CN104338543B - A kind of super acids Modified Cu oxide catalyst for removal of carbon monoxide - Google Patents
A kind of super acids Modified Cu oxide catalyst for removal of carbon monoxide Download PDFInfo
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Abstract
The invention discloses a kind of super acids Modified Cu oxide catalyst for removal of carbon monoxide. This catalyst comprises composite metal oxide and a kind of solid-state super acids of B component prepared by component A coprecipitation method, and this catalyst is expressed by the following formula: CuaBibZncXdYeOfWherein 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, with respect to Cu atom a=10,0<b≤1,0<c≤1,0<d≤30,0<e≤10, f is a number required by the oxidation state that meets each component. Catalyst of the present invention can be by the micro CO deep removal in olefin feed to 30ppb at 0 ~ 70 DEG C of reaction temperature.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method and application that removes micro CO for low temperature, more particularly, the present invention relates to a kind of for removing Catalysts and its preparation method and the application containing the micro CO of the olefin feed of plurality of impurities.
Background technology
Along with the development of polyolefin technology, highly active polyolefin catalyst, as very responsive to poisonous substance in metallocene catalyst etc., requiring polyolefin raw material is polymer grade raw material. In olefin feedstock, carbon monoxide impurity is no more than 30ppb specifically, therefore needs to develop a kind of catalyst 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 utilizing whereinxIn Lattice Oxygen come with material flow in reaction of carbon monoxide, instead of by the carbon monoxide in material and oxygen reaction; Metal oxide component MO in purification processxProgressively be reduced into elemental metals M and cause activity decreased.
In the time of deeply removing CO, need to improve on the one hand the reactivity of the catalyst of removal of carbon monoxide, need on the other hand to consider olefin feed as ethene, propylene self with trace impurity will significantly reduce the activity of catalyst as water and carbon dioxide etc.
Prior art often adopts copper Containing Oxide Catalyst, and its principle is utilized wherein component CuOxIn Lattice Oxygen react with CO in material flow, instead of by the carbon monoxide in material and oxygen reaction; CuO in purification processxProgressively be reduced into simple substance Cu and cause activity decreased. Prior art reckons without other trace impurities to removing the impact of CO. Have and require to remove the degree of depth high in the situation that at a large amount of trace impurities, needing to consider is not the catalytic activity that how to improve prior art, needs to consider the anti-trace impurity poisoning performance of existing catalysis technique yet.
Super acids is also strong solid acid of a kind of ratio 100% sulfuric acid, 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 sulfate radical type solid acid (SO of two classes as described in CN14212704 2-/ZrO2) and CN1394677 described in composite oxides type solid acid (WO3/ZrO2And MO3/ZrO2), as be mainly used in hydro carbons alkylation, isomerization and esterification. The most frequently used method of mensuration of solid super strong acid strength is Hammett indicator method and Temperature Programmed Desorption (TPD). In indicator method is measured, H0The PKa of indicator is less than-11.94, could determine that like this surface of solids exists super acids. Adopt TPD method to measure, calculate total acid content by the amount of calculating B acid and L acid, thereby determine whether to exist super acids, in addition as Tang Xinshuo (SO4 2-/ZrO2Type 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 acid of the L in super acids under certain condition 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, ZrO used2、TiO2And Fe2O3The oxide acidity making Deng oxide is large, adopts Al2O3And SnO2Can only be strong solid acids Deng the oxide obtaining, and use SiO2、Bi2O3, CuO, ZnO and MnO2The acidity of catalyst of making Deng oxide is very weak. There is no at present the application of super acids aspect Oxidation of Carbon Monoxide or purification.
As Pan Shengyun etc., (propylene is at SO4 2-/MxOyThe research of the oligomerisation process on solid super acid catalyst, Chemical Engineering and Technology, 1995, vol (1), 342～347) propose, be 1.0hr-1 and density of propylene while being 50% at 130 DEG C, 4.0MPa, LHSV, propylene conversion is up to 69.5%, nonene and laurylene selectively respectively approximately 45.5 and 41.6%. Super acids need be considered the problem of olefin(e) oligomerization for the purification of olefin feed stream, this may be also that prior art is not considered one of possible cause adopting solid super-strong acid.
