversion ratio reduces to 70% from 90%.The Hopcalite catalyst is mainly by MnO
2, CuO and other several oxides make through mixing method.Since it between 40～80 ℃ to air in trace amounts of CO good activity is arranged and once became generally the CO normal temperature that uses and eliminate catalyst.Domestic Fushun chemical industry one factory has industrial production.Its major defect is: when envionmental humidity is big, very easily lost the ability of effectively eliminating CO under the normal temperature by airborne steam poisoning and deactivation.Application shows: contain 550ppm CO in air, vapour content is a water saturation steam under the room temperature, and air is with 1000hr
-1Air speed when the Hopcalite catalyst, the normal temperature and pressure ventilation is after 6 hours, the purifying rate of CO drops to 8% by original 98%.Therefore, must increase supporting auxiliary equipment to eliminate the water vapour in the reaction gas fully when using this catalyst to eliminate airborne trace amounts of CO, perhaps reaction temperature is increased to more than 80 ℃.The relative humidity of reaction gas is less to the catalyst activity influence under this temperature.But this not only needs to increase heater, also need be aided with cooling device and regulate the temperature that purifies the back air, thereby increase the complexity and the running expense that install, and these defectives have seriously limited the further application in practice of this catalyst.76,140,872 pairs of Hopcalite catalyst of day disclosure special permission communique improve, and add Cr
2O
3, Mn
2O
3, after the auxiliary agents such as Ni, Ag, when 30 ℃ of following catalyst kept greater activity, its water-fast steam performance also increased, but air speed can not surpass 500hr
-1The 5wt%Pt/C catalyst of day disclosure special permission communique 78,119,292 reports is at room temperature and 20000hr
-1Purifying rate to 100ppm CO under the air speed is 100%; The Pd/C catalyst of report such as Hu Baomei, Chen Xianming is eliminated airborne trace amounts of CO at normal temperatures and is also obtained good result.Because the expensive price of Pt and Pd makes the big catalyst cost of these activity component load quantities higher relatively, thereby has limited its application.
In sum, existing micro CO normal temperature is eliminated catalyst, and also ubiquity is following not enough: the one pack system precious metal catalyst of (1) high capacity amount is good but cost an arm and a leg, and has limited the expansion of its range of application; (2) the multicomponent catalyst cost decreases but performance is good inadequately, can not reach practical requirement; (3) catalyst is poisoned easily to other toxic gas sensitivity in the surrounding air, causes catalyst activity reduction even inactivation.
Summary of the invention
The objective of the invention is to overcome the deficiency of existing catalyst, provide a kind of bullion content low, (moisture-proof is good, antitoxin thing SO for 5～30ppm) catalytic oxidation efficient height, long service life to micro CO in the surrounding air under the normal temperature
2, CH
3OCH
3, CCl
2F
2, CH
4Catalysts and its preparation method.Its preparation method high comprehensive performance, preparation cost is low.
The present invention realizes above-mentioned purpose by improving catalyst composition and preparation method.
(it is active component with Pd that 5～30ppm) normal temperature are eliminated catalyst to micro CO of the present invention, be selected among Li, K, P, Cu, the V one or more elements as auxiliary agent, make carrier with active carbon, the percentage by weight of Pd and active carbon is 0.1～3%, more preferably 0.3～2%, more preferably 0.5～0.8%., the atomic ratio of Pd and auxiliary element is 0.10～2.0, more preferably 0.20～1.5, more preferably 0.26～1.44.
