CN102773103A - Catalyst for deeply removing CO at low temperature as well as preparation and activation methods and application thereof - Google Patents
Catalyst for deeply removing CO at low temperature as well as preparation and activation methods and application thereof Download PDFInfo
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- CN102773103A CN102773103A CN2012102830826A CN201210283082A CN102773103A CN 102773103 A CN102773103 A CN 102773103A CN 2012102830826 A CN2012102830826 A CN 2012102830826A CN 201210283082 A CN201210283082 A CN 201210283082A CN 102773103 A CN102773103 A CN 102773103A
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Abstract
The invention relates to a catalyst for deeply removing CO at low temperature as well as the preparation and activation methods and the application thereof. The catalyst is the CuO-ZnO-ZrO2 composite catalyst which comprises 50-90wt% of CuO, 5-40wt% of ZnO and 5-40wt% of ZrO2. The copper-containing component has the reduction degree of 70-80%, and the reduction degree is represented by the ratio of the weight of the metallic copper to the total weight of the metallic copper and the copper oxide calculated according to the CuO. Compared with the prior art, the catalyst is used for removing the CO in the liquid or gaseous hydrocarbon and/or inert gas and has the characteristics of high activity at low temperature of 0-50 DEG C, high removal depth of 20ppb or lower and long service life. The process for preparing the catalyst is simple, and the cost spent in preparing the catalyst can be lowered.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method, activation method and application that from hydrocarbon or inert gas material, removes CO.The present invention is specially adapted in the petrochemical industry removing of trace amounts of CO in the alpha-olefin and saturated hydrocarbons, or the high-purity gas of electronics industry (like nitrogen, helium, argon gas etc.) preparation.
Background technology
At various industrial circles, the existence of micro CO, often harmful to reaction system, need remove as impurity.Along with the development of polyolefin technology, highly active polyolefin catalyst is very responsive to poisonous substance, and requiring the polyolefin raw material is " polymer grade " alkene, and carbon monoxide impurity is no more than 30ppb in the olefin feedstock specifically.The typical case has propylene polymerization technology, and along with the development of catalyst for polymerization of propylene, polymerisation is very responsive to various impurity in the reaction system, and wherein, CO can get into polymeric chain, influences the capacity of orientation of catalyst; Polymeric chain is stopped, reduce activity of such catalysts.In electronics industry, semiconductor components and devices manufacture view particularly needs the high-purity gas of " electronics is pure ", and contained carbon monoxide impurity requires to be lower than several ppb.
Prior art removes that the method for trace amounts of CO has the way of distillation and catalytic oxidation in the alkene.Yet installation destilling tower fund cost is high, running cost is expensive, and can't the content of CO be dropped to " polymer grade " level.And the low-temperature catalytic oxidation of CO be the most directly, simple, cheap and effectively eliminate the ways and means of CO.Advantages such as this method is simple to operate, with low cost owing to it, deep removal, very attractive to industrializing implementation.Mostly be liquid phase process based on domestic polymarization method for prodcing polyacrylates, so Catalyst for CO low temperature removes performance and have great importance, otherwise certainly will cause problems such as the device flow process increases, equipment investment increases, operation inconvenience.But the reaction temperature that big multi-catalyst is suitable for is higher, can only be applicable to gas-phase polymerization process.
Early being applied to the catalyst that micro CO removes is noble metal catalyst, and the typical case has Au, Pd, Pt etc., and particularly the Au catalyst has good low temperature active, under low temperature and even room temperature condition, the carbon monoxide oxidation reaction can take place.Disclose a kind of catalyst like US5662873, key component is Au, Ag or both, or at least a in the platinum family element, can be with the micro-H in the inert gas under 80～130 ℃
2With CO and O
2Reaction makes H
2Be lower than 10ppb, CO is lower than 5ppb.CN101371984A discloses a kind of main active component A u and has loaded on the catalyst on carrier such as the diatomite, can under room temperature to 70 ℃ condition, trace amounts of CO in alkene or the saturated hydrocarbons logistics be oxidized to CO
2Remove, but require institute to remove in the logistics CO content less than 5ppm.Yet this type of catalyst adopts like noble metals such as Au, Pd, Pt, costs an arm and a leg, and is unfavorable for industrial applications.
Non-precious metal catalyst such as copper-based catalysts remove at industrial micro CO and have a wide range of applications.The typical case has the Hopcalite catalyst that is applied to breathing mask; Belong to the copper manganese series catalyzer, have very high activity, yet this catalyst is very responsive to water for carbon monoxide and oxygen reaction; Easy inactivation under the situation that steam exists, and must have oxygen to exist.
