CN104338532A - Copper-zirconium catalyst as well as preparation method and application of copper-zirconium catalyst - Google Patents
Copper-zirconium catalyst as well as preparation method and application of copper-zirconium catalyst Download PDFInfo
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Abstract
The invention discloses a preparation method and application of a copper-zirconium catalyst. The copper-zirconium catalyst comprises 5-90wt% of CuO and 5-90wt% of ZrO2 based on100% of the total weight of the catalyst; the catalyst is prepared by virtue of supergravity neutralization, aging and hydrothermal re-aging. As the supergravity-hydrothermal combined preparation method is adopted, a copper catalyst precursor is relatively easy to wash and filter, Na<+> in the catalyst can be removed relatively easily so that the content of Na2O is less than 0.05%, and the activity of the catalyst can be guaranteed.
Description
Technical field
The present invention relates to and remove micro CO field, furtherly, relate to a kind of Cu-Zr catalyst, preparation method and application.
Background technology
Low temperature deep removal trace amounts of CO catalyst in ethene or propylene material is generally adopt Cu-series catalyst.First small CuO crystal grain has good low temperature active.Copper-based catalysts adopts the preparation of traditional coprecipitation method, is no matter and flows, just adding and instead to add, being all difficult to form uniform crystallite dimension.Secondly, in order to obtain less CuO crystal grain and larger specific surface, more difficult when often reaching washing and filtering, sandwich the Na in catalyst precursor
+must wash to Na
2o<0.1wt%, best Na
2o<0.05wt%, if Na
+effectively can not remove the activity that greatly can affect catalyst.Finally, micro Cu O grain dispersion needs to select a kind of suitable carrier, ZrO
2there is good oxygen and lack CuO and ZrO
2cooperative effect be also conducive to improving the activity of catalyst, but the Zr(OH produced in preparation process)
2often be difficult to sedimentation, cause precipitation solution cannot remove impurity Na by normal mode of washing
+, thus the serious activity reducing catalyst.
It is generally acknowledged, copper zirconium coprecipitation process is as follows:
The hydrolysis of alkali
CO
3 2-+H
2O→OH
-+HCO
3 -（1）
The generation of basic copper nitrate
2Cu(NO
3)
2+3OH
-→Cu
2(OH)
3NO
3+3NO
3 -（2）
The hydrolysis of salt
Cu
2++ H
2o → Cu (OH)
2(black presoma)+2H
+(3-1)
Cu(OH)
2→CuO+H
2O （3-2）
Colourshifting process: basic copper nitrate (blue presoma) is to the conversion Cu of basic copper carbonate (green)
2(OH)
3nO
3+ CO
3 2-→ Cu
2(CO
3) (OH)
2(amorphous)+NO
3 -+ OH
-(4)
The generation of carbon dioxide
HCO
3 -+H
2O→2OH
-+CO
2（5）
Grain growth reacts
Cu
2(CO
3) (OH)
2(amorphous) → Cu
2(CO
3) (OH)
2(crystallization) (6)
Initial reaction stage, creates the nucleus of a large amount of basic copper carbonates, and along with the prolongation in reaction time, these nucleus are constantly grown up.When in and a large amount of basic copper carbonate of generation in still, the colourshifting process after adding, OH
-and CO
3 2-consumed in a large number, pH value constantly reduces, now HCO
3 -relative concentration in the reactor constantly increases, and the direction of reacting towards being conducive to carbon dioxide generation is carried out.The hydrolysis of certain salt and the generation of basic copper carbonate are competitive reactions, it is generally acknowledged the Cu (OH) produced in said process
2be do not have activated, and basic copper carbonate produces the presoma of high activated catalyst, except reducing reaction temperature, shortens copper ion at high concentration OH
-under reaction time also particularly important.
By analyzing the time of contact shortening mantoquita and alkali above, while the generation of a large amount of nucleus, the growth of nucleus can be suppressed, and avoids the Cu (OH) of non-activity
2formation.Supergravity reactor a kind ofly microcosmic is mixed and the reactor that is greatly strengthened of mass transfer, and compared with traditional precipitation reaction, gravity Method is prepared nanometer eta particle and had the advantages such as reaction time short, granularity is little, narrow particle size distribution.
