CN104338532B - A kind of Cu-Zr catalyst, preparation method and application - Google Patents

A kind of Cu-Zr catalyst, preparation method and application Download PDF

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CN104338532B
CN104338532B CN201310346605.1A CN201310346605A CN104338532B CN 104338532 B CN104338532 B CN 104338532B CN 201310346605 A CN201310346605 A CN 201310346605A CN 104338532 B CN104338532 B CN 104338532B
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preparation
aging
hypergravity
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CN104338532A (en
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王育
刘小波
乐毅
马天石
戴伟
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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    • Y02P20/00—Technologies relating to chemical industry
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Abstract

The invention discloses the preparation method and application of a kind of Cu-Zr catalyst.Described catalyst includes: CuO and ZrO2, it is in terms of 100% by overall catalyst weight, wherein CuO content is 5～90wt%, ZrO2, content is 5～90wt%；Described catalyst be neutralize through hypergravity, aging and hydro-thermal aging techniques again prepares.The present invention uses and is easier to washing in the united preparation method of supergravity hydrothermal, beneficially copper catalyst precursor body and filters, it is easier to realize Na in catalyst+Removing, make Na2O content < 0.05%, it is ensured that the activity of catalyst.

Description

A kind of Cu-Zr catalyst, preparation method and application
Technical field
The present invention relates to remove micro CO field, furtherly, relate to a kind of Cu-Zr catalyst, Preparation method and application.
Background technology
In ethylene or propylene material, low temperature deep removal trace amounts of CO catalyst, usually uses Cu-series catalyst. The most small CuO crystal grain has good low temperature active.Copper-based catalysts uses traditional coprecipitation method Preparation, either and flow, just adding and counter add, is all difficult to form uniform crystallite dimension.Secondly, in order to obtain CuO crystal grain that must be less and bigger specific surface, often reach relatively difficult during washing and filtering, sandwiches Na in catalyst precursor+Must wash to Na2O < 0.1wt%, best Na2O < 0.05wt%, if Na+ Effectively removing can not can largely effect on the activity of catalyst.Finally, micro Cu O grain dispersion needs to select one Plant suitable carrier, ZrO2There is good oxygen and lack CuO and ZrO2Cooperative effect be also beneficial to raising and urge The activity of agent, but the Zr(OH produced in preparation process)2Often it is difficult to settle, causes precipitating molten Liquid cannot remove impurity Na by normal mode of washing+, thus seriously reduce the activity of catalyst.
It is generally believed that copper zirconium coprecipitation process is as follows:
The hydrolysis of alkali
CO3 2-+H2O→OH-+HCO3 -(1)
The generation of basic copper nitrate
2Cu(NO3)2+3OH-→Cu2(OH)3NO3+3NO3 -(2)
The hydrolysis of salt
Cu2++H2O→Cu(OH)2(black presoma)+2H+(3-1)
Cu(OH)2→CuO+H2O (3-2)
Colourshifting process: the basic copper nitrate (blue presoma) conversion to basic copper carbonate (green) Cu2(OH)3NO3+CO3 2-→Cu2(CO3)(OH)2(amorphous)+NO3 -+OH-(4)
The generation of carbon dioxide
HCO3 -+H2O→2OH-+CO2(5)
Crystal grain is grown up reaction
Cu2(CO3)(OH)2(amorphous) → Cu2(CO3)(OH)2(crystallization) (6)
Initial reaction stage, creates the nucleus of substantial amounts of basic copper carbonate, along with the prolongation in response time, these Nucleus is constantly grown up.The substantial amounts of basic copper carbonate of generation in neutralization still, the colourshifting process after adding, OH-And CO3 2-Being consumed in a large number, pH value constantly reduces, now HCO3 -Relative concentration in the reactor is not Disconnected increase, reacts the direction generated towards beneficially carbon dioxide and carries out.The hydrolysis of certain salt and basic carbonate The generation of copper is a competitive reaction, it is considered that the Cu (OH) produced in said process2Be do not have activated, And basic copper carbonate is the presoma producing high activated catalyst, except reducing in addition to reaction temperature, shorten copper from Son is in high concentration OH-Under response time the most particularly important.
Shorten mantoquita and the time of contact of alkali by above analysis, can while the generation of a large amount of nucleus, The growth of suppression nucleus, and avoid inactive Cu (OH)2Formation.It is micro-that supergravity reactor is that one makes Seeing the reactor that mixing is greatly strengthened with mass transfer, compared with tradition precipitation, gravity Method preparation is received Rice eta particle has the advantages such as the response time is short, granularity is little, narrow particle size distribution.