Catalyst carrier is through 6N salt acid soak, washes, dries the active carbon of processing, and Pd, Cu, V can be from the salt or the metals of solubility, as Pd, PdCl
2, H
2PdCl
4, CuCl
2, Cu (NO
3)
2, V
2O
5, NH
4VO
3
The Preparation of catalysts method can be used infusion process, the steps include:
(1) salt compounds with selected auxiliary element dissolves, be mixed with the aqueous solution of the concentration that requires, salting liquid through 6N salt acid soak, the active carbon of washing, dry processing and auxiliary element flooded 2～8 hours by 1: 2.5～3.5 volume ratios, dried in 50～250 ℃ of temperature ranges then;
(2),, be mixed with and contain Pd and auxiliary element is the mixed aqueous solution that requires concentration auxiliary element salt dissolving with Pd salt or dissolving metal;
(3) will contain the active carbon of auxiliary element and Pd and auxiliary element mixed solution by 1: 4～10 volume ratios dipping 2～10 hours, be heated to 30～90 ℃, and add and be selected from HCHO, H
2NNH
2H
2O, NaBH
4In a kind of reducing agent, its consumption is by excessive 1.2～5 times of stoichiometry, reduction is more than 30 minutes;
(4) remove by filter dipping reduction raffinate, oven dry obtains product.
Perhaps adopt following step preparation:
(1) salt compounds with selected auxiliary element dissolves, be mixed with the aqueous solution of the concentration that requires, through 6N salt acid soak, wash, dry acid-treated active carbon and auxiliary element salting liquid by 1: 2.5～3.5 volume ratios dipping 2～8 hours, in 50～250 ℃ of temperature ranges, dry then;
(2),, be mixed with and contain Pd and auxiliary element is the mixed aqueous solution that requires concentration selected auxiliary element salt dissolving with Pd salt or dissolving metal;
(3) will contain the active carbon of auxiliary element and Pd and auxiliary element mixed solution by 1: 4～10 volume ratios dipping 2～10 hours, filter, washing, oven dry,, obtain product 100～200 ℃ of logical hydrogen reductions.
This catalyst is compared with existing micro CO normal temperature elimination catalyst has following characteristics:
1, under the normal temperature to micro CO catalytic oxidation activity height in the air, long service life, moisture resistance properties is good, the unit interval is handled big, the antitoxin thing SO of gas flow
2, CH
3OCH
3, CCl
2F
2, CH
4Deng.
2, this catalyst is by adding among Li, K, P, Cu, the V one or more elements as auxiliary agent, make that Pd content drops to 0.1～3wt% in the catalyst, make the cost of material valency descend 70% and the catalyst combination property is unaffected at least, overcome catalyst cost height, limitation that application surface is narrow.
3, this catalyst preparation process mild condition, method is easy, and handling safety is easy to implement.
The performance of catalyst is investigated to test and is carried out in normal pressure U type fixed bed reactors, catalyst amount 2ml, and catalyst grain size 10～20 orders, the about 0.605g/ml of loading density, unstripped gas consists of: CO15～25ppm, SO
21.0ppm, CH
3COCH
3100～500ppm, CCl
2F
2100～500ppm, CH
450ppm, all the other are air.25 ℃ of reaction temperatures, unstripped gas relative humidity 60%, air speed are 12000hr
-1Catalyst activity is represented with the carbon monoxide elimination factor.The carbon monoxide elimination factor calculates by following formula:
Wherein: R (%)---carbon monoxide elimination factor;
C
InletThe CO concentration (ppm) of one trace amounts of CO reactor inlet;
C
OutletThe CO concentration (ppm) of one trace amounts of CO reactor outlet.
The specific embodiment
Further specify this catalyst and preparation method below by embodiment, but be not limitation of the present invention, used active carbon all is to remove Cl only with 6N salt acid soak after washing unless otherwise indicated in the example
-After active carbon.
Embodiment 1
Add the 50ml deionized water in the 250ml beaker, adding V concentration is the V of 0.01g/ml
2O
5Solution 4ml stirs, and takes by weighing through acid-treated active carbon 10g, pours above-mentioned V into
2O
5In the solution, stirred dipping 3 hours under the room temperature, in 50～250 ℃ of temperature ranges, dry, take out standby.