Certainly, a large amount of CO is proceeded in neutralization reaction
2during generation, the nucleus of aforesaid basic copper nitrate has carried out the growth of long period, may also occur by part basic copper carbonate simultaneously.If therefore produce a large amount of CO in supergravity reactor
2, obviously this does not play the advantage that it produces a large amount of fine particle.As much as possible the process of nucleus generation and nuclei grow is separated, the selection of individual beyond doubt comparatively reason.CN101579629A etc. disclose and adopt a kind of method adopting gravity Method to prepare CuZnAl catalyst, have a large amount of CO in supergravity reactor
2gas produces, and is obviously unfavorable for the generation of tiny crystal grains, and the problem such as filtration, washing under hypergravity precipitation is not mentioned in this invention yet.Prior art not yet considers the problem of the short residence time adopting supergravity reactor.
Zirconates is for zirconium oxychloride, as (" zirconium dioxide preparation technology and application " metallurgical industry publishing houses such as Xiong Ping Kun, 2008) described in, zirconium oxychloride easily forms zirconium hydroxide colloid in alkali lye, can well disperse the compound mantoquita sediment of sedimentation simultaneously, the foreign ion undoubtedly in colloid is as Na
+be difficult to washing removing.Gluey zirconium hydroxide needs under hydro-thermal, form the ultra-fine precipitates being easy to filter.If prior art not yet considers that the Na+ wherein wrapped up will wash to an extremely low level by the co-precipitation of copper zirconium, the problem of hydro-thermal method post processing need be adopted.
Summary of the invention
Improper for solving the catalyst activity precursor controlling existed in prior art, the problems such as catalyst precursor washing and filtering difficulty, the invention provides a kind of Cu-Zr catalyst, preparation method and application.The present invention adopts hypergravity and hydro-thermal method to combine to prepare Cu-Zr catalyst, can obtain the catalyst precursor basic copper carbonate with good catalytic activity, adopts conventional mode of washing can by Na in presoma simultaneously
2o washing, to being less than 0.05wt%, has good industrial value.
An object of the present invention is to provide a kind of Cu-Zr catalyst.
Comprise CuO and ZrO
2, in overall catalyst weight for 100%,
Wherein CuO content is 5 ~ 90wt%, is preferably 15 ~ 80wt%;
ZrO
2, content is 5 ~ 90wt%; Be preferably 15 ~ 80wt%
Wherein, described Impurities In Catalyst Na
2o content is less than 0.05wt%.
Described catalyst be through hypergravity neutralization, aging, filter, hydro-thermal is aging rear obtained again.
Two of object of the present invention is to provide a kind of preparation method of Cu-Zr catalyst.
Comprise:
(1) hypergravity neutralization: copper zirconates composite compaction technique and alkali lye are added in hypergravity revolving reaction still in the mode also flowed, react at 40 ~ 90 DEG C, the rotating speed of hypergravity revolving reaction still is 60 ~ 3000r/min, the time of staying of solution in hypergravity revolving reaction still is no more than 5 minutes, preferably more than 1 minute, more preferably no more than half a minute;
(2) aging: by hypergravity revolving reaction still feed liquid out, to carry out aging in aging still, change into after green until feed liquid, namely stop aging, filter;
(3) hydro-thermal is aging again: after the dilution of the material that step (2) obtained, and to introduce in hydro-thermal stirred tank aging 1 ~ 24 hour, temperature is 120 ~ 400 DEG C, pressure is 1 ~ 15MPa;
(4) filtration, washing, drying, roasting, shaping;
Described copper zirconium composite compaction technique is the mixed solution of mantoquita and zirconates, and copper zirconates composite compaction technique concentration is 1.5 ~ 10M, is preferably 2 ~ 7M, is more preferably 3 ~ 5M; M and mol/L.
Described alkali lye is sodium carbonate and/or sodium acid carbonate, and concentration of lye is 0.1 ~ 4M, is preferably 0.5 ~ 2M.
Specifically can adopt following steps:
(1) hypergravity reaction:
Pass into hypergravity revolving reaction still from different inlets respectively by copper mixing salt solution and alkali lye, at the porous aggregate layer of revolving bed, reacted suspension is discharged by revolving bed discharge gate.Blue copper zirconium composite compaction technique and alkali lye are added in hypergravity revolving reaction still in the mode also flowed, react at 40 ~ 90 DEG C, the rotating speed of hypergravity revolving reaction still is 60 ~ 3000r/min, the time of staying of solution in reactor is no more than 5 minutes, preferably more than 1 minute, more preferably no more than 0.5 minute.
(2) aging: by hypergravity revolving reaction still feed liquid out, to carry out aging in aging still, change into after green until feed liquid, namely stop aging.Filter: the mode adopting press filtration or centrifugal filtration.