Certainly, a large amount of CO is proceeded in neutralization reaction2During generation, the nucleus of aforesaid basic copper nitrate enters Go the growth of long period, may occur by part basic copper carbonate simultaneously.If therefore overweight Power reactor produces substantial amounts of CO2, it is clear that this does not play its advantage producing a large amount of fine particles. Process nucleus generation and nucleus grown up as far as possible separately, is undoubtedly the selection of individual more reason.CN 101579629A etc. disclose a kind of method using gravity Method to prepare CuZnAl catalyst of employing, overweight Power reactor has a large amount of CO2Gas produces, it is clear that being unfavorable for the generation of tiny crystal grains, this invention does not carries yet Filtration under precipitating to hypergravity, the problem such as washing.Prior art is not yet in view of using supergravity reactor The problem of short residence time.
Zirconates is as a example by zirconium oxychloride, such as (" zirconium dioxide preparation technology and application " metallurgical industry such as Xiong Ping Kun Publishing house, 2008) described, zirconium oxychloride easily forms zirconium hydroxide colloid in alkali liquor, can be fine The compound mantoquita precipitate that simultaneously settles of dispersion, the such as Na of the foreign ion in colloid undoubtedly+It is difficult to washing remove Go.Gluey zirconium hydroxide needs to form the ultra-fine precipitates being prone to filter under hydro-thermal.Prior art is not yet examined The Na+ wherein wrapped up being washed to an extremely low level to the co-precipitation of copper zirconium if considered, hydro-thermal need to be used The problem of method post processing.
Summary of the invention
Improper for solving catalyst activity precursor controlling present in prior art, catalyst precursor washs The problems such as filtration difficulty, the invention provides a kind of Cu-Zr catalyst, preparation method and application.The present invention adopts Combine by hypergravity and hydro-thermal method and prepare Cu-Zr catalyst, before can obtaining having the catalyst of good catalytic activity Driving body basic copper carbonate, employing conventional wash mode can be by Na in presoma simultaneously2O washs 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.
Including CuO and ZrO2, it is in terms of 100% by overall catalyst weight,
Wherein CuO content is 5～90wt%, preferably 15～80wt%；
ZrO2, content is 5～90wt%；It is preferably 15～80wt%
Wherein, described Impurities In Catalyst Na2O content is less than 0.05wt%.
Described catalyst be through hypergravity neutralize, aging, filter, hydro-thermal the most aging after prepare.
The two of the purpose of the present invention are to provide the preparation method of a kind of Cu-Zr catalyst.
Including:
(1) hypergravity neutralizes: copper zirconates composite compaction technique and alkali liquor add hypergravity rotation in manner of cocurrent flow Turning in reactor, react at 40～90 DEG C, the rotating speed of hypergravity revolving reaction still is 60～3000r/min, molten The liquid time of staying in hypergravity revolving reaction still is less than 5 minutes, preferably more than 1 minute, more excellent Choosing is less than half a minute；
(2) aging: by hypergravity revolving reaction still feed liquid out, to carry out aging in aging still, wait to expect After liquid is changed into green, i.e. stop aging, filter；
(3) hydro-thermal is the most aging: after material dilution step (2) obtained, introduce in hydro-thermal stirred tank old Changing 1～24 hour, temperature is 120～400 DEG C, pressure is 1～15MPa；
(4) filter, wash, be dried, roasting, molding；
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, preferably 2～7M, more preferably 3～5M；M i.e. mol/L.
Described alkali liquor is sodium carbonate and/or sodium bicarbonate, and concentration of lye is 0.1～4M, preferably 0.5～2M.
Specifically can use following steps:
(1) hypergravity reaction:
Copper mixing salt solution and alkali liquor are passed through hypergravity revolving reaction still from different inlets respectively, The porous aggregate layer of revolving bed, reacted suspension is discharged by revolving bed discharge gate.Blueness copper zirconium is combined Saline solution and alkali liquor add in hypergravity revolving reaction still in manner of cocurrent flow, react at 40～90 DEG C, overweight The rotating speed of power revolving reaction still is 60～3000r/min, and the solution time of staying in reactor is less than 5 points Clock, 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, wait to expect After liquid is changed into green, i.e. stop aging.Filter: use filter pressing or the mode of centrifugal filtration.