But the reacting quintessence that removes of trace amounts of CO is a chemisorbed process, the CO in material flow reacts with the active oxidation in CuO in catalyst. In view of the reaction temperature of this reaction is lower, 0～120 DEG C even can be reacted 50 DEG C of left and right, therefore can't cause the oligomerisation of alkene in so low temperature introducing super acids; Also minimum even negligible owing to removing the reaction heat that the CO of ppm magnitude produces on the other hand, therefore this reaction also can be considered catalyst stability, is better than the amorphous material of crystalline material and adopt in the time of 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 is to improve to remove the catalytic activity of CO in the material flow that contains minor amount of water, carbon dioxide, alkynes (or MAPD), thereby reaches the effect of the carbon monoxide in deep removal olefin feed stream.
Concrete technical scheme is as follows:
One of 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: CuaBibZncXdYeOfWherein 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, with respect to Cu atom a=10,0 <b≤1,0 < c≤1,0 < d≤30,0 < e≤10, f is a number required by the oxidation state that meets 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: the super acids that loads on unformed Zirconia carrier or unformed titania support with tungstic acid or molybdenum trioxide.
Component A is prepared by following methods: mantoquita, zinc compound, titanium compound/zirconium compounds and bismuth compound are mixed, then the form of mixed liquor and sodium salt stream or anti-addition is added, controlling pH value is 6.0～10.0, reaction temperature is 40～90 DEG C, afterwards aging, filter, wash to sodium oxide content lower than 0.05%, interpolation antimony oxide is dry, roasting, obtains presoma sediment A.
It is generally acknowledged that the reaction mechanism that removes trace amounts of CO is, the reaction of carbon monoxide in Lattice Oxygen and material flow in catalyst, 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, same this reaction atypical catalytic reaction process, this catalyst should be referred to as " adsorbent " more precisely, is still referred to as traditionally catalyst.
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, Zn as selected in the present invention and unformed titanium or Zirconium oxide as carrier; 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 is because heat release is 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 improve catalyst activity. Be the reasonably combined of the multiple oxide that appraises at the current rate by composite oxides on the other hand, improved better the mobility of Lattice Oxygen, as selected X component (selecting at least one element in manganese and antimony). In addition suppress the absorption (as the impact that is often considered as reducing acetylene or propine that adds of Bi) of alkynes by Bi component, thereby reduce the impact of alkynes on 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 A component copper composite oxides. Mantoquita, zinc compound, titanium compound/zirconium compounds and bismuth compound mix, then the form of mixed liquor and sodium salt stream or anti-addition is added, controlling pH value is 6.0～10.0, reaction temperature is 40～90 DEG C, afterwards aging, filter, wash to sodium oxide content lower than 0.05%, interpolation antimony oxide is dry, roasting, obtains presoma sediment A.
The preparation of second step B component solid super-strong acid. The preparation of step a) zirconium hydroxide precipitate, adopt ammoniacal liquor to do precipitating reagent, make zirconium hydroxide precipitation, b) zirconium hydroxide precipitate adopts the immersion of sour promoter after drying and grinding, acid promoter is dimolybdate salt or wolframic acid ammonium salt, c) filters afterwards, oven dry and roasting;
The 3rd step mixed-forming is after component A and B component mechanical mixture, decomposes, granulation, roasting and compression molding. Concentration and the sintering temperature of acid promoter are outbalance influence factors, and the concentration of sour promoter is generally chosen 0.1～3M, and sintering temperature is generally chosen 200～450 DEG C.
Consider that the issuable carbon dioxide of material neutralization reaction process reacts with micro-steam, likely form the carbanion of 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, thereby suppress active. 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.
The 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, 0～70 DEG C of temperature, be preferably under 20～65 DEG C and pressure 0.1～5MPa, make to contact to remove the carbon monoxide in charging containing the charging of 0.1ppm～5ppm carbon monoxide and other impurity with described catalyst, when gas-phase feed, gaseous phase volume air speed is 1～10,000h-1; When liquid phase feeding, liquid phase volume air speed is 0.1～100h-1. Described charging is ethene, propylene or liquid propylene. Described charging is to contain micro-unsaturated alkyne, carbon dioxide and water. Described unsaturated alkyne is as impurity such as acetylene, propine and butine, and wherein the content of alkynes impurity is 0.01～100ppm, is preferably 0.05～10ppm, 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, related content, for example %, ppm and ppb are by weight; Described solution all refers to the aqueous solution.