In the 250ml beaker, add the 100ml deionized water, add the PdCl of Pd concentration 0.01g/ml
2Solution 6ml, adding Cu concentration is the Cu (NO of 0.01g/ml
3)
2Solution 12ml, the back that stirs adds the above-mentioned V of containing absorbent charcoal carrier, stirs dipping under the room temperature after 5 hours, and 25 ℃ add 0.06g NaBH down
4Reaction 30min removes by filter dipping reduction raffinate, and oven dry obtains product, and its Pd content is 0.6% (wt), and Cu content is 1.2% (wt), and V content is 0.4% (wt).
Made catalyst is carried out performance according to the afore-mentioned test condition investigates, move 1080 hours continuously, catalyst to the elimination factor of micro CO always greater than 99.1%.
Embodiment 2
Add the 50ml deionized water in the 250ml beaker, adding V concentration is the V of 0.01g/ml
2O
5Solution 4ml stirs, and takes by weighing through acid-treated active carbon 10g, pours above-mentioned V into
2O
5In the solution, stirred dipping 3 hours under the room temperature, in 50～250 ℃ of temperature ranges, dry, take out standby.
In the 250ml beaker, add the 100ml deionized water, add the PdCl of Pd concentration 0.01g/ml
2Solution 6ml, adding Cu concentration is the Cu (NO of 0.01g/ml
3)
2Solution 5.2ml, the back that stirs adds the above-mentioned V of containing absorbent charcoal carrier, stirs dipping under the room temperature after 5 hours, and 25 ℃ add 0.06g NaBH down
4Reaction 30min removes by filter dipping reduction raffinate, and oven dry obtains product, and its Pd content is 0.6% (wt), and Cu content is 0.52% (wt), and V content is 0.4% (wt).
Made catalyst is carried out performance according to the afore-mentioned test condition investigates, move 1080 hours continuously, catalyst to the elimination factor of micro CO always greater than 99.99%.
Embodiment 3
Add the 50ml deionized water in the 250ml beaker, adding V concentration is the V of 0.01g/ml
2O
5Solution 4ml stirs, and takes by weighing through acid-treated active carbon 10g, pours above-mentioned V into
2O
5In the solution, stirred dipping 3 hours under the room temperature, in 50～250 ℃ of temperature ranges, dry, take out standby.
In the 250ml beaker, add the 100ml deionized water, add the PdCl of Pd concentration 0.01g/ml
2Solution 2.6ml, adding Cu concentration is the Cu (NO of 0.01g/ml
3)
2Solution 12ml, the above-mentioned V of the containing absorbent charcoal carrier of back adding stirs, stir dipping under the room temperature after 5 hours, 85 ℃ add 38% HCHO 1.6ml reaction 60min down, remove by filter dipping reduction raffinate, spend deionised water, oven dry obtains product, its Pd content is 0.26% (wt), and Cu content is 1.2% (wt), and V content is 0.4% (wt).
Made catalyst is carried out performance according to the afore-mentioned test condition investigate, move 20 hours, catalyst drops to 74% to the elimination factor of micro CO by 88%.
Embodiment 4
Add the 50ml deionized water in the 250ml beaker, adding V concentration is the V of 0.01g/ml
2O
5Solution 4ml stirs, and takes by weighing through acid-treated active carbon 10g, pours above-mentioned V into
2O
5In the solution, stirred dipping 3 hours under the room temperature, in 50～250 ℃ of temperature ranges, dry, take out standby.
In the 250ml beaker, add the 50ml deionized water, add the PdCl of Pd concentration 0.01g/ml
2Solution 30ml, adding V concentration is the V of 0.01g/ml
2O
5Solution 3.5ml, the back that stirs adds through acid-treated absorbent charcoal carrier 10g, stirs dipping under the room temperature after 16 hours, removes by filter the dipping raffinate, spends deionised water to there not being Cl
-1, oven dry is at 160 ℃ of down logical H
2Reduction 55min obtains product, and its Pd content is 3% (wt).V content is 0.75% (wt).
Made catalyst is carried out performance according to the afore-mentioned test condition investigate, move 1000 hours, catalyst is to the elimination factor 87.1% of micro CO.