(3) hydro-thermal ageing process again:
Presoma step (1) obtained is dispersed in water after filtering again, introduces in hydro-thermal stirred tank, Under 120～400 DEG C, 1～15MPa, aging 1～24 hour；After hydrothermal treatment consists, carry out filtering, after washing etc. Continuous operation.Na after washing2O content (calculates, with butt copper zirconium mixed oxide, the catalyst i.e. obtained total Restatement) should be less than 0.05wt%.
Afterwards this feed liquid filtered, wash, be dried, roasting and compression molding.Described filtration, washing, Be dried, roasting and tabletting use this area conventional method and common process conditions.
Supergravity reactor is a kind of reactor making microcosmic mixing and mass transfer be greatly strengthened, and sinks with tradition Shallow lake reaction is compared, and gravity Method is prepared nanometer eta particle and had that the response time is short, granularity is little, narrow particle size distribution Etc. advantage.Certainly, a large amount of CO is proceeded in neutralization reaction2During generation, the nucleus of aforesaid basic copper nitrate Have passed through the growth of long period, may occur by part basic copper carbonate simultaneously.If therefore existed Supergravity reactor produces substantial amounts of CO2, it is clear that this does not play it and produces the excellent of a large amount of fine particles Gesture.Process nucleus generation and nucleus grown up as far as possible separately, is undoubtedly the selection of individual more reason. Therefore, the present invention specially selects two processes are divided into hypergravity N-process and ageing process.
Supergravity reactor in the present invention is the reactor carrying out reactive liquid solution, including the charging of two kinds of materials Mouth and a liquid outlet, without gas outlet.In supergravity reactor, the neutralization response time to the greatest extent may be used Can short be allowed to occur without carbon dioxide bubble to avoid the formation of over-reactive presoma, the most also need to be in charging Distributor well feeds distribution and suitable rotating speed makes charging mixing and stirring abundant.Overweight in the present invention The filler that can use in power reactor includes, but are not limited to metal and nonmetallic materials, such as silk screen and regular Filler etc..
Described charging, uses distributor charging.
The three of the purpose of the present invention are to provide the application in removing micro CO of a kind of Cu-Zr catalyst.
The content 5wppm of the CO in feeding ethylene or propylene, preferably 2wppm, more preferably 1wppm After removing, in material stream, carbon monoxide is less than 0.1ppm, preferably smaller than 30ppb.In the present invention, if do not had Particularly pointing out, the degree of catalyst is by weight, content wppm and wppb of material impurities By weight.
The device have the advantages that as follows:
The present invention uses the method that hypergravity-hydro-thermal method prepares Cu-Zr catalyst, uses relatively brachymedial and time, control Make suitable pH value range, hypergravity neutralizes and the aging multiple method such as separately, solves existing hypergravity skill Present in art, catalyst activity precursor controlling is improper, before can obtaining having the catalyst of good catalytic activity Drive body basic copper carbonate.Use hydro-thermal method aging catalyst presoma more simultaneously, solve washing and filtering difficulty Etc. problem, can by affect catalyst performance Na2O washing, to less than 0.05wt%, substantially increases catalysis The reactivity worth of agent, 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 about data is as follows:
Catalyst n a2O content is tested: use the Atomic Absorption Spectrometer (AAS) of VARIAN Oncology Systems to analyze.
Zirconium oxychloride, copper nitrate and sodium carbonate in embodiment are analytical pure, purchased from Tianjin recovery chemistry Reagent company limited.
Embodiment 1:
Configure nitric acid and zirconium oxychloride mixed solution that 5 cubic metres of total salt molar concentrations are 2mol/L (according to urging CuO/ZrO in agent2Weight ratio is 30/70) and the sodium carbonate liquor of 5 cubic metres of 2.0mol/L, with and flow Mode joins supergravity reactor and is neutralized, and neutralizing reaction temperature is 80 DEG C, supergravity reactor rotor Rotating speed is 2000rpm, and material is 2 minutes in the time of staying of reactor, from supergravity reactor blueness out Slurry pH value is 8.5.By hypergravity revolving reaction still feed liquid out, in aging still, 80 DEG C carry out aging, After feed liquid is changed into green, i.e. stop aging.The mode using filter pressing removes mother solution.
