CN108889304A - A kind of high stability cladded type copper-based catalysts and preparation method and application - Google Patents
A kind of high stability cladded type copper-based catalysts and preparation method and application Download PDFInfo
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- CN108889304A CN108889304A CN201810801018.XA CN201810801018A CN108889304A CN 108889304 A CN108889304 A CN 108889304A CN 201810801018 A CN201810801018 A CN 201810801018A CN 108889304 A CN108889304 A CN 108889304A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/154—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing copper, silver, gold, or compounds thereof
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Abstract
A kind of high stability cladded type copper-based catalysts, by mass percentage, consisting of CuO 36-59%, ZnO 24-40%, SiO21-40%.The present invention have it is at low cost, production process is simple, high stability, and the advantages of polymolecularity.
Description
Technical field
The invention belongs to field of catalyst preparation, in particular to a kind of copper-based method for preparing catalyst of high stability cladded type
And its application.
Background technique
Copper-based catalysts have been widely used in many industrialization reactions, such as synthesis gas system due to its high reactivity
Methanol, synthesis gas ethyl alcohol, methanol gasifying reform, CO oxidation or hydrogenation reaction, water gas shift reaction, Dehydrogenating reaction of alcohol etc..
Therefore, the research of copper-based catalysts is persistently widely paid close attention to, and is had become a hot topic of research, and many high-performance are copper-based urges
Agent is come into being.
However due to copper self-characteristic, such catalyst stability is relatively poor, easily inactivates during the reaction
Phenomenon.Such as CuZnO/Al2O3, it has been widely used in the methanol synthesis reaction in industry at present.However, within 1000h,
Catalyst can inactivate nearly 1/3, the main reason is that copper species particle growth causes active bits number to reduce in reaction process, draw
Sending out catalyst activity reduces.Currently, domestic and foreign scholars propose two kinds of machines at present for particle growth phenomenon in copper-based catalysts
Reason.The first is migration Agglomeration Mechanism, this refers to that temperature-rise period will lead to metal mass center and shift and then close to each other, wherein
It can mutually be touched apart from lesser active metal and agglomeration occurs.Second of mechanism is then due to curing mechanism.The mechanism
Think, metallic particles is grown up unrelated with grain spacing, is grown up mainly by the inhomogenous institute of metal particle size in catalyst
It causes.Because different for partial size its surface metal concentration of metallic particles are different, it is considered that the smaller surface of metal partial size
Metal concentration is bigger.Therefore, it will form metal concentration gradient in the metal surface of different-grain diameter, cause bulky grain bigger, generation
Valence is little particle disappearance.For above two particle growth mechanism, existing scholar proposes several solutions at present.Such as, add
Adding carrier is promoted active metal dispersion and is acted on using the confinement of carrier duct to prevent metal from growing up；To the catalyst after load
It carries out organically-modified preventing metal from growing up to hinder metal migration, touch with this.
The hollow anti-type of ringing a bell/silica core-shell that 106064239 A of Chinese patent CN discloses a high degree of dispersion is received
Rice grain preparation method.But this method preparation step is relatively cumbersome, uses organic metal salt as metal during the preparation process
Source, higher cost is difficult to realize to be produced in enormous quantities.
105576207 A of Chinese patent CN discloses a kind of hollow nano combined material of copper-tin alloy silica core-shell
Preparation method for material and application only use a kind of organic solvent of ethyl alcohol although the method is during the preparation process, relatively environment-friendly.However by
In needs previously prepared " core ", therefore coat uneven.
105170995 A of Chinese patent CN discloses a kind of method of coated with silica gold-silver alloy nano particle.So
And the method is core as silicon source, higher cost, and the selection relatively preferable electrum of stability using tetraethyl orthosilicate, it is just real
Show in preparation process and has more equably coated.
Summary of the invention
The object of the present invention is to provide a kind of at low cost, production process is simple, high stability, and the cladded type of polymolecularity
Copper-based catalysts and preparation method and application.
High stability cladded type copper-based catalysts of the invention, by mass percentage, consisting of CuO 36-59%,
ZnO 24-40%,SiO21-40%.