Embodiment 5
Add the 50ml deionized water in the 250ml beaker, adding Li concentration is the LiCl solution 4ml of 0.01g/ml, stirs, take by weighing through acid-treated active carbon 10g, pour in the above-mentioned LiCl solution, stirred dipping 3 hours under the room temperature, in 50～250 ℃ of temperature ranges, dry, take out standby.
In the 250ml beaker, add the 250ml deionized water, add the H of Pd concentration 0.01g/ml
2PdCl
4Solution 6ml, adding Li concentration is the LiCl solution 12ml of 0.01g/ml, and the back that stirs adds the above-mentioned Li of containing absorbent charcoal carrier, stirs dipping under the room temperature after 5 hours, and 250 ℃ add 0.1gH down
2NNH
2H
2O reacts 30min, removes by filter dipping reduction raffinate, and oven dry obtains product, and its Pd content is 0.6% (wt), and Li content is 1.8% (wt).
Made catalyst is carried out performance according to the afore-mentioned test condition investigate, move 1080 hours, catalyst is to the elimination factor 78.0% of micro CO.
Embodiment 6
Add the 50ml deionized water in the 250ml beaker, adding V concentration is the V of 0.01g/ml
2O
5Solution 4ml stirs, and takes by weighing through acid-treated active carbon 10g, pours above-mentioned V into
2O
5In the solution, stirred dipping 3 hours under the room temperature, in 50～250 ℃ of temperature ranges, dry, take out standby.
In the 250ml beaker, add the 100ml deionized water, add the PdCl of Pd concentration 0.01g/ml
2Solution 6ml, adding Cu concentration is the Cu (NO of 0.01g/ml
3)
2Solution 12ml, the back that stirs adds the above-mentioned V of containing absorbent charcoal carrier, stirs dipping under the room temperature after 5 hours, and 85 ℃ add 38% HCHO 1.6ml reaction 60min down, remove by filter dipping reduction raffinate, spend deionised water to there not being Cl
-1, oven dry obtains product, and its Pd content is 0.6% (wt), and Cu content is 1.2% (wt), and V content is 0.4% (wt), is numbered the A catalyst.All the other preparation methods are with the A catalyst, and unique difference is that reducing agent is 40%H
2NNH
2H
2O
5, reaction 80min is numbered the B catalyst.
Made catalyst is carried out performance according to the afore-mentioned test condition investigate, move 20 hours, the A catalyst drops to 74% to the elimination factor of micro CO by 90%.The elimination factor of B catalyst then drops to 78% by 87%.
Embodiment 7
In the 250ml beaker, add the 100ml deionized water, add the PdCl of Pd concentration 0.01g/ml
2Solution 5.5ml, adding Cu concentration is the Cu (NO of 0.01g/ml
3)
2Solution 11ml, adding V concentration is the V of 0.01g/ml
2O
5Solution 4.5ml, the back that stirs adds through acid-treated absorbent charcoal carrier 10g, stirs dipping under the room temperature after 10 hours, and 35 ℃ add 0.07g NaBH down
4Reaction 45min removes by filter dipping reduction raffinate, spends deionised water to there not being Cl
-1, oven dry obtains product, and its Pd content is 0.55% (wt), and Cu content is 1.1% (wt), and V content is 0.45% (wt).
Made catalyst is carried out performance according to the afore-mentioned test condition investigate, move 18 hours, catalyst drops to 60% to the elimination factor of micro CO by 88%.
Embodiment 8
In the 250ml beaker, add the 100ml deionized water, add the PdCl of Pd concentration 0.01g/ml
4Solution 5.2ml, adding Li concentration is the LiCl solution 3.0ml of 0.01g/ml, and adding K concentration is the KCl solution 1.0ml of 0.01g/ml, and the back that stirs adds through acid-treated absorbent charcoal carrier 10g, stir dipping under the room temperature after 11 hours, 35 ℃ add 0.07g NaBH down
4Reaction 55min removes by filter dipping reduction raffinate, spends deionised water to there not being Cl
-1, oven dry obtains product, and its Pd content is 0.52% (wt), and Li content is 0.3% (wt), and K content is 0.1% (wt).