The presoma above-mentioned operation obtained is dispersed in water after filtering again, uses deionized water by above-mentioned thing After material dilution, introduce in hydro-thermal stirred tank that to carry out hydro-thermal the most aging, 200 DEG C, under 10MPa, aging 12 Hour.Afterwards to this feed liquid carry out 80 DEG C of sedimentation washings, 120 DEG C be dried 12 hours, roast under 400 DEG C of roastings Burn 8 hours and compression molding.Na after washing2O content (calculating with butt copper zirconium mixed oxide) is 0.042wt%.Made catalyst is 1#, component content is 30wt%CuO/70wt%ZrO2
Embodiment 2:
Other conditions are with embodiment 1.Supergravity reactor rotor speed is 2000rpm, material stopping at reactor Staying the time is 0.5 minute, is 7.5 from supergravity reactor slurry pH value out.Serosity the most out is Become green slurry.Na after washing2O content (calculating with butt copper zirconium mixed oxide) is 0.048wt%.Made catalyst is 2#.Component content is 30wt%CuO/70wt%ZrO2。
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, supergravity reactor rotor speed is 100rpm, and material is 5 minutes in the time of staying of reactor, from Supergravity reactor slurry pH value out is 6.5.Serosity the most out has turned into green slurry.Washing Na afterwards2O content (calculating with butt copper zirconium mixed oxide) is as 0.042wt%.Made catalyst It is 3#.Component content is 15wt%CuO/85wt%ZrO2
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, supergravity reactor rotor speed is 100rpm, and material is 5 minutes in the time of staying of reactor, from Supergravity reactor slurry pH value out is 6.5.Serosity the most out has turned into green slurry.Washing Na afterwards2O content (calculating with butt copper zirconium mixed oxide) is as 0.038wt%.Made catalyst It is 4#.Component content is 85wt%CuO/15wt%ZrO2。
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, supergravity reactor rotor speed is 1,000rpm, and material is 5 minutes in the time of staying of reactor, It is 7.5 from supergravity reactor slurry pH value out.Serosity the most out has turned into green slurry.
The condition that hydro-thermal is the most aging is, 120 DEG C, under 2MPa, aging 24 hours.Na after washing2O Content (calculating with butt copper zirconium mixed oxide) is as 0.042wt%.Made catalyst is 5#.Component contains Amount is 75wt%CuO/25wt%ZrO2。
Embodiment 6:
Other conditions are with embodiment 1.Complex copper zirconium mixing salt solution concentration is 4.5M, sodium carbonate liquor concentration For 3.5M, supergravity reactor rotor speed is 2,500rpm, and material is 5 minutes in the time of staying of reactor, It is 8.0 from supergravity reactor slurry pH value out.Serosity the most out has turned into green slurry.
The condition that hydro-thermal is the most aging is, 300 DEG C, under 12.5MPa, aging 2 hours.After washing Na2O content (calculating with butt copper zirconium mixed oxide) is as 0.035wt%.Made catalyst is 6#.Group Part content is 40wt%CuO/60wt%ZrO2。
Comparative example 1
Other conditions are with embodiment 1.Supergravity reactor rotor speed is 30rpm, and material is in the stop of reactor Time is 10 minutes, is 8.5 from supergravity reactor slurry pH value out.Serosity the most out becomes For black serosity.Na after washing2O content (calculating with butt copper zirconium mixed oxide) is as 0.039wt%. Made catalyst is 7#, component content is 30wt%CuO/70wt%ZrO2。
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 super Gravity reactor serosity the most out has turned into black serosity.Na after washing2O content is (with butt copper Zirconium mixed oxide calculates) it is 0.032wt%.Made catalyst is 8#, component content is 30wt%CuO/70wt%ZrO2。
Comparative example 3
Other conditions are with embodiment 1.Material after aging does not filters, and is directly entered hydrothermal aging operation, Serosity after hydrothermal aging is black.Na after washing2O content (calculates with butt copper zirconium mixed oxide) For 0.037wt%.Made catalyst is 9#, component content is 30wt%CuO/70wt%ZrO2。
Comparative example 4
Other conditions are with embodiment 1.Do not carry out hydrothermal aging, use normal ageing, owing to settling, adopt Filter with centrifuge washing, the Na after washing2O content (calculating with butt copper zirconium mixed oxide) is 4.08wt%.Made catalyst is 10#, component content is 30wt%CuO/70wt%ZrO2。
Test:
With the catalyst prepared by embodiment and comparative example, carry out the removing test of trace amounts of CO respectively.Fixing Bed flowing tubular reactor continuously carries out evaluating catalyst.Loaded catalyst is 500mL, in reactor Footpath is 40mm, and filling height is 30mm.After Catalyst packing, purge at 120 DEG C with high-purity nitrogen 12 hours.Material is the liquid propylene containing 2200ppbCO, and reaction pressure is 2.5MPa, and reaction temperature is 40 DEG C, air speed is 30hr-1, carry out the evaluation of 200 hours.Raw material and product use the micro-of AMETEK company Amount carbonyl analyzer detection.Result of the test is shown in Table 1.
