CN108499566A - A kind of preparation method and application of CuNi bases catalyst - Google Patents
A kind of preparation method and application of CuNi bases catalyst Download PDFInfo
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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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- 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
- B01J23/74—Iron group metals
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- C07C231/00—Preparation of carboxylic acid amides
- C07C231/10—Preparation of carboxylic acid amides from compounds not provided for in groups C07C231/02 - C07C231/08
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Abstract
The present invention provides a kind of preparation method and application of CuNi bases catalyst, and the preparation method includes：In reflux, urea or concentrated ammonia liquor or both mixed liquor and mantoquita, nickel salt and carrier or auxiliary agent are stirred evenly, metal precipitates are obtained by ammonia still process method, using centrifugation, washing, drying, roasting, reduction can must prepare CuNi base catalyst.The mass percent of each component is in the CuNi bases catalyst：CuO：30~50%, NiO：5~25%, carrier or auxiliary agent：30~60%.CuNi base catalyst activity components prepared by the present invention are not lost in, stable in catalytic performance, are used for CO2Add hydrogen and HN (CH3)2(DMA) DMF yields are high when reaction synthesis DMF, while required cost of material is cheap and easily-available, and preparation method is simple, easy to operate, and process costs are low, and repetitive rate is high, therefore have good application prospect.
Description
Technical field
The invention belongs to domain of inorganic chemistry, are related to a kind of preparation method and application of catalyst, more particularly to one kind
The preparation method of CuNi base catalyst and its in CO2Hydrogen is added to react the application in synthesis DMF with dimethylamine.
Background technology
CO2It is that a large amount of existing hydrocarbons, rich reserves are easy to get, are cheap, is nontoxic, is renewable in nature, it will
It, which is converted into valuable chemicals or fuel, can not only alleviate energy shortage, be expected to solve asking for greenhouse-gas control
Topic.In CO2Numerous path for transformation in, hydrogenation reaction occupies an important position, and formic acid, formates can be made by hydrogenation reaction
And the pluralities of fuels such as derivative, methanol, dimethyl ether, carbon monoxide and methane and chemicals.
N,N-Dimethylformamide (DMF), be a kind of colourless, higher boiling, hygroscopicity, fishlike smell liquid, be a kind of pole
Property non-proton, high dielectric amount organic solvent, extractant and industrial chemicals, reel off raw silk from cocoons in medicine, polyurethane synthesis and polyacrylonitrile
Etc. have important application in production processes.The production method of DMF has very much, mainly there is formic acid esterification two-step method, methanol dehydrogenation two
Footwork and dimethylamine and CO one-step method.Formic acid esterification method be formic acid with methanol carry out esterification generate methyl formate again with dimethylamine gas
Phase reaction generates DMF, and the method is simple for process, cost of equipment is low but of high cost, and product purity is low.Methanol dehydrogenation method is and methanol
Dehydrogenation reaction generates methyl formate, then is reacted with dimethylamine and generate DMF, and method production cost valence compared with old technique is much lower.
Currently, in the industrial production, mostly passing through CO and dimethylamine one-step synthesis method with sodium methoxide, KF/ZnO, Cu salt etc. for catalyst
DMF, the method low in raw material price, production technology is advanced, saves the energy, product purity is higher, but CO is toxic, does not meet green
The idea of development of chemistry.
The synthetic route for being expected to substitute toxic CO one-step method at present is CO in the presence of dimethylamine2Hydrogenation, patent
US4269998 report with Raney Ni, Raney Cu, Raney Co, copper chromite and Pt, Pd of load, Rh, Ru,
Os, Ir, Re are catalyst CO2、H2Different types of dialkylformamide, including DMF are synthesized with corresponding dialkylamine,
Yield highest 37%.Haynes in 1970 etc. uses homogeneous catalyst Pd (CO3)[P(C6H5)3]2By CO2、H2It is synthesized with dimethylamine
DMF.Although now to CO2、H2With dimethylamine synthesize DMF research goed deep into, but due to largely be precious metal catalyst
Agent is very difficult to apply in actual production.Han et al. recent studies have shown that Cu/ZnO catalyst is from CO2、H2It is closed with dimethylamine
At DMF effective catalysts, up to 97%, but due to Related Technical Issues such as catalyst stabilities, which is still trying DMF yields
Test conceptual phase.
