CN104338543A - Super acid modified copper oxide catalyst used for removing carbon monoxide - Google Patents
Super acid modified copper oxide catalyst used for removing carbon monoxide Download PDFInfo
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Abstract
The invention discloses a super acid modified copper oxide catalyst used for removing carbon monoxide. The catalyst includes a component A and a component B, the component A is a composite metal oxide prepared by a coprecipitation method, and the component B is a solid super acid; the catalyst is represented by the following formula: CuaBibZncXdYeOf, wherein the X is at least one element selected from the group consisting of manganese and antimony, Y is at least one element selected from the group consisting of titanium and zirconium, a, b, c, d, e and f represent atomic ratio number of the elements, and based on the atomic ratio number a of Cu being 10, 0<b<=1,0<c<=1,0<d<=30,0<e<=10, and f is a number needed to meet the oxidation state of the components. The catalyst can realize deep removal of trace carbon monoxide in an olefin material to below 30ppb at a reaction temperature of 0 to 70 DEG C.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method and the application that remove micro CO for low temperature, more particularly, the present invention relates to a kind of for removing Catalysts and its preparation method containing the micro CO in the olefin feed of plurality of impurities and application.
Background technology
Along with the development of polyolefin technology, highly active polyolefin catalyst, as very responsive to poisonous substance in metallocene catalyst etc., require that polyolefinic raw materials is polymer grade raw material.In olefin feedstock, carbon monoxide impurities is no more than 30ppb specifically, therefore needs the catalyst developing a kind of deeply removing CO impurity.
Prior art often adopts copper system or co-containing mixed oxide catalyst, and its principle is the metal oxide component MO utilized wherein
xin Lattice Oxygen come and the reaction of carbon monoxide in material flow, instead of by the carbon monoxide in material and oxygen reaction; Metal oxide component MO in purification process
xprogressively be reduced into elemental metals M and cause active reduction.
When deeply removing CO, need on the one hand the reactivity of the catalyst improving removal of carbon monoxide, need on the other hand to consider olefin feed as ethene, propylene self with trace impurity such as water and carbon dioxide etc. significantly will reduce the activity of catalyst.
Prior art often adopts copper Containing Oxide Catalyst, and its principle utilizes wherein component CuO
xin Lattice Oxygen come to react, instead of by the carbon monoxide in material and oxygen reaction with CO in material flow; CuO in purification process
xprogressively be reduced into simple substance Cu and cause active reduction.Prior art reckons without other trace impurities to the impact removing CO.When a large amount of trace impurity exist and require to remove the degree of depth high, needing to consider is not the catalytic activity how improving prior art, needs the anti-trace impurity poisoning performance considering existing catalysis technique yet.
Super acids is the solid acid that a kind of ratio 100% sulfuric acid is also strong, but have advantage that liquid acid do not possess as with separation of products easily, non-corrosiveness and less etc. to environmental hazard.Super acids mainly comprises the sulfuric acid root type solid acid (SO of two classes as described in CN1421270
4 2-/ ZrO
2) and composite oxides type solid acid (WO described in CN1394677
3/ ZrO
2and MO
3/ ZrO
2or), as being mainly used in hydro carbons alkylation, isomerization and esterification.The method that the mensuration of solid super strong acid strength is the most frequently used is Hammett indicator method and Temperature Programmed Desorption (TPD).In indicator method measures, H
0the PKa of indicator is less than-11.94, could determine that the surface of solids exists super acids like this.Adopt TPD method to measure, calculated by the amount calculating B acid and L acid and measure at long last, thus determine whether there is super acids, in addition as Tang Xinshuo (SO
4 2-/ ZrO
2type super acids acid site formation mechanism study, Chinese science B collects 1994, vol (24), 584 ~ 595) point out, super acids center has two or more acid sites and forms group's cooperative effect and produce, and the L acid under certain condition in super acids and B acid can be changed mutually.As Jiang Wenwei (progress of super acidic catalyst, fine chemistry industry, 1997, vol(1), 46 ~ 49) described in, use ZrO
2, TiO
2and Fe
2o
3the oxide acidity obtained Deng oxide is large, adopts Al
2o
3and SnO
2can only be strong solid acids etc. the oxide obtained, and use SiO
2, Bi
2o
3, CuO, ZnO and MnO
2the acidity of catalyst made Deng oxide is very weak.There is no the application of super acids in Oxidation of Carbon Monoxide or purification at present.