(3) hydro-thermal ageing process again:
The presoma that step (1) obtained is scattered in water after filtering again, introduces in hydro-thermal stirred tank, 120 ~ 400 DEG C, under 1 ~ 15MPa, aging 1 ~ 24 hour; After hydrothermal treatment consists, carry out filtering, the subsequent handling such as washing.Na after washing
2o content (calculating the overall catalyst weight namely obtained in butt copper zirconium mixed oxide) should be less than 0.05wt%.
Afterwards this feed liquid filtered, wash, dry, roasting and compression molding.Described filtration, washing, drying, roasting and compressing tablet adopt this area conventional method and common process conditions.
Supergravity reactor a kind ofly microcosmic is mixed and the reactor that is greatly strengthened of mass transfer, and compared with traditional precipitation reaction, gravity Method is prepared nanometer eta particle and had the advantages such as reaction time short, granularity is little, narrow particle size distribution.Certainly, a large amount of CO is proceeded in neutralization reaction
2during generation, the nucleus of aforesaid basic copper nitrate have passed through the growth of long period, may also occur by part basic copper carbonate simultaneously.If therefore produce a large amount of CO in supergravity reactor
2, obviously this does not play the advantage that it produces a large amount of fine particle.As much as possible the process of nucleus generation and nuclei grow is separated, the selection of individual beyond doubt comparatively reason.Therefore, the present invention specially selects two processes to be divided into hypergravity N-process and ageing process.
Supergravity reactor in the present invention is the reactor carrying out reactive liquid solution, comprises charging aperture and a liquid outlet of two kinds of materials, without gas vent.In supergravity reactor, the neutralization reaction time, short as far as possible making it did not occur that carbon dioxide bubble is to avoid the formation of over-reactive presoma, also charging mixing and stirring need be made abundant in feed distributor good charging distribution and suitable rotating speed simultaneously.In supergravity reactor of the present invention, operable filler includes, but are not limited to metal and nonmetallic materials, as silk screen and structured packing etc.
Described charging, adopts distributor charging.
Three of object of the present invention is to provide a kind of Cu-Zr catalyst and is removing the application in micro CO.
Han Liang≤the 5wppm of the CO in feeding ethylene or propylene, after You Xuan≤2wppm, Geng You Xuan≤1wppm removes, in material flow, carbon monoxide is less than 0.1ppm, is preferably less than 30ppb.In the present invention, if do not particularly not pointed out, the degree of catalyst is by weight, and content wppm and wppb of material impurities by weight.
The beneficial effect that the present invention has is as follows:
The present invention adopts hypergravity-hydro-thermal method to prepare the method for Cu-Zr catalyst, adopt the pH value range suitable compared with brachymedial and time, control, hypergravity neutralization and agingly the multiple method such as to separate, solve the catalyst activity precursor controlling existed in existing high-gravity technology improper, the catalyst precursor basic copper carbonate with good catalytic activity can be obtained.Adopt hydro-thermal method aging catalyst presoma more simultaneously, solve the problems such as washing and filtering difficulty, can by affect catalyst performance Na
2o washing, to being less than 0.05wt%, substantially increasing the reactivity worth of catalyst, has good industrial value.
Detailed description of the invention
Below in conjunction with embodiment, further illustrate the present invention.
In embodiments of the invention, the method for testing of relevant data is as follows:
Catalyst n a
2o content measuring: adopt the Atomic Absorption Spectrometer (AAS) of VARIAN Oncology Systems to analyze.
It is pure that zirconium oxychloride in embodiment, copper nitrate and sodium carbonate are analysis, recovers chemical reagent Co., Ltd purchased from Tianjin.
Embodiment 1:
Configure nitric acid and zirconium oxychloride mixed solution that 5 cubic metres of total salt molar concentrations are 2mol/L (according to CuO/ZrO in catalyst
2weight ratio is 30/70) and the sodium carbonate liquor of 5 cubic metres of 2.0mol/L, with and the mode of flowing joins supergravity reactor neutralizes, neutralization reaction temperature is 80 DEG C, supergravity reactor rotor speed is 2000rpm, material is 2 minutes in the time of staying of reactor, is 8.5 from supergravity reactor blue slurry pH value out.By hypergravity revolving reaction still feed liquid out, in aging still, 80 DEG C are carried out aging, change into after green until feed liquid, namely stop aging.The mode of press filtration is adopted to remove mother liquor.