US5625116 disclose a kind of from alpha-olefin and saturated hydrocarbons the method below the deep removal CO to 0.03ppm, this catalyst belongs to the copper chromium-based catalysts, this catalyst preparation process adopts chromic salts, environmental pollution is serious, is not suitable for large-scale industrial application.
WO95/21146 discloses a kind of cupric or copper Mn catalyst; While removal of carbon monoxide and arsenic from hydrocarbon material; Can under low temperature to 40 ℃, carbon monoxide be removed to less than 1ppb, be the situation of tens of ppb yet this catalyst is fit to the content of CO in the material handling, when the content of CO in the material reaches the ppm magnitude; Remove depth value and become big, only can use about one month simultaneously.
CN1044599C discloses a kind of copper zinc catalyst (being the domestic BR9201 catalyst that has been applied in the industry), from alpha-olefin and saturated hydrocarbons, removes CO only to 0.1ppm; For deep removal CO, this catalyst still need improve.
CN1681583A and US2005/0241478 disclose a kind of adsorbent of copper zinc zirconium and from streams, have removed carbon monoxide; This adsorbent only can be removed carbon monoxide with the mode of absorption; The more important thing is the degree of depth that removes that does not have embodiment to come clear reaction condition and trace amounts of CO, also do not know the service life of this adsorbent etc.
CN101642707A and CN101462057A disclose three component catalysts of a kind of bi-component copper-zirconium catalyst or cupric zirconium, can the propylene that contain 5ppm CO be removed to below the 30ppb under gas phase and liquid phase state.Yet disclosed is the preparation of catalyst precursor, clearly unsuitable activation method, and this is a requisite key technology in such Preparation of Catalyst.
Therefore, need a kind of low temperature high activity of development, high stability, synthetic simultaneously cost is low, be easy to industrialized micro CO deep purifying catalyst, and studies its activation method and reaction process, industry practice such as polyolefin used have great importance.
Summary of the invention
The object of the invention is exactly to provide in order to overcome the defective that above-mentioned prior art exists that a kind of cost is low, Catalysts and its preparation method, activation method and the application of the low temperature deep removal CO that is easy to industrialization.
The object of the invention can be realized through following technical scheme: the catalyst of a kind of low temperature deep removal CO is characterized in that this catalyst is by CuO, ZnO, ZrO
2Composite oxides form CuO-ZnO-ZrO
2Composite catalyst is 100% in total catalyst weight, wherein CuO:50～90wt%; ZnO:5～40wt%; ZrO
2: 5～40wt%, wherein to have reduction degree be 70～80% to the cupric component, said reduction degree is to represent in metallic copper and metallic copper with the weight ratio of the summation of the Cu oxide of CuO.
The Preparation of catalysts method of a kind of low temperature deep removal CO is characterized in that, this method may further comprise the steps:
(1) preparation of slaine and aqueous slkali: take by weighing a certain amount of mantoquita, zinc salt, zirconates and water, mix after being mixed with mantoquita, zinc salt and the zirconium salt solution that concentration is 0.2～3mol/L respectively, be stirred well to evenly, obtain mixing salt solution, with CuO, ZnO and ZrO
2Meter, wherein CuO50～90wt%, ZnO5～40wt%, ZrO
25～40wt%; Take by weighing alkali and water, be mixed with the aqueous slkali that concentration is 0.2～3mol/L;
(2) deposition: mixing salt solution and aqueous slkali that step (1) is made adopt cocurrent process or suitable addition hybrid reaction, obtain deposition and are catalyst precursor;
(3) aging: the catalyst precursor of step (2) gained is fully stirred, under 60～85 ℃ of temperature, aging 30～240min;
(4) with step (3) gained deposition through cyclic washing, centrifugal after in 110 ℃ of dry 12-16h;
(5) with the product after step (4) oven dry in 300～600 ℃ of roastings 6 hours, promptly get CuO-ZnO-ZrO
2Composite catalyst.
The described mantoquita of step (1) comprises one or more in copper nitrate, copper sulphate, Schweinfurt green or the copper chloride; Described zinc salt comprises one or both in zinc nitrate or the zinc sulfate, and described zirconates comprises one or more in zirconium nitrate, zirconium sulfate, zirconium oxychloride or the acetic acid zirconium; Described alkali comprises one or more in sodium carbonate, sodium acid carbonate, NaOH, ammoniacal liquor or the ammonium carbonate.