As Pan Shengyun etc., (propylene is at SO
4 2-/ M
xo
ythe research of the oligomerization on solid super acid catalyst, Chemical Engineering and Technology, 1995, vol (1), 342 ~ 347) propose, 130 DEG C, 4.0MPa, LHSV be 1.0hr-1 and density of propylene be 50% time, propylene conversion up to 69.5%, nonene and laurylene selective respectively about 45.5 and 41.6%.Super acids is used for the problem that the purification of olefin feed stream need consider olefin(e) oligomerization, and this may also be that prior art does not consider one of possible cause adopting solid super-strong acid.
But the reacting quintessence that removes of trace amounts of CO is a chemisorbed process, and the active oxidation namely in the CO in material flow and the CuO in catalyst is reacted.In view of the reaction temperature of this reaction is lower, namely 0 ~ 120 DEG C even can be reacted at about 50 DEG C, therefore introduces in so low temperature the oligomerisation that super acids can't cause alkene; Reaction heat on the other hand due to the CO generation removing ppm magnitude is also minimum even negligible, and therefore this reaction also can consider catalyst stability, and adopts the amorphous material being better than crystalline material when dispersed activity species.
Therefore, removal of carbon monoxide catalyst must carried on highly active basis, considers the impact of anti-minor amount of water, carbon dioxide and other impurity, ensures good removal of carbon monoxide effect.
Summary of the invention
The problem to be solved in the present invention be improve remove containing minor amount of water, carbon dioxide, alkynes (or MAPD) material flow in the catalytic activity of CO, thus reach the effect of the carbon monoxide in deep removal olefin feed stream.
Concrete technical scheme is as follows:
An object of the present invention is to provide a kind of super acids Modified Cu oxide catalyst for removal of carbon monoxide.
Described catalyst comprises composite metal oxide and a kind of solid-state super acids of component (B) prepared by component (A) coprecipitation method, and this catalyst can be expressed by the following formula: Cu
abi
bzn
cx
dy
eo
fwherein X is selected from least one element in manganese and antimony, Y selects at least one element in titanium and zirconium, a, b, c, d, e and f represent the atomic ratio number of its element, relative to Cu atom a=10, and 0<b≤1,0<c≤1,0<d≤30,0<e≤10, f is the number needed for the oxidation state meeting each component; B component is wherein selected from compound oxide type inorganic type super acids, super acids acid strength pKa<-11.94.
The preferred antimony element of X.
The preferred titanium elements of Y, this titanium elements is from unformed shape titanium oxide.
B component is selected from following at least one: with tungstic acid or the molybdenum trioxide load super acids at unformed Zirconia carrier or unformed titania support.
Component A is prepared by following methods: mantoquita, zinc compound, titanium compound/zirconium compounds and bismuth compound are mixed, then by mixed liquor and sodium salt and flow or or the form of anti-addition add, control ph is 6.0 ~ 10.0, reaction temperature is 40 ~ 90 DEG C, afterwards aging, filter, wash to sodium oxide content lower than 0.05%, add antimony oxide drying, roasting, obtain presoma sediment A.
It is generally acknowledged that the reaction mechanism removing trace amounts of CO is, the Lattice Oxygen in catalyst and the reaction of carbon monoxide in material flow, thus form carbon dioxide, reach the object of removal of carbon monoxide.Because the oxygen in material flow at low temperatures can not be activated, Lattice Oxygen in catalyst cannot be restored, therefore this oxidation reaction does not meet mechanism, this reaction same atypical catalytic reaction process, this catalyst should be referred to as " adsorbent " more precisely, is still referred to as catalyst traditionally.