Invention content
In view of the foregoing deficiencies of prior art, the purpose of the present invention is to provide a kind of preparations of CuNi bases catalyst
Methods and applications prepare the synthesis difunctional alloy catalysts of CuNi by ammonia still process method, and the catalyst activity component which prepares is not
It is lost in, performance is stablized, and preparation method is simple, easy to operate, and process costs are low, and repetitive rate is high.
In order to achieve the above objects and other related objects, the present invention provides a kind of CuNi bases catalyst, in the catalyst
The mass percent of each component is：CuO：30~50%；NiO：5~25%；Carrier or auxiliary agent：30~60%.
A kind of scheme of optimization as CuNi bases catalyst of the present invention, the carrier are gas phase SiO2、Al2O3Microballoon or
Zirconia ball, the auxiliary agent are Ludox, aluminum nitrate or zirconyl nitrate, and the carrier and auxiliary agent are not limited to cited type.
The present invention also provides a kind of preparation method of CuNi bases catalyst, the preparation method includes at least：
1) it by urea or the mixed liquor of concentrated ammonia liquor or urea and concentrated ammonia liquor, is mixed with mantoquita and nickel salt, mixing is made
Solution；
2) carrier or auxiliary agent are added in the mixed solution, material to be aging is made；
3) material to be aging is poured into reflux oil bath reaction kettle, sediment is generated by ammonia still process back flow reaction；
4) sediment is prepared after centrifugation, washing, drying, roasting, reduction to CuNi base catalyst successively.
The mixed liquor by urea or concentrated ammonia liquor or urea and concentrated ammonia liquor is needed in the step 1), with mantoquita and nickel salt
After mixing, it is stirred to uniform.After carrier or auxiliary agent is added in the step 2), it is again stirring for uniformly, being made to be aging
Material.
A kind of scheme of optimization of preparation method as CuNi bases catalyst of the present invention, it is described in the step 1)
Mantoquita is copper nitrate, copper chloride or basic copper carbonate, and the nickel salt is nickel nitrate or nickel chloride.
A kind of scheme of optimization of preparation method as CuNi bases catalyst of the present invention, in the step 1), mantoquita with
And the molar ratio of the Cu and Ni of nickel salt are (0.5~6)：1.
A kind of scheme of optimization of preparation method as CuNi bases catalyst of the present invention, in the step 1), urea or
The NH that the mixed liquor of concentrated ammonia liquor or urea and concentrated ammonia liquor is provided4 +Mole and Cu and Ni integral molar quantity ratios be (20~8)：
1。
A kind of scheme of optimization of preparation method as CuNi bases catalyst of the present invention, it is described mixed in the step 1)
Close a concentration of 0.5~3M of solution.
A kind of scheme of optimization of preparation method as CuNi bases catalyst of the present invention, in the step 2), the load
Body is gas phase SiO2、Al2O3Microballoon (10 μm or so) or zirconia ball (10 μm or so), the auxiliary agent be Ludox (preferably
40wt%SiO2), aluminum nitrate or zirconyl nitrate.
A kind of scheme of optimization of preparation method as CuNi bases catalyst of the present invention, the carrier or auxiliary agent and Ni's
Molar ratio is (2~15)：1.
A kind of scheme of optimization of preparation method as CuNi bases catalyst of the present invention will be described in the step 3)
Material to be aging pour into reflux oil bath reaction kettle in reflux digestion, reflux temperature be 50~150 DEG C, ageing time be 6~for 24 hours.
A kind of scheme of optimization of preparation method as CuNi bases catalyst of the present invention, in the step 4), the roasting
The condition of burning is 400~600 DEG C, and constant temperature time is 2~8h.It is preferred that heating rate is 1 DEG C/mi.
A kind of scheme of optimization of preparation method as CuNi bases catalyst of the present invention, in the step 4), it is described also
Former condition is that 400~600 DEG C are warming up in restoring atmosphere, and the recovery time is 2~8h.It is preferred that heating rate is 1 DEG C/min.
The preferred hydrogen of reducing atmosphere.
In addition, the present invention also provides a kind of application of CuNi bases catalyst, it to be used for CO2With HN (CH3)2Hydrogenation reaction is closed
In being reacted at DMF, using autoclave, reaction condition is for the reaction：Reaction pressure is 2~10MPa, and reaction temperature is
100~200 DEG C, the reaction time 2~for 24 hours, H2/CO2Molar ratio is 1：1.