The presoma that above-mentioned operation obtained is scattered in water after filtering again, adopts deionized water by after above-mentioned material dilution, introduces in hydro-thermal stirred tank that to carry out hydro-thermal aging again, 200 DEG C, under 10MPa, aging 12 hours.Afterwards roasting 8 hours and compression molding under 80 DEG C of sedimentation washings, 120 DEG C of dryings, 12 hours, 400 DEG C roastings is being carried out to this feed liquid.Na after washing
2o content (calculating with butt copper zirconium mixed oxide) is for 0.042wt%.Made catalyst is 1
#, component content is 30wt%CuO/70wt%ZrO
2
Embodiment 2:
Other conditions are with embodiment 1.Supergravity reactor rotor speed is 2000rpm, and material is 0.5 minute in the time of staying of reactor, is 7.5 from supergravity reactor slurry pH value out.Now slurries out become green slurry.Na after washing
2o content (calculating with butt copper zirconium mixed oxide) is for 0.048wt%.Made catalyst is 2
#.Component content is 30wt%CuO/70wt%ZrO
2.
Embodiment 3:
Other conditions are with embodiment 1.Complex copper zirconium mixing salt solution concentration is 5M, and sodium carbonate liquor concentration is 0.5M, and supergravity reactor rotor speed is 100rpm, and material is 5 minutes in the time of staying of reactor, is 6.5 from supergravity reactor slurry pH value out.Now slurries out become green slurry.Na after washing
2o content (calculating with butt copper zirconium mixed oxide) is for 0.042wt%.Made catalyst is 3
#.Component content is 15wt%CuO/85wt%ZrO
2
Embodiment 4:
Other conditions are with embodiment 1.Complex copper zirconium mixing salt solution concentration is 7M, and sodium carbonate liquor concentration is 0.5M, and supergravity reactor rotor speed is 100rpm, and material is 5 minutes in the time of staying of reactor, is 6.5 from supergravity reactor slurry pH value out.Now slurries out become green slurry.Na after washing
2o content (calculating with butt copper zirconium mixed oxide) is for 0.038wt%.Made catalyst is 4
#.Component content is 85wt%CuO/15wt%ZrO
2.
Embodiment 5:
Other conditions are with embodiment 1.Complex copper zirconium mixing salt solution concentration is 3M, and sodium carbonate liquor concentration is 1.5M, and supergravity reactor rotor speed is 1,000rpm, and material is 5 minutes in the time of staying of reactor, is 7.5 from supergravity reactor slurry pH value out.Now slurries out become green slurry.
The condition that hydro-thermal is aging is again, 120 DEG C, under 2MPa, aging 24 hours.Na after washing
2o content (calculating with butt copper zirconium mixed oxide) is for 0.042wt%.Made catalyst is 5
#.Component content is 75wt%CuO/25wt%ZrO
2.
Embodiment 6:
Other conditions are with embodiment 1.Complex copper zirconium mixing salt solution concentration is 4.5M, and sodium carbonate liquor concentration is 3.5M, and supergravity reactor rotor speed is 2,500rpm, and material is 5 minutes in the time of staying of reactor, is 8.0 from supergravity reactor slurry pH value out.Now slurries out become green slurry.
The condition that hydro-thermal is aging is again, 300 DEG C, under 12.5MPa, aging 2 hours.Na after washing
2o content (calculating with butt copper zirconium mixed oxide) is for 0.035wt%.Made catalyst is 6
#.Component content is 40wt%CuO/60wt%ZrO
2.
Comparative example 1
Other conditions are with embodiment 1.Supergravity reactor rotor speed is 30rpm, and material is 10 minutes in the time of staying of reactor, is 8.5 from supergravity reactor slurry pH value out.Now slurries have out become black slurries.Na after washing
2o content (calculating with butt copper zirconium mixed oxide) is for 0.039wt%.Made catalyst is 7
#, component content is 30wt%CuO/70wt%ZrO
2.
Comparative example 2
Other conditions are with embodiment 1.Configure the copper zirconium mixed solution that total salt molar concentration is 1.0mol/L, from supergravity reactor now slurries out become black slurries.Na after washing
2o content (calculating with butt copper zirconium mixed oxide) is for 0.032wt%.Made catalyst is 8
#, component content is 30wt%CuO/70wt%ZrO
2.
Comparative example 3
Other conditions are with embodiment 1.Material after aging does not filter, and directly enters hydrothermal aging operation, and the slurries after hydrothermal aging are black.Na after washing
2o content (calculating with butt copper zirconium mixed oxide) is for 0.037wt%.Made catalyst is 9
#, component content is 30wt%CuO/70wt%ZrO
2.