In order to improve the mobility of Lattice Oxygen, on the one hand by selecting suitable component to reach the object of disperseing CuO tiny crystal grains and cooperative effect, the Zn selected by the present invention and as the unformed titanium of carrier or Zirconium oxide; Because reaction temperature is lower, the content of reactant CO is only ppm magnitude in addition, and therefore exothermic heat of reaction is also negligible.General catalytic reaction due to heat release violent, consider the factor of the stability of catalyst, often select the carrier material of crystal formation, the present invention considers that the particularity of this reaction adopts unformed titanium dioxide or zirconium dioxide to have more Large ratio surface, is more conducive to improving catalyst activity.Reasonably combined on the other hand by composite oxides and the multiple oxide that appraises at the current rate, improves the mobility of Lattice Oxygen, better as selected X component (selecting at least one element in manganese and antimony).In addition suppressed the absorption (as Bi add the impact being often considered as reducing acetylene or propine) of alkynes by Bi component, thus reduce alkynes to the impact of reactivity; Suppress the formation of alkynes copper simultaneously, better ensure the security that catalyst uses.
Second object of the present invention is to provide a kind of preparation method of the super acids Modified Cu oxide catalyst for removal of carbon monoxide.The preparation process of this catalyst comprises three steps:
The preparation of first step component A copper composite oxides.Mantoquita, zinc compound, titanium compound/zirconium compounds and bismuth compound mix, then by mixed liquor and sodium salt and flow or or the form of anti-addition add, control ph is 6.0 ~ 10.0, reaction temperature is 40 ~ 90 DEG C, afterwards aging, filter, wash to sodium oxide content lower than 0.05%, add antimony oxide drying, roasting, obtain presoma sediment A.
The preparation of second step B component solid super-strong acid.Prepared by step a) zirconium hydroxide precipitate, adopt ammoniacal liquor to do precipitating reagent, obtained precipitated zirconium hydroxide, b) zirconium hydroxide precipitate is through drying and adopting sour promoter to soak after grinding, acid promoter is dimolybdate salt or wolframic acid ammonium salt, filters, dries and roasting c);
3rd step mixed-forming by after component A and B component mechanical mixture, carry out decomposing, granulation, roasting and compression molding.Concentration and the sintering temperature of acid promoter are outbalance influence factors, and the concentration of sour promoter generally chooses 0.1 ~ 3M, and sintering temperature generally chooses 200 ~ 450 DEG C.
Consider that the issuable carbon dioxide of material neutralization reaction process reacts with the steam of trace, likely form the carbanion covering active sites, the present invention introduces super acids to play the effect of restrain adsorption carbonate.Consider that sulfate ion may react with Cu in preparation process, thus inhibit activities.The present invention adopts the super acids of compound oxide type.
The acidity of the super acids in the present invention adopts Hammett indicator method to measure.
3rd object of the present invention is to provide a kind of application process of the super acids Modified Cu oxide catalyst for removal of carbon monoxide.Removal of carbon monoxide in the present invention, temperature 0 ~ 70 DEG C, under being preferably 20 ~ 65 DEG C and pressure 0.1 ~ 5MPa, make containing the charging of 0.1ppm ~ 5ppm carbon monoxide and other impurity and described catalyst exposure to remove the carbon monoxide in charging, during gas-phase feed, gaseous phase volume air speed is 1 ~ 10,000h
-1; During liquid phase feeding, liquid phase volume air speed is 0.1 ~ 100h
-1.Described charging is ethene, propylene or liquid propylene.Described charging is unsaturated alkyne, carbon dioxide and water containing trace.Described unsaturated alkyne is as impurity such as acetylene, propine and butine, and wherein the content of alkyne impurities is 0.01 ~ 100ppm, is preferably 0.05 ~ 10ppm, is more preferably 0.1 ~ 1ppm; Described carbon dioxide content is 0.1 ~ 50ppm, preferably 1 ~ 5ppm; Described described water content is 0.1 ~ 50ppm, preferably 1 ~ 10ppm.
In description of the present invention and claims, involved content, such as %, ppm and ppb are by weight; Described solution all refers to the aqueous solution.
Catalyst of the present invention has following beneficial effect:
1. improve the activity of the catalyst of removal of carbon monoxide;
2. avoid other impurity in material, if unsaturated alkyne, carbon dioxide and water are to the negative effect of catalyst activity.
Detailed description of the invention
In embodiments of the invention, the method for testing of relevant data is as follows:
XRD(X-ray diffraction, X-ray diffraction): the X pert MPD type X-ray diffractometer analysis of catalyst phase structure adopting Dutch Philips company, radiation source is CuK α, and sweep limits is 20 ~ 80 DEG C.Scherrer formula is adopted to calculate size of microcrystal.