Catalyst of the present invention has following beneficial effect:
1. improved the activity of the catalyst of removal of carbon monoxide;
2. other impurity in material have been avoided, as the negative effect to catalyst activity of unsaturated alkyne, carbon dioxide and water.
Detailed description of the invention
In embodiments of the invention, the method for testing of relevant data is as follows:
XRD(X-raydiffraction, X-ray diffraction): adopt the XpertMPD type X-ray diffractometer analysis of catalyst phase structure of Dutch Philips company, radiation source is CuK α, and sweep limits is 20～80 DEG C. Adopt Scherrer formula to calculate size of microcrystal.
Specific surface test: adopt the physical adsorption appearance of the Nova3000e of Kang Ta company of the U.S., carry out specific surface area analysis. At liquid nitrogen temperature-196 DEG C, use N2Determination of adsorption method surface area and pore-size distribution, sample vacuumizes pretreatment to pressure and is less than 10 at 300 DEG C-3Pa, assay method is static method. Adopt BET method to calculate specific surface according to adsorption isotherm.
Super acids acid strength assay method: adopt the general super acids acid strength measuring method of prior art. Detailed process is: tested sample is immersed in benzole soln, and add the not acidity indicator of known pKa of the same race. The minimum pKa value that presents 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, antimony oxide, manganese nitrate, zinc nitrate, sodium carbonate, ammoniacal liquor, zirconium oxychloride and bismuth nitrate in embodiment, be analysis pure, purchased from recover chemical reagent Co., Ltd in Tianjin; Butyl titanate, ammonium tungstate and metamolybdic acid ammonium be analyze pure, purchased from Beijing chemical reagent factory.
Further explain the preferred embodiment in the scope of the invention in the mode of embodiment below.
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 the sodium carbonate liquor of mixed liquor and 1 mol/L stream are joined in the container of 30L to precipitate, precipitation temperature is 80 DEG C, and pH value is controlled at 8.5 ± 0.5. Then in strong agitation situation aging 2 hours, aging temperature was 80 DEG C. Then filter, at 80 DEG C, wash at least six times by deionized water, to Na2O content, lower than 0.05%, adds antimony oxide afterwards in filter cake. At 110 DEG C, be dried 12 hours, at 350 DEG C, roasting 4 hours, makes component A.
By the zirconium oxychloride wiring solution-forming of 1M, make precipitating reagent with 1M ammoniacal liquor, make zirconium hydroxide precipitation, through oven dry precipitation and levigate after ammonium tungstate solution immersion, filtration, 110 DEG C of oven dry, the 350 DEG C of roasting 4h of use 0.5mol/L, make B component. By A and the moulding of B two parts mixed pressuring plate, obtain 75wt%CuO/10wt%ZnO/0.5wt%Bi2O3/0.5wt%Sb2O3/5wt%WO3/9wt%ZrO2, be labeled as 1#Catalyst. Analyze through BET, specific surface is 125m2/ g, acid strength is-12.4.
Embodiment 2
Adopt the mode Kaolinite Preparation of Catalyst identical with embodiment 1, different: to adopt butyl titanate, replace zirconium oxychloride, obtain 75wt%CuO/10wt%ZnO/0.5wt%Bi2O3/0.5wt%Sb2O3/5wt%WO3/9wt%TiO2，2#Catalyst. Analyze through BET, specific surface is 128m2/ g, acid strength is-12.0.
Embodiment 3
Adopt the mode Kaolinite Preparation of Catalyst identical with embodiment 1, different: to adopt metamolybdic acid ammonium to replace ammonium tungstate, obtain 75wt%CuO/10wt%ZnO/0.5wt%Bi2O3/0.5wt%Sb2O3/5wt%MoO3/9wt%ZrO2, be labeled as 3#Catalyst. Analyze through BET, specific surface is 132m2/ g, acid strength is-12.4.