Made catalyst is carried out performance according to the afore-mentioned test condition investigate, move 1080 hours, catalyst is to the elimination factor 77.9% of micro CO.
Embodiment 9
In the 250ml beaker, add the 100ml deionized water, add the PdCl of Pd concentration 0.01g/ml
2Solution 5.8ml, adding Cu concentration is the Cu (NO of 0.01g/ml
3)
2Solution 12ml, adding V concentration is the V of 0.01g/ml
2O
5Solution 4.2ml, adding P concentration is the H of 0.01g/ml
3PO
4Solution 1ml, the back that stirs adds through acid-treated absorbent charcoal carrier 10g, stirs dipping under the room temperature after 15 hours, and 65 ℃ add 0.07g NaBH down
4Reaction 85min removes by filter dipping reduction raffinate, spends deionised water to there not being Cl
-1, oven dry obtains product, and its Pd content is 0.58% (wt), and Cu content is 1.2% (wt), and V content is 0.42% (wt), P content is 0.1% (wt).
Made catalyst is carried out performance according to the afore-mentioned test condition investigate, move 20 hours, the A catalyst is to the elimination factor 96.1% of micro CO.
Embodiment 10
In the 250ml beaker, add the 100ml deionized water, add the PdCl of Pd concentration 0.01g/ml
4Solution 6ml, adding Li concentration is the LiCl solution 3.0ml of 0.01g/ml, and adding K concentration is the KCl solution 1.0ml of 0.01g/ml, and adding Cu concentration is the Cu (NO of 0.01g/ml
3)
2Solution 1ml, adding V concentration is the V of 0.01g/ml
2O
5Solution 1ml, adding P concentration is the H of 0.01g/ml
3PO
4Solution 1ml, the back that stirs adds through acid-treated absorbent charcoal carrier 10g, stirs dipping under the room temperature after 10 hours, and 65 ℃ add 0.1gNaBH down
4Reaction 85min removes by filter dipping reduction raffinate, spends deionised water to there not being Cl
-1, oven dry obtains product, and its Pd content is 0.6% (wt), and Li content is 0.3% (wt), and K content is that 0.1% (wt) Cu content is 0.1% (wt), and V content is 0.1% (wt), and P content is 0.1% (wt).
Made catalyst is carried out performance according to the afore-mentioned test condition investigate, move 1080 hours, catalyst is to the elimination factor 88.9% of micro CO.
Embodiment 11
In the 250ml beaker, add the 100ml deionized water, add the PdCl of Pd concentration 0.01g/ml
4Solution 6ml, adding Li concentration is the LiCl solution 3.0ml of 0.01g/ml, and adding K concentration is the KCl solution 1.0ml of 0.01g/ml, and adding Cu concentration is the Cu (NO of 0.01g/ml
3)
2Solution 1ml, adding V concentration is the V of 0.01g/ml
2O
5Solution 1ml, adding P concentration is the H of 0.01g/ml
3PO
4Solution 1ml, the back that stirs adds through acid-treated absorbent charcoal carrier 10g, stirs dipping under the room temperature and removes by filter the dipping raffinate after 11 hours, spends deionised water to there not being Cl
-1, oven dry is at 155 ℃ of down logical H
2Reduction 65min obtains product, and its Pd content is 0.6% (wt), and Li content is 0.3% (wt), and K content is that 0.1% (wt) Cu content is 0.1% (wt), and V content is 0.1% (wt), and P content is 0.1% (wt).
Made catalyst is carried out performance according to the afore-mentioned test condition investigate, move 1080 hours, catalyst is to the elimination factor 84.9% of micro CO.