The preparation method of catalyst of the present invention, includes the following steps：
The metal salt mixed aqueous solution that distilled water is made into concentration 1-2M is added in copper nitrate and zinc nitrate by step 1, and ultrasound is molten
Solution obtains solution A to clear；
Step 2, by Na2CO3With Na2SiO3Mixing, is made into aqueous solution that anion concentration is 1-2 M as precipitating reagent B,
Middle Na2CO3With Na2SiO3Molar ratio be 0.5-100, in addition with concentration be 1-2 M Na2CO3Aqueous solution is as precipitating reagent
C；
Solution A is added drop-wise in water, while precipitating reagent is added dropwise by step 3 at 60-80 DEG C with rate of addition 60-80r/min
Precipitant solution C is added dropwise rapidly in B after precipitant solution B is added dropwise, entire that process control is added dropwise in pH between 7-9,
After being added dropwise, continue aging 1-3h, filter, washs, it is dry, then in 350-450 DEG C of temperature lower calcination, cupper-based catalyst is made
Agent.
Catalyst of the invention is suitable for fixed bed reactors CO2Catalyst is packed into continuous fixed by synthesizing methanol by hydrogenating
Bed reactor in, first 240-280 DEG C, normal pressure, also Primordial Qi percent by volume be 5-10% H2With 90-95% N2Mixing
In gas, prereduction in 4-6 hours is carried out, wherein gaseous mixture air speed is 9000-12000 mL/ (gh)；It is passed through CO later2、H2With
The mixed gas of inert atmosphere composition is reacted, and 240-280 DEG C of reaction temperature, reaction pressure 3.0-5.0MPa, air speed are
9000-12000mL/ (gh), percent by volume shared by feed components are：H272-78%, CO213-24%, indifferent gas
Atmosphere 4-10%.
Inert atmosphere as described above is N2Or Ar.
The invention discloses a kind of preparation methods of cladded type copper-based catalysts, and the catalyst is used for CO2Add hydrogen system
In standby methanol reaction, beneficial effects of the present invention are：
（1）The present invention prepares cladded type copper-based catalysts using the method for hydrolytic precipitation.With tradition with silica supported system
Standby catalyst is compared, using this method prepare catalyst it is more uniform, realize during the preparation process active metal with
SiO2Uniform mixing, promote the dispersion of active metal.
（2）The present invention uses the catalyst of hydrolysis methods preparation, living compared with the catalyst of traditional co-precipitation method preparation
Property component dispersion is more uniform, size is more uniform, while active metal is coated in silica shell, growth restriction, because
This stability gets a promotion.
（3）The present invention can be with one-step method compared with other coated catalysts using the catalyst of hydrolysis methods preparation
Active metal is coated on SiO2In shell, it is easy to operate it is easy, low energy consumption for production process, low in cost and environmentally protective, because
This market application prospect is wide.
Preparation method disclosed in this patent is further described below by specific embodiment, but the present invention is not by following
The limitation of embodiment.
Embodiment 1
22.5g copper nitrate will be weighed and 14.9g zinc nitrate is placed in a beaker, the metal that a certain amount of distilled water is made into concentration 2M is added
Mixed salt solution, ultrasonic dissolution 1h obtain blue clear transparent solutions A, weigh 0.5g sodium silicate nanahydrate and 15g sodium carbonate,
It is made into the precipitant solution B of 2 M of anion concentration, is in addition the Na of 2M with 200mL concentration is taken2CO3Precipitant solution C is spare.
At 60 DEG C under the conditions of water-bath, solution A and solution B are added drop-wise to jointly in 400mL water, wherein the molten A drop acceleration of metal salt
Precipitant solution C is added dropwise rapidly in 80r/min after mixed precipitant solution B is added dropwise, and protects whole process control pH value of solution
It holds 9 ± 0.1, and is stirred continuously.After solution A is added dropwise, stops that precipitating reagent is added dropwise immediately and continue aging 1h, filter, wash
It washs.80 DEG C after drying 12 hours, 350 DEG C temperature lower calcination 4 hours, catalyst is made.The mass fraction percentage of the catalyst
Become than group：CuO 59%; ZnO 40%; SiO2 1%。
The catalyst is in CO2Add hydrogen to prepare the reducing condition of methanol, activity rating condition and evaluation result and sees attached list 1, tool
Steps are as follows for body：
Firstly, it is to be evaluated that the catalyst tabletting made is sieved into 20-40 mesh.Then catalyst 0.5g sieved, is placed in
In fixed bed reactors, the quartz sand of 30 mesh is loaded at the both ends of reactor.In normal pressure, certain temperature, certain volume percentage
Gaseous mixture is restored to restore 4-6h under certain air speed.After the completion of reduction, 100 DEG C or less are naturally cooling to temperature of reactor and (is prevented
Only antedating response), reducing gas is switched to unstripped gas, wherein the volume ratio of unstripped gas be certain value, then certain temperature,
Methanolizing reaction is carried out under pressure and space velocities, is terminated after reacting a period of time.