Embodiment 4
Adopt the mode Kaolinite Preparation of Catalyst identical with embodiment 1, by changing solution component proportioning, obtain 65wt%CuO/18wt%ZnO/0.1wt%Bi2O3/0.1wt%Sb2O3/1.8wt%MoO3/15wt%ZrO2, be labeled as 4#Catalyst. Analyze through BET, specific surface is 225m2/ g, acid strength is-12.4.
Comparative example 1
The preparation of A part is identical with embodiment 1, does not add B part.
Make 75wt%CuO/15wt%ZnO/0.5wt%Bi2O3/0.5wt%Sb2O3/9wt%ZrO2, be labeled as 5#Catalyst. Analyze through BET, specific surface is 125m2/ g. Acid strength is not measured, and thinks and is not super acids.
Comparative example 2
The preparation of A part is identical with embodiment 2, does not add B part.
Obtain 75wt%CuO/15wt%ZnO/0.5wt%Bi2O3/0.5wt%Sb2O3/9wt%TiO2, be labeled as 6#Catalyst. Analyze through BET, specific surface is 128m2/ g. Acid strength is not measured, and thinks and is not super acids.
Comparative example 3
Adopt the mode Kaolinite Preparation of Catalyst identical with embodiment 1, different: not add Bi, obtain 75wt%CuO/10.5wt%ZnO/0.5wt%Sb2O3/5wt%WO3/9wt%ZrO2, be labeled as 7#Catalyst. Analyze through BET, specific surface is 125.4m2/ g, acid strength is-12.4.
Comparative example 4
Adopt the mode Kaolinite Preparation of Catalyst identical with embodiment 1, different: not add Sb, obtain 75wt%CuO/10.5wt%ZnO/0.5wt%Bi2O3/5wt%WO3/9wt%ZrO2, be labeled as 8#Catalyst. Analyze through BET, specific surface is 126m2/ g, acid strength is-12.4.
Comparative example 5
Adopt the mode Kaolinite Preparation of Catalyst identical with embodiment 1, different: in preparation process, not add zirconium oxychloride, add crystal of zirconium oxide and mix with filter cake, obtain 75wt%CuO/10.5wt%ZnO/0.5wt%Sb2O3/5wt%WO3/9wt%ZrO2, be labeled as 9#Catalyst. Analyze through BET, specific surface is 25m2/ g. Acid strength is not measured, and thinks and is not super acids.
The application 1 of catalyst
With embodiment 1～4 and the prepared catalyst of comparative example 1～5, carry out respectively the test that removes of trace amounts of CO. In fixed bed continuous-flow tubular reactor, carry out evaluating catalyst 1000 hours. 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 propylene containing 2ppmCO, contains in addition the carbon dioxide of 5ppm, water, the propine of 3ppm and the allene of 5ppm of 10ppm. 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 with the micro CO analyzer detection of AMETEK company. Result of the test is listed in table 1.
Table 1 result of the test
As seen from Table 1,
(1) contrast 1～3#With 5～6#Catalyst. Do not add super acids, catalyst activity obviously reduces.
(2) contrast 1#With 7#Catalyst, does not add Bi, and catalyst activity obviously reduces.
(3) contrast 1#With 8#Catalyst, does not add Sb, and catalyst activity slightly reduces.
(4) contrast 1#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. In material impurity content difference, it is 1 identical that experimental condition and catalyst are applied, the impurity composition 2ppmCO of propylene material, the CO of 5ppm2H with 10ppm2O, does not contain 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#, in the time existing without MAPD in material, in catalyst, whether contain Bi, on catalytic activity without impact.
Catalyst application 3
The present embodiment be under different material condition removal of carbon monoxide remove test. In material impurity content difference, it is 1 identical that experimental condition and catalyst are applied, the impurity composition 2ppmCO of propylene material and the MAPD of 10ppm, in propylene containing other impurity.
Table 3 result of the test
Contrast 1～4#With 5～6#, in the time existing without carbon dioxide and water in material, in catalyst, whether contain super acids, 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. In material impurity content difference, it is 1 identical that experimental condition and catalyst are applied, the impurity composition 2ppmCO of propylene material, in propylene containing other impurity.
Table 4 result of the test
Contrast 1～4#With 5～8#, in the time existing without carbon dioxide, water and MAPD in material, in catalyst, whether contain super acids and Bi, catalytic activity is not had a significant effect.