Specific surface is tested: the physical adsorption appearance adopting the Nova3000e of Kang Ta company of the U.S., carries out specific surface area analysis.At liquid nitrogen temperature-196 DEG C, use N
2determination of adsorption method surface area and pore-size distribution, sample vacuumizes pretreatment and is less than 10 to pressure at 300 DEG C
-3pa, assay method is static method.BET method is adopted to calculate specific surface according to adsorption isotherm.
Super acids acid strength assay method: adopt the super acids acid strength measuring method that prior art is general.Detailed process is: tested sample immersed in benzole soln, and adds the acidity indicator of known pKa not of the same race.Namely the minimum pKa value presenting acid color thinks the acid strength of this sample.Acidity indicator comprises: meta-nitrotoluene (-12.0), para-nitrotoluene (-12.4), paranitrochlorobenzene (-12.7), m-chloronitrobenzene (-13.2), 2,4-dinitrotoluene (DNT) (-13.8) and 1,3,5-trinitrobenzen (-16.0).
Copper nitrate in embodiment, antimony oxide, manganese nitrate, zinc nitrate, sodium carbonate, ammoniacal liquor, zirconium oxychloride and bismuth nitrate, be analysis pure, recovers chemical reagent Co., Ltd purchased from Tianjin; Butyl titanate, ammonium tungstate and metamolybdic acid ammonium be analyze pure, purchased from Beijing chemical reagent factory.
Explain the preferred embodiment in the scope of the invention below by way of example further.
Embodiment 1
Adopt coprecipitation Kaolinite Preparation of Catalyst
The copper nitrate of 1 mol/L, zinc nitrate, zirconium oxychloride and bismuth nitrate solution are mixed, then by the sodium carbonate liquor of mixed liquor and 1 mol/L and stream joins to precipitate in the container of 30L, precipitation temperature is 80 DEG C, and pH value controls 8.5 ± 0.5.Then in strong agitation situation aging 2 hours, aging temperature was 80 DEG C.Then filter, at 80 DEG C, spend deionized water at least six times, to Na
2o content, lower than 0.05%, adds antimony oxide afterwards in filter cake.Drying 12 hours at 110 DEG C, roasting 4 hours at 350 DEG C, obtained component A.
By the zirconium oxychloride wiring solution-forming of 1M, make precipitating reagent with 1M ammoniacal liquor, obtained precipitated zirconium hydroxide, after drying precipitation and be levigate with the ammonium tungstate solution of 0.5mol/L soak, filter, 110 DEG C of oven dry, 350 DEG C of roasting 4h, obtain B component.By shaping for A and B two parts mixed pressuring plate, obtain 75wt%CuO/10wt%ZnO/0.5wt%Bi
2o
3/ 0.5wt%Sb
2o
3/ 5wt%WO
3/ 9wt%ZrO
2, be labeled as 1
#catalyst.Analyze through BET, specific surface is 125m
2/ g, acid strength is-12.4.
Embodiment 2
Adopt the mode Kaolinite Preparation of Catalyst identical with embodiment 1, unlike: adopt butyl titanate, replace zirconium oxychloride, obtain 75wt%CuO/10wt%ZnO/0.5wt%Bi
2o
3/ 0.5wt%Sb
2o
3/ 5wt%WO
3/ 9wt%TiO
2, 2
#catalyst.Analyze through BET, specific surface is 128m
2/ g, acid strength is-12.0.
Embodiment 3
Adopt the mode Kaolinite Preparation of Catalyst identical with embodiment 1, unlike: adopt metamolybdic acid ammonium to replace ammonium tungstate, obtain 75wt%CuO/10wt%ZnO/0.5wt%Bi
2o
3/ 0.5wt%Sb
2o
3/ 5wt%MoO
3/ 9wt%ZrO
2, be labeled as 3
#catalyst.Analyze through BET, specific surface is 132m
2/ g, acid strength is-12.4.
Embodiment 4
Adopting the mode Kaolinite Preparation of Catalyst identical with embodiment 1, by changing solution component proportioning, obtaining 65wt%CuO/18wt%ZnO/0.1wt%Bi
2o
3/ 0.1wt%Sb
2o
3/ 1.8wt%MoO
3/ 15wt%ZrO
2, be labeled as 4
#catalyst.Analyze through BET, specific surface is 225m
2/ g, acid strength is-12.4.