Comparative example 4
Other conditions are with embodiment 1.Do not carry out hydrothermal aging, adopt normal ageing, due to cannot sedimentation, adopt centrifuge washing to filter, the Na after washing
2o content (calculating with butt copper zirconium mixed oxide) is for 4.08wt%.Made catalyst is 10
#, component content is 30wt%CuO/70wt%ZrO
2.
Test:
With the catalyst prepared by embodiment and comparative example, that carries out trace amounts of CO respectively removes test.Evaluating catalyst is carried out in fixed bed continuous-flow tubular reactor.Loaded catalyst is 500mL, and reactor inside diameter is 40mm, and loading height is 30mm.After Catalyst packing, at 120 DEG C, purge 12 hours with high-purity nitrogen.Material is the liquid propylene containing 2200ppbCO, and reaction pressure is 2.5MPa, and reaction temperature is 40 DEG C, and air speed is 30hr
-1, carry out the evaluation of 200 hours.Raw material and product adopt the micro CO analyzer of AMETEK company to detect.Result of the test is listed in table 1.
Table 1 result of the test
As can be seen from Table 1,
1) in strict accordance with preparation method's process of the present invention, the highly active catalyst removing trace amounts of CO can just be obtained.
Catalyst 1 prepared by embodiment 1 supergravity hydrothermal method
#there is good reactivity;
In comparative example 7
#with 8
#catalyst, for various reasons as overstand or charging salinity too low etc., to cause from supergravity reactor precursor solution blackening out, thus reactionless activity.
Comparative example 9
#catalyst due to the mother liquor from the hypergravity not removed high ph-values of precursor solution out, cause its in hydro-thermal reaction further reaction cause solution blackening, thus completely lose activity.
Comparative example 10
#catalyst, owing to not carrying out hydrothermal aging, causes its slurries cannot filtration washing, thus the Na in catalyst
2o too high levels, thus completely lose activity.
2) although 7 ~ 8
#na in catalyst
2o content is compared with 1 ~ 2
#low, but comparative example obtains black Cu (OH) in preparation process
2presoma, activity is extremely low thus; And embodiment 1 ~ 2
#obtain suitable presoma (basic copper carbonate) through hydrothermal aging after obtaining blue presoma (basic copper nitrate) and green presoma (basic copper carbonate) respectively, basic copper carbonate presoma of preparing as is well understood in the art is the key obtaining high activity co-precipitation copper catalyst.Therefore as described in background technology and description, the presoma controlling parameter in preparation process suitable is also vital.
Claims (10)
1. a preparation method for Cu-Zr catalyst, is characterized in that:
Described catalyst comprises: CuO and ZrO
2, in overall catalyst weight for 100%,
Wherein CuO content is 5 ~ 90wt%, ZrO
2, content is 5 ~ 90wt%;
Described catalyst be through hypergravity neutralization, aging and hydro-thermal again aging techniques obtain.
2. Cu-Zr catalyst as claimed in claim 1, is characterized in that:
CuO content is 15 ~ 80wt%; ZrO
2content is 15 ~ 80wt%;
Described Impurities In Catalyst Na
2o content is less than 0.05wt%.
3. Cu-Zr catalyst as claimed in claim 1 or 2, is characterized in that described catalyst is prepared by the method comprised the following steps:
(1) hypergravity neutralization: copper zirconium composite compaction technique and alkali lye are added in hypergravity revolving reaction still in the mode also flowed, react at 40 ~ 90 DEG C, the rotating speed of hypergravity revolving reaction still is 60 ~ 3000r/min, and the time of staying of solution in hypergravity revolving reaction still is no more than 5 minutes;
(2) aging: by hypergravity revolving reaction still feed liquid out, to carry out aging in aging still, change into after green until feed liquid, namely stop aging, filter;
(3) hydro-thermal is aging again: after the dilution of the material that step (2) obtained, and to introduce in hydro-thermal stirred tank aging 1 ~ 24 hour, temperature is 120 ~ 400 DEG C, pressure is 1 ~ 15MPa;
(4) filtration, washing, drying, roasting, shaping;
Described copper zirconium composite compaction technique is the mixed solution of mantoquita and zirconates, and the concentration of copper zirconium composite compaction technique is 1.5 ~ 10M;
Described alkali lye is sodium carbonate and/or sodium acid carbonate, and concentration of lye is 0.1 ~ 4M.