Described mantoquita is a copper nitrate, and described zinc salt is a zinc nitrate, and described zirconates is a zirconium nitrate, and described alkali is ammonium carbonate.
The described cocurrent process of step (2) is: mixing salt solution and aqueous slkali are added in the container simultaneously, under 50～85 ℃ of temperature, react, deposition pH value 6.0～8.0, the mol ratio of mixing salt solution and aqueous slkali addition 1: 1;
Described along addition for aqueous slkali is added in the salting liquid, under 50～85 ℃ of temperature, react titration end-point pH value 6.0～8.0.
The temperature of the described roasting of step (5) is 320～500 ℃.
Step (5) gained CuO-ZnO-ZrO
2Can mix with adhesive before composite catalyst uses, through stone roller and after compression molding, screening, to be activated; Described adhesive is the various adhesives that shaping of catalyst can be used, and the addition of adhesive is 0.1～5wt%.
Described adhesive is a graphite.
Preparation of catalysts method of the present invention, the preferred sal volatile of the aqueous slkali of dropping adopts ammonium carbonate to M (NO
3) catalyst that makes of x coprecipitation, the active ingredient copper good dispersion degree, surface active composition content is high, has redox property preferably, therefore adopts ammonium carbonate to M (NO
3) to take off the CO catalyst better for x coprecipitation preparation.
Preparation of catalysts method of the present invention, the preferred cocurrent process of the coprecipitation mode of salting liquid and aqueous slkali, the catalyst that adopts cocurrent process to prepare, the crystal composition homogeneous of formation, ZrO
2Exist with amorphous component, the active ingredient copper decentralization is high.
The activation method of the catalyst of a kind of low temperature deep removal CO is characterized in that, this method is: with said catalyst at 1～10%H
2Constant temperature after being warming up to 120～220 ℃ in the/inert gas flow, reduction 1～12h.
Preferred 160 ℃ of described reduction temperature, preferred 3～6h of recovery time, the activated back of described catalyst reduction degree is 70～80%, said reduction degree is to represent in metallic copper and metallic copper with the weight ratio of the summation of the Cu oxide of CuO.
For catalyst of the present invention, reduction activation is absolutely necessary a step, if reduce improper; Can cause the sintering of catalyst maybe can not reach reducing condition preferably; Catalyst such as activation that potential is good again are bad, and activity can be not high, even can cause reacting the termination of operation.With the Cu in the said catalyst
2+Partly be reduced to Cu
+, Cu, and activation is to certain reduction degree.Said reduction degree is to represent in metallic copper and metallic copper with the weight ratio of the summation of the Cu oxide of CuO:
Metallic copper
Metallic copper+in the Cu oxide of CuO
CuO-ZnO-ZrO
2The reduction degree of CuO can be measured by three kinds of methods in the catalyst: (1) H
2H among the-TPR
2Consumption; (2) O in the thermogravimetric
2The weight that loses; (3) detect the amount of CuO minimizing and the amount that Cu generates among the XRD.
The activation method of catalyst of the present invention, preferred 160 ℃ of reduction temperature.Different reduction temperatures can make active Cu species change at surface distributed, the valence state of catalyst.Reduction temperature is 160 ℃ can make its active Cu species partial reduction, and suitable reduction degree is 70～80%.
The Application of Catalyst of a kind of low temperature deep removal CO; It is characterized in that; With said catalyst applications trace amounts of CO in removing hydrocarbon and/or inert gas, concrete grammar is: in temperature is 0～150 ℃, and reaction pressure is under the condition of 0.1～5MPa; Make the material that contains trace amounts of CO contact liquid phase air speed 0.1～100h with said catalyst
- 1, gas phase air speed 10～100000h
-1, the CO that removes in the material makes its content≤20ppb.
Described catalyst is converted into CO with CO
2, the said material that contains trace amounts of CO comprises alpha-olefin, saturated hydrocarbons, cinnamic gas phase or liquid phase or N
2, the content of CO is 0.02ppm～1000ppm in the described material that contains trace amounts of CO; When the described material that contains trace amounts of CO was the liquid phase state hydrocarbon, reaction temperature was 0～50 ℃.
Preferred 0.02ppm～the 100ppm of content of CO in the described material that contains trace amounts of CO.
Of the present invention remove hydrocarbon with or inert gas in Catalysts and its preparation method, activation and the application of micro CO, compared with prior art have the following advantages:
One, Preparation of catalysts method of the present invention, the catalyst activity constituent content that makes is big and decentralization is high, has improved the remove degree of depth of catalyst to CO greatly, can be in big content range CO be removed to be low to moderate 20ppb; Preparation process is simple simultaneously, has reduced the Preparation of catalysts cost, is easy to suitability for industrialized production.