Comparative example 1
Part A preparation is identical with embodiment 1, does not add part B.
Obtained 75wt%CuO/15wt%ZnO/0.5wt%Bi
2o
3/ 0.5wt%Sb
2o
3/ 9wt%ZrO
2, be labeled as 5
#catalyst.Analyze through BET, specific surface is 125m
2/ g.Acid strength is not measured, and not thinks it is super acids.
Comparative example 2
Part A preparation is identical with embodiment 2, does not add part B.
Obtain 75wt%CuO/15wt%ZnO/0.5wt%Bi
2o
3/ 0.5wt%Sb
2o
3/ 9wt%TiO
2, be labeled as 6
#catalyst.Analyze through BET, specific surface is 128m
2/ g.Acid strength is not measured, and not thinks it is super acids.
Comparative example 3
Adopt the mode Kaolinite Preparation of Catalyst identical with embodiment 1, unlike: do not add Bi, obtain 75wt%CuO/10.5wt%ZnO/0.5wt%Sb
2o
3/ 5wt%WO
3/ 9wt%ZrO
2, be labeled as 7
#catalyst.Analyze through BET, specific surface is 125.4m
2/ g, acid strength is-12.4.
Comparative example 4
Adopt the mode Kaolinite Preparation of Catalyst identical with embodiment 1, unlike: do not add Sb, obtain 75wt%CuO/10.5wt%ZnO/0.5wt%Bi
2o
3/ 5wt%WO
3/ 9wt%ZrO
2, be labeled as 8
#catalyst.Analyze through BET, specific surface is 126m
2/ g, acid strength is-12.4.
Comparative example 5
Adopt the mode Kaolinite Preparation of Catalyst identical with embodiment 1, unlike: do not add zirconium oxychloride in preparation process, add crystal of zirconium oxide and mix with filter cake, obtain 75wt%CuO/10.5wt%ZnO/0.5wt%Sb
2o
3/ 5wt%WO
3/ 9wt%ZrO
2, be labeled as 9
#catalyst.Analyze through BET, specific surface is 25m
2/ g.Acid strength is not measured, and not thinks it is super acids.
The application 1 of catalyst
With the catalyst prepared by embodiment 1 ~ 4 and comparative example 1 ~ 5, that carries out trace amounts of CO respectively removes test.Evaluating catalyst is carried out 1000 hours in fixed bed continuous-flow tubular reactor.Loaded catalyst is 500mL, and reactor inside diameter is 40mm, and loading height is 400mm.After Catalyst packing, at 120 DEG C, purge 12 hours with high-purity nitrogen.Material is the allene of the propylene containing 2ppm CO, the carbon dioxide in addition containing 5ppm, the water of 10ppm, the propine of 3ppm and 5ppm.Reaction pressure is 2.5MPa, and reaction temperature is 40 DEG C, and air speed is 100hr
-1.Raw material and product first adopt gas chromatograph Varian3890 to analyze, and this gas chromatograph is with methanation reburner and hydrogen flame detector; After outlet CO content is lower than 0.1ppm, then detect with the micro CO analyzer of AMETEK company.Result of the test is listed in table 1.
Table 1 result of the test
As seen from Table 1,
(1) 1 ~ 3 is contrasted
#with 5 ~ 6
#catalyst.Do not add super acids, catalyst activity obviously reduces.
(2) 1 is contrasted
#with 7
#catalyst, does not add Bi, and catalyst activity obviously reduces.
(3) 1 is contrasted
#with 8
#catalyst, does not add Sb, and catalyst activity slightly reduces.
(4) 1 is contrasted
#with 9
#catalyst, catalyst adopts crystal formation zirconia, and active component crystal grain increases, and without super acids effect, catalyst is non-activity almost.
Catalyst application 2
The present embodiment be under different material condition removal of carbon monoxide remove test.Except impurity content difference in material, experimental condition is identical with catalyst application 1, the impurity composition 2ppm CO of propylene material, the CO of 5ppm
2with the H of 10ppm
2o, not containing other impurity in propylene.
Table 2 result of the test
From the Data Comparison of table 2, can find out:
Contrast 1 ~ 4
#with 7
#, when existing without MAPD in material, whether containing Bi in catalyst, on catalytic activity without impact.