Claims (2)
1, a kind of air micro CO normal temperature that is used for is eliminated catalyst, as active component, selects V element by the Pd noble metal for use, perhaps two kinds of elements of V and Cu, perhaps three kinds of elements of V, Cu and P, perhaps several elements of Li, V, Cu, P and K are as auxiliary agent, make carrier with active carbon, it is characterized in that; When selecting two kinds of elements of V and Cu for use, when perhaps several elements of Li, V, Cu, P and K were as auxiliary agent, Pd was 0.6% with respect to the percentage by weight of active carbon; When selecting V, Cu and P element as auxiliary agent for use, Pd is 0.58% with respect to the percentage by weight of active carbon; When selecting V element as auxiliary agent for use, Pd is 3% with respect to the percentage by weight of active carbon, and the atomic ratio of Pd and auxiliary element is 0.1～2.0, and this catalyst adopts following method to make,
Preparation process is:
(1) compound with selected auxiliary element dissolves, be mixed with the aqueous solution of the concentration that requires, through 6N salt acid soak, wash and the compound solution that dries the active carbon of processing and auxiliary element by 1: 2.5～3.5 volume ratios dipping 2～8 hours, in 50～250 ℃ of scopes, dry then;
(2),, be mixed with and contain Pd and auxiliary element is the mixed aqueous solution that requires concentration the dissolving of the compound of auxiliary element with Pd salt or dissolving metal;
(3) active carbon that will contain auxiliary element floods in the compound aqueous solution of Pd and auxiliary element, it contains the active carbon of auxiliary element and the compound aqueous solution volume ratio of Pd and auxiliary element is 1: 4～10, flood and be heated to 30～90 ℃ after 2～10 hours, add the NaBH4 reducing agent, its consumption is by excessive 1.2～5 times of stoichiometry, and reduction is more than 30 minutes;
(4) remove by filter dipping reduction raffinate, oven dry obtains product; Perhaps,
Preparation process is:
(1) compound with selected auxiliary element dissolves, be mixed with the aqueous solution of the concentration that requires, through 6N salt acid soak, wash and the compound solution that dries the active carbon of processing and auxiliary element by 1: 2.5～3.5 volume ratios dipping 2～8 hours, in 50～250 ℃ of scopes, dry then;
(2),, be mixed with and contain Pd and auxiliary element is the mixed aqueous solution that requires concentration the dissolving of the compound of auxiliary element with Pd salt or dissolving metal;
(3) active carbon that will contain auxiliary element floods in the compound aqueous solution of Pd and auxiliary element, it contains the active carbon of auxiliary element and the compound aqueous solution volume ratio of Pd and auxiliary element is 1: 4～10, flood after 2～10 hours and filter, wash, dry, 100～200 ℃ of logical hydrogen reductions, obtain product;
Wherein, the compound of described auxiliary element V is V
2O
5Or NH
4VO
3, the compound of auxiliary element Cu is CuCl
2Or Cu (NO
3)
2, the compound of auxiliary element P is H
3PO
4, the compound of auxiliary element Li is LiCl, the compound of auxiliary element K is KCl.
2, by the described catalyst of claim 1, it is characterized in that: the atomic ratio of Pd and auxiliary element is 0.20～1.5.
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| CN101081303B (en) * | 2007-06-28 | 2010-12-01 | 湖南科技大学 | Method for fathering submarine discharge gas through air self-cleaning |
| CN101722009B (en) * | 2008-10-24 | 2012-10-24 | 中国石油化工股份有限公司 | Nano-gold catalyst for deeply removing carbon monoxide, preparing method and application thereof |
| CN102059115A (en) * | 2010-12-20 | 2011-05-18 | 上海纳米技术及应用国家工程研究中心有限公司 | CO normal-temperature catalytic oxidation catalyst and preparation method thereof |
| CN103962150B (en) * | 2013-02-06 | 2016-06-22 | 中国中化股份有限公司 | A kind of Catalysts and its preparation method for preparing chlorinated aromatic amine |
| CN111068725B (en) * | 2018-10-18 | 2023-05-02 | 中国石油化工股份有限公司 | Catalyst for preparing 1,4-cyclohexane dicarboxylic acid and application thereof |
| CN114515580B (en) * | 2022-03-09 | 2023-07-11 | 嘉庚创新实验室 | Supported catalyst for CO oxidation reaction and preparation method and application thereof |
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