Two, catalyst low-temperature activity of the present invention is high, can be particularly useful for hydrocarbon to remove at liquid phase state in low temperature even normal temperature (0～50 ℃) operation down, can shorten the device flow process, reduces equipment investment.
Three, the activation method of catalyst of the present invention, activation effect is good, and the activity of such catalysts component is controlled at more excellent reducing condition effectively, has more excellent CO after making catalyst precursor activated to remove performance.
The specific embodiment
Embodiment 1～7
CuO/ZnO/ZrO
2The preparation of composite oxide catalysts presoma
According to proportioning: CuO: ZnO: ZrO
2=x: y: (1-x-y) take by weighing raw material, x, y value are weight percentage, and be as shown in table 1.
After the nitrate of Cu, Zn, Zr metal is prepared into certain density solution, mix under stirring; Precipitate under stirring and uniform temperature through certain coprecipitation mode and sal volatile, after deposition finishes, the pH value of regulation system; The catalyst precursor of gained is aging at a certain temperature, fully stir; Take out solid product with the deionized water cyclic washing of uniform temperature, centrifugal after, place 110 ℃ of dried overnight of drying box hollow air-flow; 350～550 ℃ of following roastings 6.0 hours, be cooled to room temperature, promptly get the CuO/ZnO/ZrO of roasting
2The composite oxides product;
Wherein coprecipitation mode comprises cocurrent process; Along addition, described cocurrent process is: mixing salt solution and aqueous slkali are added in the container simultaneously, under 50～85 ℃ of temperature, react; Deposition pH value 6.0～8.0, the mol ratio of mixing salt solution and aqueous slkali addition is 1: 1;
Described along addition for aqueous slkali is added in the salting liquid, under 50～85 ℃ of temperature, react titration end-point pH value 6.0～8.0.
Comparative example 1～2
According to proportioning: CuO: ZnO=x: (1-x) take by weighing raw material, the x value is weight percentage, and is as shown in table 1.
After the nitrate of Cu and/or Zn metal is prepared into certain density solution, mix under stirring; Precipitate under stirring and uniform temperature through certain coprecipitation mode and aqueous slkali, after deposition finishes, the pH value of regulation system; The catalyst precursor of gained is aging at a certain temperature, fully stir; Take out solid product with the deionized water cyclic washing of uniform temperature, centrifugal after, place 110 ℃ of dried overnight of drying box hollow air-flow; 350～550 ℃ of following roastings 6.0 hours, be cooled to room temperature, promptly get comparative sample;
Table 1 Preparation of Catalyst experimental result
The XRD test shows, the ZrO among gained embodiment 1, embodiment 3, the embodiment 5～7
2Exist with amorphous.With instance 5 is example, sees table 2.
Table 2 embodiment 5XRD data
Confirm that from table 1 composition of composite oxides, precipitating reagent, coprecipitation mode and sintering temperature are different, the decentralization of synthetic product crystalline form, copper particle and reducible character are different.Control more excellent preparation factor, can synthesize the CuO/ZnO/ZrO that obtains having greater activity copper decentralization and easy reduction
2Composite oxide catalysts removes performance thereby have more excellent CO.
Embodiment 8～11
CuO/ZnO/ZrO
2The activation of composite oxide catalysts
To after implementing 5 composite oxide catalysts that make and carrying out compressing tablet, fragmentation, the sieve particle that sieves out 80～100 order granularities carries out activation.
Fixed-bed catalytic reactor is adopted in activation, and reactor is a stainless steel tube, and the catalyst that embodiment 5 is prepared carries out reduction activation; The used process conditions of activation are: loaded catalyst 3mL, and activation temperature is 100～200 ℃, pressure is normal pressure; Soak time 4h, raw material are 10%H
2/ N
2, volume space velocity is 4000 hours
-1Through characterizing, different activation temperatures are as shown in table 3 to the reduction degree influence of catalyst.
Table 3 activation results
Embodiment 12
The examination that trace amounts of CO low temperature removes in the hydrocarbon
Adopt fixed-bed catalytic reactor; Reactor is a stainless steel tube, the catalyst of embodiment 8～11 is carried out CO respectively remove the performance examination, checks and rates used process conditions and is: loaded catalyst 3mL; Reaction temperature is 40 ℃; Reaction pressure is 3MPa, and raw material is the liquid propylene that contains 20ppm CO, and the liquid phase air speed is 8.0 hours
-1Product adopts helium ion detector GC9560 on-line analysis through after reducing pressure, and appraisal result is as shown in table 4.