Claims (6)
1. for a super acids Modified Cu oxide catalyst for removal of carbon monoxide, it is characterized in that this catalysisAgent comprises composite metal oxide and a kind of solid-state super acids of component (B) prepared by component (A) coprecipitation method,(A) is expressed by the following formula for this Components of Catalysts: CuaBibZncXdYeOf, wherein X is antimony, Y selects titaniumWith at least one element in zirconium, a, b, c, d, e and f represent the atomic ratio number of its element, with respect to CuAtom a=10,0 <b≤1,0 < c≤1,0 < d≤30,0 < e≤10, f is required by the oxidation state that meets each componentOne number; Component (B) is wherein selected from compound oxide type inorganic type super acids, super acids acid strengthpKa<-11.94。
2. a kind of super acids Modified Cu oxide catalysis for removal of carbon monoxide according to claim 1Agent, is characterized in that described solid-state super acids is selected from following at least one: with tungstic acid or molybdenum trioxideLoad on the super acids of unformed zirconia or unformed titanium dioxide.
3. a kind of super acids Modified Cu oxide catalysis for removal of carbon monoxide according to claim 1Agent, is characterized in that described component (A) is prepared by following method: by mantoquita, zinc compound,Titanium compound/zirconium compounds and bismuth compound mix, then by the shape of mixed liquor and sodium salt stream or anti-additionFormula adds, and controlling pH value is 6.0～10.0, and reaction temperature is 40～90 DEG C, afterwards aging, filter, washTo sodium oxide content, lower than 0.05%, interpolation antimony oxide is dry, roasting, obtains component (A).
4. a kind of super acids Modified Cu oxide catalysis for removal of carbon monoxide according to claim 1Agent, is characterized in that Y is titanium elements, and this titanium elements is from unformed shape titanium oxide.
5. the described a kind of super acids Modified Cu oxide for removal of carbon monoxide of one of claim 1-4 is urgedThe preparation method of agent, comprises the following steps:
(1) preparation of component (A) composite metal oxide: by mantoquita, zinc compound, titanium compound/zirconiumAfter compound and bismuth compound mix with alkali lye with and stream or the form of anti-addition add, control pH value 6.0～10.0 and 40～90 DEG C of temperature, afterwards aging, filter, washing, add that antimony oxide is dry, roasting, obtain groupDivide (A);
(2) preparation of component (B) super acids: a) zirconium hydroxide precipitate preparation adopts ammoniacal liquor to do precipitating reagent,Make zirconium hydroxide precipitation, b) sour promoter is soaked: after drying and grinding, adopt the immersion of sour promoter, acidPromoter is dimolybdate salt or wolframic acid ammonium salt, c) post processing: filter afterwards, oven dry and roasting;
(3) mixed-forming: by after component (A) and component (B) mechanical mixture, decompose, granulation,Roasting and compression molding.
6. the described a kind of super acids Modified Cu oxide for removal of carbon monoxide of one of claim 1-4 is urgedAgent is removing the application of carbon monoxide in material.
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| US6204218B1 (en) * | 1998-09-04 | 2001-03-20 | Basf Aktiengesellschaft | Catalyst and process for purifying streams of materials |
| CN101642707A (en) * | 2008-08-07 | 2010-02-10 | 中国石油化工股份有限公司 | Bi-component copper-zirconium catalyst for deeply removing CO |
| CN101722009A (en) * | 2008-10-24 | 2010-06-09 | 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 |
| CN102728366A (en) * | 2011-04-02 | 2012-10-17 | 中国石油化工股份有限公司 | Silanization treated carbon monoxide removal catalyst, and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6204218B1 (en) * | 1998-09-04 | 2001-03-20 | Basf Aktiengesellschaft | Catalyst and process for purifying streams of materials |
| CN101642707A (en) * | 2008-08-07 | 2010-02-10 | 中国石油化工股份有限公司 | Bi-component copper-zirconium catalyst for deeply removing CO |
| CN101722009A (en) * | 2008-10-24 | 2010-06-09 | 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 |
| CN102728366A (en) * | 2011-04-02 | 2012-10-17 | 中国石油化工股份有限公司 | Silanization treated carbon monoxide removal catalyst, and preparation method and application thereof |
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