Embodiment 2
22.5g copper nitrate will be weighed and 14.9g zinc nitrate is placed in a beaker, the metal that a certain amount of distilled water is made into concentration 1M is added
Mixed salt solution, ultrasonic dissolution 1h obtain blue clear transparent solutions A.Weigh 5.3g sodium silicate nanahydrate and 13.2g carbonic acid
Sodium is made into the precipitant solution B of 1 M of anion concentration, is in addition the Na of 2M with 200mL concentration is taken2CO3Precipitant solution C is standby
With.At 65 DEG C under the conditions of water-bath, solution A and solution B are added drop-wise to jointly in 400mL water, wherein the molten A drop of metal salt accelerates
60 r/min are spent, precipitant solution C is added dropwise rapidly after mixed precipitant solution B is added dropwise, whole process is made to control solution
PH is maintained at 7.5 ± 0.1, and is stirred continuously.After solution A is added dropwise, stops that precipitating reagent is added dropwise immediately and continues aging 1.5h,
Filtering, washing.80 DEG C after drying 12 hours, 350 DEG C temperature lower calcination 4 hours, catalyst is made.The quality of the catalyst point
Number percentage group becomes：CuO 53%; ZnO 37%; SiO2 10%。
The catalyst is in CO2Add hydrogen to prepare the reducing condition of methanol, activity rating condition and evaluation result and sees attached list 1, tool
Body step is as described in Example 1.
Embodiment 3
22.5g copper nitrate will be weighed and 14.9g zinc nitrate is placed in a beaker, the gold that a certain amount of distilled water is made into concentration 1.5M is added
Belong to mixed salt solution, ultrasonic dissolution 1h obtains blue clear transparent solutions A.Weigh 11.8g sodium silicate nanahydrate and 10.8g carbon
Sour sodium is made into the precipitant solution B of 1.5 M of anion concentration, is in addition the Na of 2M with 200mL concentration is taken2CO3Precipitant solution
C is spare.At 80 DEG C under the conditions of water-bath, solution A and solution B are added drop-wise to jointly in 400mL water, wherein the molten A drop of metal salt
Precipitant solution C is added dropwise rapidly after mixed precipitant solution B is added dropwise, makes whole process control by 75 r/min of acceleration
PH value of solution is maintained at 7 ± 0.1, and is stirred continuously.After solution A is added dropwise, stops that precipitating reagent is added dropwise immediately and continues aging 3h,
Filtering, washing.80 DEG C after drying 12 hours, 400 DEG C temperature lower calcination 4 hours, catalyst is made.The quality of the catalyst point
Number percentage group becomes：CuO 47%; ZnO 33%; SiO2 20%。
The catalyst is in CO2Add hydrogen to prepare the reducing condition of methanol, activity rating condition and evaluation result and sees attached list 1, tool
Body step is as described in Example 1.
Embodiment 4
22.5g copper nitrate will be weighed and 14.9g zinc nitrate is placed in a beaker, the metal that a certain amount of distilled water is made into concentration 2M is added
Mixed salt solution, ultrasonic dissolution 1h obtain blue clear transparent solutions A.Weigh 20.3g sodium silicate nanahydrate and 7.6g carbonic acid
Sodium is made into the precipitant solution B of 2 M of anion concentration, is in addition the Na of 2M with 200mL concentration is taken2CO3Precipitant solution C is standby
With.At 75 DEG C under the conditions of water-bath, solution A and solution B are added drop-wise to jointly in 400mL water, wherein the molten A drop of metal salt accelerates
70 r/min are spent, precipitant solution C is added dropwise rapidly after mixed precipitant solution B is added dropwise, whole process is made to control solution
PH is maintained at 8 ± 0.1, and is stirred continuously.After solution A is added dropwise, stops that precipitating reagent is added dropwise immediately and continue aging 3h, mistake
Filter, washing.80 DEG C after drying 12 hours, 450 DEG C temperature lower calcination 4 hours, catalyst is made.The mass fraction of the catalyst
Percentage group becomes：CuO 41%; ZnO 29%; SiO2 30%。
The catalyst is in CO2Add hydrogen to prepare the reducing condition of methanol, activity rating condition and evaluation result and sees attached list 1, tool
Body step is as described in Example 1.