The result that trace amounts of CO removes in table 4 liquid propylene
Embodiment 13
The stability examination that trace amounts of CO low temperature removes in the hydrocarbon
Adopt fixed-bed catalytic reactor; Reactor is a stainless steel tube, and the catalyst of embodiment 10 is carried out the examination that CO removes performance for stability, checks and rates used process conditions and is: loaded catalyst 3mL; Reaction temperature is 40 ℃; Reaction pressure is 3MPa, and raw material is the liquid propylene that contains 20ppm CO, and the liquid phase air speed is 8.0 hours
-1Product adopts helium ion detector GC9560 on-line analysis through after reducing pressure.
CO can remove and be low to moderate≤20ppb, moves 2 months continuously, and catalyst stability is good.
Embodiment 14
The Preparation of catalysts method of a kind of low temperature deep removal CO, this method may further comprise the steps:
(1) preparation of slaine and aqueous slkali: take by weighing a certain amount of copper sulphate, zinc sulfate, zirconium sulfate and water, being mixed with concentration respectively is to mix behind the 0.5mol/L salting liquid, is stirred well to evenly, obtains mixing salt solution, with CuO, ZnO and ZrO
2Meter, wherein CuO 50wt%, ZnO 40wt%, ZrO
210wt%; Take by weighing sodium acid carbonate and water, be mixed with the sodium bicarbonate solution that concentration is 0.5mol/L;
(2) deposition: mixing salt solution and aqueous slkali that step (1) is made add in the container simultaneously, under 50 ℃ of temperature, react, and precipitate pH value 6.0～8.0, and the mol ratio of mixing salt solution and aqueous slkali addition is 1: 1;
(3) aging: the catalyst precursor of step (2) gained is fully stirred, under 60 ℃ of temperature, aging 240min;
(4) with step (3) gained deposition through cyclic washing, centrifugal after in 110 ℃ of dry 12h;
(5) with the product after step (4) oven dry in 300 ℃ of roastings 6 hours, promptly get CuO-ZnO-ZrO
2Composite catalyst.
Gained CuO-ZnO-ZrO
2Can mix with adhesive before composite catalyst uses, through stone roller and after compression molding, screening, to be activated; Described adhesive is a graphite, and the addition of graphite is 0.5wt%.
With the gained catalyst at 1%H
2Constant temperature after being warming up to 120 ℃ in the/inert gas flow, reduction 12h.The activated back of described catalyst reduction degree is 70%, and the assay method of reduction degree is: H
2H among the-TPR
2Consumption;
Catalyst activated is applied to remove trace amounts of CO in hydrocarbon and/or the inert gas, and concrete grammar is: in temperature is 0 ℃, and reaction pressure is under the condition of 0.1MPa, makes the alpha-olefin that contains trace amounts of CO contact gas phase air speed 5000h with said catalyst
-1, the CO that removes in the material makes its content≤20ppb.
Embodiment 15
The Preparation of catalysts method of a kind of low temperature deep removal CO, this method may further comprise the steps:
(1) preparation of slaine and aqueous slkali: take by weighing certain amount of copper acetate master, copper sulphate, copper nitrate, zinc sulfate, zinc nitrate, zirconium nitrate, zirconium sulfate, zirconium oxychloride, acetic acid zirconium and water, be mixed with respectively and contain Cu
2+Concentration is 2mol/L, Zn
2+Concentration is 2mol/L, Zr
2+Concentration is to mix behind the salting liquid of 2mol/L, is stirred well to evenly, obtains mixing salt solution, with CuO, ZnO and ZrO
2Meter, wherein CuO90wt%, ZnO5wt%, ZrO
25wt%; Weighing sodium hydroxide and water are mixed with the sodium hydroxide solution that concentration is 2mol/L;
(2) deposition: the sodium hydroxide solution that step (1) is made adds in the mixing salt solution, under 85 ℃ of temperature, reacts titration end-point pH value 6.0～8.0;
(3) aging: the catalyst precursor of step (2) gained is fully stirred, under 85 ℃ of temperature, aging 30min;
(4) with step (3) gained deposition through cyclic washing, centrifugal after in 110 ℃ of dry 16h;
(5) with the product after step (4) oven dry in 600 ℃ of roastings 6 hours, promptly get CuO-ZnO-ZrO
2Composite catalyst.