The invention discloses a kind of preparation method of CuNi bases catalyst with it in CO2Add hydrogen and HN (CH3)2Reaction synthesis
The application of DMF reactions.In reflux, with urea or concentrated ammonia liquor or both mixed liquor and mantoquita, nickel salt and carrier or help
Agent is raw material, and metal precipitates are obtained by ammonia still process circumfluence method, and using centrifugation, washing, drying, roasting, reduction can must make
Standby DMF catalyst.The mass percent of each component is in the CuNi bases catalyst：CuO：30~50%, NiO：5~25%,
Carrier or auxiliary agent：30~60%.CuNi base catalyst performances prepared by the present invention are stablized, and DMF yields are high, while required raw material valence
Lattice are cheap and easily-available, and preparation method is simple, easy to operate, and process costs are low, and repetitive rate is high, therefore have good application prospect.
Description of the drawings
Fig. 1 is the flow diagram of the preparation method of CuNi bases catalyst of the present invention.Wherein, S1~S4 indicates step.
Specific implementation mode
Illustrate that embodiments of the present invention, those skilled in the art can be by this specification below by way of specific specific example
Disclosed content understands other advantages and effect of the present invention easily.The present invention can also pass through in addition different specific realities
The mode of applying is embodied or practiced, the various details in this specification can also be based on different viewpoints with application, without departing from
Various modifications or alterations are carried out under the spirit of the present invention.
It should be clear that in the following example not specifically dated process equipment or device be all made of conventional equipment in the art or
Device；All pressure values and range all refer to relative pressure.
In addition, it should also be understood that, one or more method and step mentioned in the present invention does not repel before and after the combination step
It can also be inserted into other methods step there may also be other methods step or between these explicitly mentioned steps, unless separately
It is described；It should also be understood that the combination connection relation between one or more equipment/device mentioned in the present invention is not repelled
The front and back two equipment/devices specifically mentioned there may also be other equipment/device or at these of the unit equipment/device it
Between can also be inserted into other equipment/device, unless otherwise indicated.Moreover, unless otherwise indicated, the number of various method steps is only
Differentiate the convenient tool of various method steps, rather than to limit the ordering of various method steps or limiting the enforceable model of the present invention
It encloses, relativeness is altered or modified, and without material changes in technical content, when being also considered as, the present invention is enforceable
Scope.
The present invention provides a kind of preparation method and application of CuNi bases catalyst, as shown in Figure 1, the preparation method is at least
Including：
S1 mixes urea or the mixed liquor of concentrated ammonia liquor or urea and concentrated ammonia liquor with mantoquita and nickel salt, and mixing is made
Solution；
Carrier or auxiliary agent are added in the mixed solution, material to be aging are made by S2；
S3, the material to be aging is poured into reflux oil bath reaction kettle, and sediment is generated by ammonia still process back flow reaction；
The sediment is prepared the catalysis of CuNi bases by S4 after centrifugation, washing, drying, roasting, reduction successively
Agent.
In addition, the present invention also provides a kind of application of CuNi bases catalyst, it to be used for CO2With HN (CH3)2Hydrogenation reaction is closed
In being reacted at DMF, using autoclave, reaction condition is for the reaction：Reaction pressure is 2~10MPa, and reaction temperature is
100~200 DEG C, the reaction time 2~for 24 hours, H2/CO2Molar ratio is 1：1.
The preparation method and application of the CuNi base catalyst of the present invention are illustrated with specific embodiment below.
【Embodiment 1】
Take appropriate copper nitrate, nickel nitrate, 40%Wt% Ludox and concentrated ammonia liquor by Cu:Ni=1：1, SiO2：Ni=10：1,
Concentrated ammonia liquor：(Cu+Ni)=15：1 (molar ratio) is configured to the mixed material of 1M.Mixed material is placed in three with condensing reflux pipe
In mouth flask, under oil bath heating, reaction solution is centrifuged, is washed, is dry, obtained by the reflux digestion 16h under the conditions of 80 DEG C
Solid sediment rises to 500 DEG C by 1 DEG C/min heating rates, roasts 6h, obtain metal oxide precursor.Weigh 0.20g gold
Belong to oxide precursor to be fitted into reduction tube, in H2It is restored under atmosphere, reducing condition is：500 are risen to by 1 DEG C/min heating rates
DEG C, restore 3h, H2Flow velocity 20ml/min obtains CuNi base catalyst after reduction, wherein the CuNi base catalyst includes
CuOWt%：28.5%, NiOWt%:24.3%, SiO2Wt%:47.2%.