Embodiment 5
22.5g copper nitrate will be weighed and 14.9g zinc nitrate is placed in a beaker, the gold that a certain amount of distilled water is made into concentration 1.2M is added
Belong to mixed salt solution, ultrasonic dissolution 1h obtains blue clear transparent solutions A.It weighs 31.6g sodium silicate nanahydrate and 7.6g is anhydrous
Sodium carbonate is made into the precipitant solution B of 2 M of anion concentration, is in addition the Na of 1.2M with 200mL concentration is taken2CO3Precipitating reagent is molten
Liquid C is spare.At 70 DEG C under the conditions of water-bath, solution A and solution B are added drop-wise to jointly in 400mL water, wherein the molten A liquid of metal salt
Precipitant solution C is added dropwise rapidly after mixed precipitant solution B is added dropwise, makes whole process control by 65 r/min of rate of addition
PH value of solution processed is maintained at 8.5 ± 0.1, and is stirred continuously.After solution A is added dropwise, stops that precipitating reagent is added dropwise immediately and continue old
Change 3h, filters, washing.80 DEG C after drying 12 hours, 450 DEG C temperature lower calcination 4 hours, catalyst is made.The catalyst
Mass fraction percentage group becomes：CuO 36%; ZnO 24%; SiO2 40%。
The catalyst is in CO2Add hydrogen to prepare the reducing condition of methanol, activity rating condition and evaluation result and sees attached list 1, tool
Body step is as described in Example 1.
Comparative example 1
22.5g copper nitrate will be weighed and 14.9g zinc nitrate is placed in a beaker, the metal that a certain amount of distilled water is made into concentration 1M is added
Mixed salt solution, ultrasonic dissolution 1h obtain blue clear transparent solutions A.18.2 g natrium carbonicum calcinatums are weighed, it is dense to be made into anion
Spend the precipitant solution B of 1 M.At 70 DEG C under the conditions of water-bath, solution A and solution B cocurrent are added drop-wise in 400mL water, wherein
Molten 65 r/min of A drop acceleration of metal salt, control precipitant solution B rate of addition make that procedure pH value of solution guarantor is entirely added dropwise
It holds 7.5 ± 0.1, and is stirred continuously.After solution A is added dropwise, stops that precipitating reagent is added dropwise immediately and continues aging 1h, filter,
Washing.80 DEG C after drying 12 hours, 400 DEG C temperature lower calcination 4 hours, catalyst is made.The mass fraction hundred of the catalyst
Dividing becomes than group：CuO 65%; ZnO 35%.
The catalyst is in CO2Add hydrogen to prepare the reducing condition of methanol, activity rating condition and evaluation result and sees attached list 1, tool
Body step is as described in Example 1.
Comparative example 2
22.5g copper nitrate will be weighed and 14.9g zinc nitrate is placed in a beaker, the metal that a certain amount of distilled water is made into concentration 1M is added
Mixed salt solution, ultrasonic dissolution 1h obtain blue clear transparent solutions A.18.2 g natrium carbonicum calcinatums are weighed, it is dense to be made into anion
Spend the precipitant solution B of 1 M.It weighs 2.5g fumed silica and is added to uniform stirring in 70 DEG C of water of 400mL, then will
Solution A and solution B cocurrent are added drop-wise in 400mL water, wherein molten 65 r/min of A drop acceleration of metal salt, and control precipitating reagent is molten
Liquid B rate of addition, which makes procedure pH value of solution entirely is added dropwise, is maintained at 7.5 ± 0.1, and is stirred continuously.After solution A is added dropwise,
Stop that precipitating reagent is added dropwise immediately and continue aging 1h, filters, washing.80 DEG C after drying 12 hours, in 400 DEG C of temperature lower calcinations 4
Hour, catalyst is made.The mass fraction percentage group of the catalyst becomes：CuO 47%; ZnO 33%; SiO2 20%。
The catalyst is in CO2Add hydrogen to prepare the reducing condition of methanol, activity rating condition and evaluation result and sees attached list 1, tool
Body step is as described in Example 1.
As the evaluation result data of embodiment 1 to 5 in table 1 it is found that first being increased using the presentation of catalyst activity made from this law
Its reason of the trend reduced after adding is active specy can be promoted to disperse when the incorporation of a small amount of silicon, when silicone content is excessively high, activity
Metal is largely covered by silica shell, can not touch reaction gas, therefore reactivity reduces.
By the evaluation result data of embodiment 1 to 5 in table 1 and the evaluation result data of comparative example 1 it is found that using this legal system
The catalyst stability obtained is better than common coprecipitation, this is because enhancing for silica promotes between active specy
Interaction force and silica shell inhibit active metal particles to grow up, and then promote catalyst stabilization raising.