Gained CuO-ZnO-ZrO
2Can mix with adhesive before composite catalyst uses, through stone roller and after compression molding, screening, to be activated; Described adhesive is a graphite, and the addition of graphite is 2wt%.
With the gained catalyst at 10%H
2Constant temperature after being warming up to 220 ℃ in the/inert gas flow, reduction 1h.The activated back of described catalyst reduction degree is 80%.
CuO-ZnO-ZrO
2The reduction degree of CuO can be measured by following method in the catalyst: O in (2) thermogravimetric
2The weight that loses.
Catalyst activated is applied to remove trace amounts of CO in hydrocarbon and/or the inert gas, and concrete grammar is: in temperature is 150 ℃, and reaction pressure is under the condition of 0.1MPa, makes the styrene that contains trace amounts of CO contact gas phase air speed 100000h with said catalyst
-1, the CO that removes in the material makes its content≤20ppb.
Embodiment 16
The Preparation of catalysts method of a kind of low temperature deep removal CO, this method may further comprise the steps:
(1) preparation of slaine and aqueous slkali: take by weighing certain amount of copper acetate master, zinc sulfate, acetic acid zirconium and water, being mixed with concentration respectively is to mix behind the 0.2mol/L salting liquid, is stirred well to evenly, obtains mixing salt solution, with CuO, ZnO and ZrO
2Meter, wherein CuO80wt%, ZnO10wt%, ZrO
210wt%; Weighing sodium hydroxide, ammoniacal liquor and water are mixed with OH
-Concentration is the aqueous slkali of 0.2mol/L;
(2) deposition: the aqueous slkali that step (1) is made adds in the mixing salt solution, under 85 ℃ of temperature, reacts titration end-point pH value 6.0～8.0;
(3) aging: the catalyst precursor of step (2) gained is fully stirred, under 80 ℃ of temperature, aging 120min;
(4) with step (3) gained deposition through cyclic washing, centrifugal after in 110 ℃ of dry 13h;
(5) with the product after step (4) oven dry in 400 ℃ of roastings 6 hours, promptly get CuO-ZnO-ZrO
2Composite catalyst.
Gained CuO-ZnO-ZrO
2Can mix with adhesive before composite catalyst uses, through stone roller and after compression molding, screening, to be activated; Described adhesive is a graphite, and the addition of graphite is 0.1wt%.
With the gained catalyst at 10%H
2Constant temperature after being warming up to 220 ℃ in the/inert gas flow, reduction 1h.The activated back of described catalyst reduction degree is 70%.
CuO-ZnO-ZrO
2The reduction degree of CuO can be measured by following method in the catalyst: detect the amount of CuO minimizing and the amount that Cu generates among the XRD.
Catalyst activated is applied to remove trace amounts of CO in hydrocarbon and/or the inert gas, and concrete grammar is: in temperature is 50 ℃, and reaction pressure is under the condition of 5.0MPa, makes the styrene that contains trace amounts of CO contact liquid phase air speed 0.1h with said catalyst
-1, the CO that removes in the material makes its content≤20ppb.
Embodiment 17
The Preparation of catalysts method of a kind of low temperature deep removal CO, this method may further comprise the steps:
(1) preparation of slaine and aqueous slkali: take by weighing certain amount of copper acetate master, zinc sulfate, acetic acid zirconium and water, being mixed with concentration respectively is to mix behind the 3mol/L salting liquid, is stirred well to evenly, obtains mixing salt solution, with CuO, ZnO and ZrO
2Meter, wherein CuO80wt%, ZnO10wt%, ZrO
210wt%; Weighing sodium hydroxide, ammoniacal liquor and water are mixed with OH
-Concentration is the aqueous slkali of 3mol/L;
(2) deposition: the aqueous slkali that step (1) is made adds in the mixing salt solution, under 85 ℃ of temperature, reacts titration end-point pH value 6.0～8.0;
(3) aging: the catalyst precursor of step (2) gained is fully stirred, under 80 ℃ of temperature, aging 120min;
(4) with step (3) gained deposition through cyclic washing, centrifugal after in 110 ℃ of dry 13h;
(5) with the product after step (4) oven dry in 400 ℃ of roastings 6 hours, promptly get CuO-ZnO-ZrO
2Composite catalyst.
Gained CuO-ZnO-ZrO
2Can mix with adhesive before composite catalyst uses, through stone roller and after compression molding, screening, to be activated; Described adhesive is a graphite, and the addition of graphite is 5wt%.
With the gained catalyst at 10%H
2Constant temperature after being warming up to 220 ℃ in the/inert gas flow, reduction 1h.The activated back of described catalyst reduction degree is 78%.