4. a preparation method for the Cu-Zr catalyst as described in one of claims 1 to 3, is characterized in that described method comprises:
(1) hypergravity neutralization: copper zirconium composite compaction technique and alkali lye are added in hypergravity revolving reaction still in the mode also flowed, react at 40 ~ 90 DEG C, the rotating speed of hypergravity revolving reaction still is 60 ~ 3000r/min, and the time of staying of solution in hypergravity revolving reaction still is no more than 5 minutes;
(2) aging: by hypergravity revolving reaction still feed liquid out, to carry out aging in aging still, change into after green until feed liquid, namely stop aging, filter;
(3) hydro-thermal is aging again: after the dilution of the material that step (2) obtained, and to introduce in hydro-thermal stirred tank aging 1 ~ 24 hour, temperature is 120 ~ 400 DEG C, pressure is 1 ~ 15MPa;
(4) filtration, washing, drying, roasting, shaping;
Described copper zirconium composite compaction technique is the mixed solution of mantoquita and zirconates, and the concentration of copper zirconium composite compaction technique is 1.5 ~ 10M;
Described alkali lye is sodium carbonate and/or sodium acid carbonate, and concentration of lye is 0.1 ~ 4M.
5. the preparation method of Cu-Zr catalyst as claimed in claim 4, is characterized in that:
The concentration of copper zirconium composite compaction technique is 2 ~ 7M; Concentration of lye is 0.5 ~ 2M.
6. the preparation method of Cu-Zr catalyst as claimed in claim 5, is characterized in that:
The concentration of copper zirconium composite compaction technique is 3 ~ 5M.
7. the preparation method of Cu-Zr catalyst as claimed in claim 4, is characterized in that:
In step (1), be no more than 1 minute in the time of staying of solution in hypergravity revolving reaction still.
8. the preparation method of Cu-Zr catalyst as claimed in claim 7, is characterized in that:
In step (1), be no more than half a minute in the time of staying of solution in hypergravity revolving reaction still.
9. the preparation method of Cu-Zr catalyst as claimed in claim 4, is characterized in that:
The described charging joining hypergravity revolving reaction still, adopts distributor charging.
10. the Cu-Zr catalyst as described in one of claims 1 to 3 is removing the application in micro CO, it is characterized in that:
Reaction temperature is 0 ~ 150 DEG C, and reaction pressure is 0.1 ~ 5Mpa, and gas-phase reaction air speed is 100 ~ 10,000h
-1, liquid phase reactor air speed is 0.5 ~ 100h
-1; CO content in logistics material is less than 5ppm, and after removing, in material flow, CO content is less than 0.1ppm, is preferably less than 30ppb.
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| CN101462057A (en) * | 2007-12-21 | 2009-06-24 | 中国石油化工股份有限公司 | Copper-zirconium based catalyst for removing trace amounts of carbon monoxide, as well as preparation method and use thereof |
| 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 |
| CN102031021A (en) * | 2010-11-30 | 2011-04-27 | 天津长芦汉沽盐场有限责任公司 | Process for preparing super-thin high-purity magnesium hydroxide fire retardant by supergravity-hydrothermal method |
| CN102145924A (en) * | 2011-04-28 | 2011-08-10 | 同济大学 | Method for preparing alkaline cobalt carbonate under hyper-gravity hydrothermal condition |
| CN102309965A (en) * | 2010-06-25 | 2012-01-11 | 中国石油化工股份有限公司 | Cu-based catalyst for removing trace gas impurity as well as preparation method and application thereof |
-
2013
- 2013-08-09 CN CN201310346605.1A patent/CN104338532B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101462057A (en) * | 2007-12-21 | 2009-06-24 | 中国石油化工股份有限公司 | Copper-zirconium based catalyst for removing trace amounts of carbon monoxide, as well as preparation method and use thereof |
| 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 |
| CN102309965A (en) * | 2010-06-25 | 2012-01-11 | 中国石油化工股份有限公司 | Cu-based catalyst for removing trace gas impurity as well as preparation method and application thereof |
| CN102031021A (en) * | 2010-11-30 | 2011-04-27 | 天津长芦汉沽盐场有限责任公司 | Process for preparing super-thin high-purity magnesium hydroxide fire retardant by supergravity-hydrothermal method |
| CN102145924A (en) * | 2011-04-28 | 2011-08-10 | 同济大学 | Method for preparing alkaline cobalt carbonate under hyper-gravity hydrothermal condition |
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