By the evaluation result data of embodiment 3 in table 1 and the evaluation result data of comparative example 2 it is found that using hydrolytic precipitation
Although the catalyst activity of method preparation is slightly below the catalyst of comparative example 2, stability has obtained greatly being promoted.This is because
The catalyst of coprecipitation preparation, active metal is primarily present in carrier outer surface, therefore catalyst activity is higher, however easily
Reunion is grown up, and catalyst inactivation is induced.And the catalyst of cladding process preparation, although active metal, which is wrapped in inside silicon shell, to be caused
Activity is declined slightly, however the presence of silicon shell can the reunion of greatly inhibitory activity metal grow up phenomenon, make catalyst stabilization
Property gets a promotion.
The foregoing is merely the preferred embodiment of the embodiment of the present invention, the present invention is not limited to above-described embodiment, for
For those skilled in the art, the present invention can have transformation and replacement, such as be prepared using this method preparation using other silicon sources
Coated catalyst etc..Therefore, any modification for being made under the principle of all embodiments described in the method for the present invention and spirit, equivalent
Replacement, improvement etc., belong to protection scope of the present invention.
Table 1
Note：The ratio of activity decline is relative to initial activity, activity rating 60h, activity decline 6-19%, active down ratio
It is smaller, it is better to represent stability.
Claims (4)
1. a kind of high stability cladded type copper-based catalysts, it is characterised in that high stability cladded type cupper-based catalyst of the invention
Agent, by mass percentage, consisting of CuO 36-59%, ZnO 24-40%, SiO2 1-40%。
2. a kind of preparation method of high stability cladded type copper-based catalysts as described in claim 1, it is characterised in that including
Following steps：
The metal salt mixed aqueous solution that distilled water is made into concentration 1-2M, ultrasonic dissolution is added in copper nitrate and zinc nitrate by step 1
To clear, solution A is obtained；
Step 2, by Na2CO3With Na2SiO3Mixing, being made into anion concentration is the aqueous solution of 1-2 M as precipitating reagent B, wherein
Na2CO3With Na2SiO3Molar ratio be 0.5-100, in addition with concentration be 1-2 M Na2CO3Aqueous solution is as precipitating reagent C；
Solution A is added drop-wise in water, while precipitating reagent B is added dropwise by step 3 at 60-80 DEG C with rate of addition 60-80r/min,
Precipitant solution C is added dropwise rapidly after precipitant solution B is added dropwise, entire that process control is added dropwise in pH between 7-9, dropwise addition
After, continue aging 1-3h, filter, washs, it is dry, then in 350-450 DEG C of temperature lower calcination, copper-based catalysts are made.
3. a kind of application of high stability cladded type copper-based catalysts as described in claim 1, it is characterised in that including as follows
Step：
Catalyst is suitable for fixed bed reactors CO2Catalyst is fitted into continuous fixed bed reactors by synthesizing methanol by hydrogenating, first
First 240-280 DEG C, normal pressure, also Primordial Qi percent by volume be 5-10% H2With 90-95% N2Gaseous mixture in, carry out 4-6 it is small
When prereduction, wherein gaseous mixture air speed be 9000-12000 mL/ (gh)；It is passed through CO later2And H2, wherein H2：CO2Volume
Than for 3-6：1,240-280 DEG C of reaction temperature, reaction pressure 3.0-5.0MPa, air speed are 9000-12000mL/ (gh), raw material
Percent by volume shared by each component is：H272-78%, CO213-24%, inert atmosphere 4-10%.
4. a kind of application of high stability cladded type copper-based catalysts as claimed in claim 3, it is characterised in that described is lazy
Property atmosphere be N2Or Ar.
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| CN114618499A (en) * | 2022-03-24 | 2022-06-14 | 山东亮剑环保新材料有限公司 | Doped CO2Preparation method of hydrogenation catalyst |
| CN115532270A (en) * | 2022-10-26 | 2022-12-30 | 常州大学 | Dynamic copper-zinc catalyst, and preparation method and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114618499A (en) * | 2022-03-24 | 2022-06-14 | 山东亮剑环保新材料有限公司 | Doped CO2Preparation method of hydrogenation catalyst |
| CN115532270A (en) * | 2022-10-26 | 2022-12-30 | 常州大学 | Dynamic copper-zinc catalyst, and preparation method and application thereof |
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