CuO-ZnO-ZrO
2The reduction degree of CuO can be measured by following method in the catalyst: detect the amount of CuO minimizing and the amount that Cu generates among the XRD.
Catalyst activated is applied to remove trace amounts of CO in hydrocarbon and/or the inert gas, and concrete grammar is: in temperature is 40 ℃, and reaction pressure is under the condition of 0.1MPa, makes the styrene that contains trace amounts of CO contact gas phase air speed 10h with said catalyst
-1, the CO that removes in the material makes its content≤20ppb.
Claims (13)
1. the catalyst of a low temperature deep removal CO is characterized in that, this catalyst is by CuO, ZnO, ZrO
2Composite oxides form CuO-ZnO-ZrO
2Composite catalyst is 100% in total catalyst weight, wherein CuO:50～90wt%; ZnO:5～40wt%; ZrO
2: 5～40wt%, wherein to have reduction degree be 70～80% to the cupric component, said reduction degree is to represent in metallic copper and metallic copper with the weight ratio of the summation of the Cu oxide of CuO.
2. the Preparation of catalysts method of a low temperature deep removal CO according to claim 1 is characterized in that, this method may further comprise the steps:
(1) preparation of slaine and aqueous slkali: take by weighing a certain amount of mantoquita, zinc salt, zirconates and water, being mixed with concentration respectively is to mix behind 0.2～3mol/L salting liquid, is stirred well to evenly, obtains mixing salt solution, with CuO, ZnO and ZrO
2Meter, wherein CuO 50～90wt%, ZnO 5～40wt%, ZrO
25～40wt%; Take by weighing alkali and water, be mixed with the aqueous slkali that concentration is 0.2～3mol/L;
(2) deposition: mixing salt solution and aqueous slkali that step (1) is made adopt cocurrent process or suitable addition hybrid reaction, obtain deposition and are catalyst precursor;
(3) aging: the catalyst precursor of step (2) gained is fully stirred, under 60～85 ℃ of temperature, aging 30～240min;
(4) with step (3) gained deposition through cyclic washing, centrifugal after in 110 ℃ of drying 12～16h;
(5) with the product after step (4) oven dry in 300～600 ℃ of roastings 6 hours, promptly get CuO-ZnO-ZrO
2Composite catalyst.
3. the Preparation of catalysts method of low temperature deep removal CO according to claim 2; It is characterized in that; The described mantoquita of step (1) comprises one or more in copper nitrate, copper sulphate, Schweinfurt green or the copper chloride; Described zinc salt comprises one or both in zinc nitrate or the zinc sulfate, and described zirconates comprises one or more in zirconium nitrate, zirconium sulfate, zirconium oxychloride or the acetic acid zirconium; Described alkali comprises one or more in sodium carbonate, sodium acid carbonate, NaOH, ammoniacal liquor or the ammonium carbonate.
4. the Preparation of catalysts method of low temperature deep removal CO according to claim 3 is characterized in that, described mantoquita is a copper nitrate, and described zinc salt is a zinc nitrate, and described zirconates is a zirconium nitrate, and described alkali is ammonium carbonate.
5. the Preparation of catalysts method of low temperature deep removal CO according to claim 2; It is characterized in that; The described cocurrent process of step (2) is: add mixing salt solution and aqueous slkali in the container simultaneously; Under 50～85 ℃ of temperature, react, deposition pH value 6.0～8.0, the mol ratio of mixing salt solution and aqueous slkali addition is 1: 1;
Described along addition for aqueous slkali is added in the salting liquid, under 50～85 ℃ of temperature, react titration end-point pH value 6.0～8.0.
6. the Preparation of catalysts method of low temperature deep removal CO according to claim 2 is characterized in that, the temperature of the described roasting of step (5) is 320～500 ℃.
7. the Preparation of catalysts method of low temperature deep removal CO according to claim 2 is characterized in that, step (5) gained CuO-ZnO-ZrO
2Can mix with adhesive before composite catalyst uses, through stone roller and after compression molding, screening, to be activated; Described adhesive is the various adhesives that shaping of catalyst can be used, and the addition of adhesive is 0.1～5wt%.
8. the Preparation of catalysts method of low temperature deep removal CO according to claim 7 is characterized in that, described adhesive is a graphite.
9. the activation method of the catalyst of a low temperature deep removal CO as claimed in claim 1 is characterized in that, this method is: with said catalyst at 1～10%H
2Constant temperature after being warming up to 120～220 ℃ in the/inert gas flow, reduction 1～12h.