Catalyst application 3
The present embodiment be under different material condition removal of carbon monoxide remove test.Except impurity content difference in material, experimental condition is identical with catalyst application 1, and the MAPD of impurity composition 2ppm CO and 10ppm of propylene material, not containing other impurity in propylene.
Table 3 result of the test
Contrast 1 ~ 4
#with 5 ~ 6
#, when existing without carbon dioxide and water in material, whether containing super acids in catalyst, catalytic activity is not had a significant effect.
Catalyst application 4
The present embodiment be under different material condition removal of carbon monoxide remove test.Except impurity content difference in material, experimental condition is identical with catalyst application 1, and the impurity composition 2ppm CO of propylene material, not containing other impurity in propylene.
Table 4 result of the test
Contrast 1 ~ 4
#with 5 ~ 8
#, when existing without carbon dioxide, water and MAPD in material, whether containing super acids and Bi in catalyst, catalytic activity is not had a significant effect.
Claims (7)
1. the super acids Modified Cu oxide catalyst for removal of carbon monoxide, it is characterized in that this catalyst comprises composite metal oxide and a kind of solid-state super acids of component (B) prepared by component (A) coprecipitation method, this catalyst can be expressed by the following formula: Cu
abi
bzn
cx
dy
eo
fwherein X is selected from least one element in manganese and antimony, Y selects at least one element in titanium and zirconium, a, b, c, d, e and f represent the atomic ratio number of its element, relative to Cu atom a=10, and 0<b≤1,0<c≤1,0<d≤30,0<e≤10, f is the number needed for the oxidation state meeting each component; B component is wherein selected from compound oxide type inorganic type super acids, super acids acid strength pKa<-11.94.
2. a kind of super acids Modified Cu oxide catalyst for removal of carbon monoxide according to claim 1, is characterized in that described solid-state super acids is selected from following at least one: with tungstic acid or the molybdenum trioxide load super acids at unformed zirconia or unformed titanium dioxide.
3. a kind of super acids Modified Cu oxide catalyst for removal of carbon monoxide according to claim 1, it is characterized in that described component (A) is prepared by following method: by copper mixing salt solution and alkali lye with and to flow or the form of anti-addition adds, control ph 6.0 ~ 10.0 and temperature 40 ~ 90 DEG C, afterwards aging, filter, washing, to add antimony oxide dry, obtains presoma sediment A.
4. a kind of super acids Modified Cu oxide catalyst for removal of carbon monoxide according to claim 3, it is characterized in that mantoquita, zinc compound, titanium compound/zirconium compounds and bismuth compound mix, then by mixed liquor and sodium salt and flow or or the form of anti-addition add, control ph is 6.0 ~ 10.0, reaction temperature is 40 ~ 90 DEG C, afterwards aging, filter, wash to sodium oxide content lower than 0.05%, add that antimony oxide is dry, roasting, obtain presoma sediment A.
5. a kind of super acids Modified Cu oxide catalyst for removal of carbon monoxide according to claim 1, is characterized in that the preferred titanium elements of Y, this titanium elements from unformed shape titanium oxide, the preferred antimony element of X.
6. the preparation method of a kind of super acids Modified Cu oxide catalyst for removal of carbon monoxide that one of claim 1-5 is described, comprises the following steps:
(1) component A cobalt composite oxide preparation: after mantoquita, zinc compound, titanium compound/zirconium compounds and bismuth compound are mixed with alkali lye also to flow or the form of anti-addition adds, control ph 6.0 ~ 10.0 and temperature 40 ~ 90 DEG C, afterwards aging, filter, washing, add that antimony oxide is dry, roasting, obtain presoma sediment A;
(2) preparation of B component super acids: a) zirconium hydroxide precipitate preparation adopts ammoniacal liquor to do precipitating reagent, obtained precipitated zirconium hydroxide, b) sour promoter steeps for and dries and grind the immersion of the sour promoter of rear employing, and sour promoter is dimolybdate salt or wolframic acid ammonium salt c) filter after the post processing such as roasting, dry and roasting;
(3) mixed-forming: after A and B mechanical mixture, carry out decomposing, granulation, roasting and compression molding.
7. a kind of super acids Modified Cu oxide catalyst for removal of carbon monoxide that one of claim 1-5 is described is in the application removing carbon monoxide in material.
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