CuNi base catalyst 0.2g after above-mentioned reduction is fitted into autoclave, 3.519g DMA methanol solutions are added,
From air inlet 3MPa H2Air in kettle is replaced, is operated 3 times repeatedly.Then 1：1 pours CO2And H2To pressure 6MPa, close
Air intake valve is closed, stirring in kettle is reached 500 revs/min, 140 DEG C is risen to 1 DEG C/min heating rates, reacts 6h.Reaction terminates
Postcooling is detached catalyst and product liquid to room temperature, using high speed centrifugation, and to liquid product into chromatography.Reaction knot
Fruit is shown in Table 1.
【Embodiment 2】
Take appropriate copper nitrate, nickel nitrate, 40%Wt% Ludox and urea by Cu:Ni=3：1, SiO2：Ni=10：1, urine
Element：(Cu+Ni)=8：1 (molar ratio) is configured to the mixed material of 1.5M.Mixed material is placed in three mouthfuls with condensing reflux pipe
In flask, under oil bath heating, reaction solution is centrifuged, is washed, is dry by the reflux digestion 16h under the conditions of 80 DEG C, consolidate
Body sediment rises to 600 DEG C by 1 DEG C/min heating rates, roasts 3h, obtain metal oxide precursor.Weigh 0.20g metals
Oxide precursor is fitted into reduction tube, in H2It is restored under atmosphere, reducing condition is：600 are risen to by 1 DEG C/min heating rates
DEG C, restore 3h, H2Flow velocity 20ml/min obtains CuNi base catalyst after reduction, wherein the CuNi base catalyst includes
CuOWt%：30.5%, NiOWt%：9.8%, SiO2Wt%：59.7%.
CuNi base catalyst 0.2g after above-mentioned reduction is fitted into autoclave, 3.5g DMA methanol solutions are added, from
Air inlet 3MPa H2Air in kettle is replaced, is operated 3 times repeatedly.Then 1：1 pours CO2And H2To pressure 6MPa, close
Stirring in kettle is reached 500 revs/min, rises to 140 DEG C with 1 DEG C/min heating rates, react 6h by air intake valve.After reaction
It is cooled to room temperature, is detached catalyst and product liquid using high speed centrifugation, and to liquid product into chromatography.Reaction result
It is shown in Table 1.
【Embodiment 3】
Take appropriate copper nitrate, nickel nitrate, 40%Wt% Ludox and urea by Cu:Ni=5：1, SiO2：Ni=10：1, urine
Element：(Cu+Ni)=8：1 (molar ratio) is configured to the mixed material of 1.5M.Mixed material is placed in three mouthfuls with condensing reflux pipe
In flask, under oil bath heating, reaction solution is centrifuged, is washed, is dry by the reflux digestion 16h under the conditions of 80 DEG C, consolidate
Body sediment rises to 500 DEG C by 1 DEG C/min heating rates, roasts 3h, obtain metal oxide precursor.Weigh 0.20g metals
Oxide precursor is fitted into reduction tube, in H2It is restored under atmosphere, reducing condition is：500 are risen to by 1 DEG C/min heating rates
DEG C, restore 6h, H2Flow velocity 20ml/min obtains CuNi base catalyst after reduction, wherein the CuNi base catalyst includes
CuOWt%：49.2%, NiOWt%：6.3%, SiO2Wt%：44.5%.
CuNi base catalyst 0.2g after above-mentioned reduction is fitted into autoclave, 3.5g DMA methanol solutions are added, from
Air inlet 3MPa H2Air in kettle is replaced, is operated 3 times repeatedly.Then 1：1 pours CO2And H2To pressure 6MPa, close
Stirring in kettle is reached 500 revs/min, rises to 140 DEG C with 1 DEG C/min heating rates, react 6h by air intake valve.After reaction
It is cooled to room temperature, is detached catalyst and product liquid using high speed centrifugation, and to liquid product into chromatography.Reaction result
It is shown in Table 1.
【Embodiment 4】
Take appropriate copper nitrate, nickel nitrate, aluminum nitrate and urea by Cu:Ni=5：1, Al：Ni=3：1, urea：(Cu+Ni)
=8：1 (molar ratio) is configured to the mixed material of 0.5M.Mixed material is placed in the three-necked flask with condensing reflux pipe, in oil
Under bath heating, reaction solution is centrifuged, is washed, is dry, obtained solid sediment, press by the reflux digestion 16h under the conditions of 80 DEG C
1 DEG C/min heating rates rise to 500 DEG C, roast 3h, obtain metal oxide precursor.Weigh 0.20g metallic oxide precursors
Body is fitted into reduction tube, in H2It is restored under atmosphere, reducing condition is：500 DEG C are risen to by 1 DEG C/min heating rates, restores 3h, H2
Flow velocity 20ml/min obtains CuNi base catalyst after reduction, wherein the CuNi base catalyst includes CuOWt%：35.0%,
NiOWt%：6.8%, Al2O3Wt%：58.2%.