10. the activation method of the catalyst of low temperature deep removal CO according to claim 9; It is characterized in that; Preferred 160 ℃ of described reduction temperature; Preferred 3～6h of recovery time, the activated back of described catalyst reduction degree is 70～80%, said reduction degree is to represent in metallic copper and metallic copper with the weight ratio of the summation of the Cu oxide of CuO.
11. the Application of Catalyst of a low temperature deep removal CO as claimed in claim 1; It is characterized in that; With said catalyst applications trace amounts of CO in removing hydrocarbon and/or inert gas, concrete grammar is: in temperature is 0～150 ℃, and reaction pressure is under the condition of 0.1～5MPa; Make the material that contains trace amounts of CO contact liquid phase air speed 0.1～100h with said catalyst
-1, gas phase air speed 10～100000h
-1, the CO that removes in the material makes its content≤20ppb.
12. the Application of Catalyst of low temperature deep removal CO according to claim 11 is characterized in that described catalyst is converted into CO with CO
2, the said material that contains trace amounts of CO comprises alpha-olefin, saturated hydrocarbons, cinnamic gas phase or liquid phase or N
2, the content of CO is 0.02ppm～1000ppm in the described material that contains trace amounts of CO; When the described material that contains trace amounts of CO was the liquid phase state hydrocarbon, reaction temperature was 0～50 ℃.
13. the Application of Catalyst of low temperature deep removal CO according to claim 11 is characterized in that, the preferred 0.02ppm～100ppm of content of CO in the described material that contains trace amounts of CO.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105251498A (en) * | 2015-10-09 | 2016-01-20 | 合肥学院 | Preparation method of Cu-Zn-ZrO2 catalytic material |
| CN105478005A (en) * | 2014-09-16 | 2016-04-13 | 中国石油化工股份有限公司 | Trace CO removal method |
| CN104549317B (en) * | 2013-10-23 | 2017-02-01 | 中国石油化工股份有限公司 | Shell catalyst of framework copper oxide, preparation method and application of shell catalyst |
| CN111437821A (en) * | 2020-04-30 | 2020-07-24 | 上海化工研究院有限公司 | Reverse-loading catalyst for removing carbon monoxide at low temperature and preparation method thereof |
| CN111744499A (en) * | 2020-06-19 | 2020-10-09 | 上海汇允环境科技有限公司 | Low-temperature catalytic oxidation VOCs catalyst and preparation method and application thereof |
| CN115400721A (en) * | 2022-09-30 | 2022-11-29 | 西安元创化工科技股份有限公司 | Activation, application and regeneration method of adsorbent for deeply removing CO |
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| CN101384356A (en) * | 2006-02-14 | 2009-03-11 | 巴斯夫欧洲公司 | Adsorption composition and process for removal of CO from material streams |
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| CN101384356A (en) * | 2006-02-14 | 2009-03-11 | 巴斯夫欧洲公司 | Adsorption composition and process for removal of CO from material streams |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104549317B (en) * | 2013-10-23 | 2017-02-01 | 中国石油化工股份有限公司 | Shell catalyst of framework copper oxide, preparation method and application of shell catalyst |
| CN105478005A (en) * | 2014-09-16 | 2016-04-13 | 中国石油化工股份有限公司 | Trace CO removal method |
| CN105478005B (en) * | 2014-09-16 | 2018-08-17 | 中国石油化工股份有限公司 | A method of removing trace amounts of CO |
| CN105251498A (en) * | 2015-10-09 | 2016-01-20 | 合肥学院 | Preparation method of Cu-Zn-ZrO2 catalytic material |
| CN111437821A (en) * | 2020-04-30 | 2020-07-24 | 上海化工研究院有限公司 | Reverse-loading catalyst for removing carbon monoxide at low temperature and preparation method thereof |
| CN111437821B (en) * | 2020-04-30 | 2023-04-07 | 上海化工研究院有限公司 | Reverse-loading catalyst for removing carbon monoxide at low temperature and preparation method thereof |
| CN111744499A (en) * | 2020-06-19 | 2020-10-09 | 上海汇允环境科技有限公司 | Low-temperature catalytic oxidation VOCs catalyst and preparation method and application thereof |
| CN115400721A (en) * | 2022-09-30 | 2022-11-29 | 西安元创化工科技股份有限公司 | Activation, application and regeneration method of adsorbent for deeply removing CO |
| CN115400721B (en) * | 2022-09-30 | 2023-10-27 | 西安元创化工科技股份有限公司 | Activation, application and regeneration method of adsorbent for deeply removing CO |
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