Table 1 result of the test
As it can be seen from table 1
1) in strict accordance with preparation method process of the present invention, highly active removing trace can just be obtained The catalyst of CO.
Catalyst 1 prepared by embodiment 1 supergravity hydrothermal method#There is good reactivity；
In comparative example 7#With 8#Catalyst, as long in the time of staying for various reasons or charging salinity mistake Low etc., cause from supergravity reactor precursor solution blackening out, thus reactionless activity.
Comparative example 9#Catalyst, due to the mother solution from the hypergravity not removed high ph-values of precursor solution out, is led Cause its further reaction in hydro-thermal reaction and cause solution blackening, thus completely lose activity.
Comparative example 10#Catalyst owing to not carrying out hydrothermal aging, cause its serosity cannot filtration washing, thus urge Na in agent2O content is too high, thus completely loses activity.
2) although 7～8#Na in catalyst2O content relatively 1～2#Low, but comparative example obtains in preparation process Black Cu (OH)2Presoma, the most active extremely low;And embodiment 1～2#Respectively obtain the presoma of blueness Obtain suitably through hydrothermal aging after (basic copper nitrate) and green presoma (basic copper carbonate) Presoma (basic copper carbonate), basic copper carbonate presoma of preparing as is well understood in the art is Obtain the key of high activity co-precipitation copper catalyst.Therefore as described in background technology and description, controlling The suitable presoma of parameter in preparation process processed also it is critical that.

Claims (7)

1. the preparation method of a Cu-Zr catalyst, it is characterised in that described method includes:
(1) hypergravity neutralizes: copper zirconium composite compaction technique and alkali liquor are added hypergravity in manner of cocurrent flow and rotates In reactor, reacting at 40～90 DEG C, the rotating speed of hypergravity revolving reaction still is 60～3000r/min, solution The time of staying in hypergravity revolving reaction still is less than 5 minutes；
(2) aging: by hypergravity revolving reaction still feed liquid out, to carry out aging in aging still, wait to expect After liquid is changed into green, i.e. stop aging, filter；
(3) hydro-thermal is the most aging: after material dilution step (2) obtained, introduce in hydro-thermal stirred tank old Changing 1～24 hour, temperature is 120～400 DEG C, pressure is 1～15MPa；
(4) filter, wash, be dried, roasting, molding；
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 liquor is sodium carbonate and/or sodium bicarbonate, and concentration of lye is 0.1～4M；
Described catalyst includes: CuO and ZrO2, it is in terms of 100% by overall catalyst weight,
Wherein CuO content is 5～90wt%, ZrO2Content is 5～90wt%.
2. the preparation method of Cu-Zr catalyst as claimed in claim 1, it is characterised in that:
The concentration of copper zirconium composite compaction technique is 2～7M；Concentration of lye is 0.5～2M.
3. the preparation method of Cu-Zr catalyst as claimed in claim 2, it is characterised in that:
The concentration of copper zirconium composite compaction technique is 3～5M.
4. the preparation method of Cu-Zr catalyst as claimed in claim 1, it is characterised in that:
In step (1), the solution time of staying in hypergravity revolving reaction still is less than 1 minute.
5. the preparation method of Cu-Zr catalyst as claimed in claim 4, it is characterised in that:
In step (1), the solution time of staying in hypergravity revolving reaction still is less than half a minute.
6. the preparation method of Cu-Zr catalyst as claimed in claim 1, it is characterised in that:
The described charging joining hypergravity revolving reaction still, uses distributor charging.
7. the preparation method of Cu-Zr catalyst as claimed in claim 1, it is characterised in that:
Wherein CuO content is 15～80wt%；ZrO2Content is 15～80wt%；
Described Impurities In Catalyst Na2O content is less than 0.05wt%.
CN201310346605.1A 2013-08-09 2013-08-09 A kind of Cu-Zr catalyst, preparation method and application Active CN104338532B (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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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