CuNi base catalyst 0.2g after above-mentioned reduction is fitted into autoclave, 3.5g DMA methanol solutions are added, from
Air inlet 3MPa H2Air in kettle is replaced, is operated 3 times repeatedly.Then 1：1 pours CO2And H2To pressure 6MPa, close
Stirring in kettle is reached 500 revs/min, rises to 140 DEG C with 1 DEG C/min heating rates, react 6h by air intake valve.After reaction
It is cooled to room temperature, is detached catalyst and product liquid using high speed centrifugation, and to liquid product into chromatography.Reaction result
It is shown in Table 1.
【Embodiment 5】
Take appropriate copper nitrate, nickel nitrate, 40%Wt% Ludox, concentrated ammonia liquor and urea by Cu:Ni=3：1, SiO2：Ni=
8：1, NH4 +：(Cu+Ni)=9：1, concentrated ammonia liquor：Urea=1.5：1 (molar ratio), is configured to the mixed material of 1M.By mixed material
Be placed in the three-necked flask with condensing reflux pipe, under oil bath heating, the reflux digestion 6h under the conditions of 120 DEG C, by reaction solution from
Heart separation, washing, drying, obtain solid sediment, rise to 600 DEG C by 1 DEG C/min heating rates, roast 3h, obtain metal oxygen
Compound presoma.It weighs 0.20g metal oxide precursors to be fitted into reduction tube, in H2It is restored under atmosphere, reducing condition is：It presses
1 DEG C/min heating rates rise to 500 DEG C, restore 3h, H2Flow velocity 20ml/min obtains CuNi base catalyst after reduction, wherein should
CuNi base catalyst includes CuOWt%：37.5%, NiOWt%：10.2%, SiO2Wt%：52.3%.
CuNi base catalyst 0.2g after above-mentioned reduction is fitted into autoclave, 3.5g DMA methanol solutions are added, from
Air inlet 3MPa H2Air in kettle is replaced, is operated 3 times repeatedly.Then 1：1 pours CO2And H2To pressure 6MPa, close
Stirring in kettle is reached 500 revs/min, rises to 140 DEG C with 1 DEG C/min heating rates, react 6h by air intake valve.After reaction
It is cooled to room temperature, is detached catalyst and product liquid using high speed centrifugation, and to liquid product into chromatography.Reaction result
It is shown in Table 1.
【Embodiment 6】
Take appropriate copper nitrate, nickel nitrate, 40%Wt% Ludox and urea by Cu:Ni=3：1, SiO2：Ni=8：1, urine
Element：(Cu+Ni)=8：1 (molar ratio) is configured to the mixed material of 1.5M.Mixed material is placed in three mouthfuls with condensing reflux pipe
In flask, under oil bath heating, reflux digestion for 24 hours, reaction solution is centrifuged, is washed, is dry under the conditions of 65 DEG C, consolidate
Body sediment rises to 500 DEG C by 1 DEG C/min heating rates, roasts 3h, obtain metal oxide precursor.Weigh 0.20g metals
Oxide precursor is fitted into reduction tube, in H2It is restored under atmosphere, reducing condition is：500 are risen to by 1 DEG C/min heating rates
DEG C, restore 3h, H2Flow velocity 20ml/min obtains CuNi base catalyst after reduction, wherein the CuNi base catalyst includes
CuOWt%：38.3%, NiOWt%：9.6%, SiO2Wt%：52.1%.
CuNi base catalyst 0.2g after above-mentioned reduction is fitted into autoclave, 3.5g DMA methanol solutions are added, from
Air inlet 3MPa H2Air in kettle is replaced, is operated 3 times repeatedly.Then 1：1 pours CO2And H2To pressure 4MPa, close
Stirring in kettle is reached 500 revs/min, rises to 140 DEG C with 1 DEG C/min heating rates, react 18h by air intake valve.After reaction
It is cooled to room temperature, is detached catalyst and product liquid using high speed centrifugation, and to liquid product into chromatography.Reaction result
It is shown in Table 1.
【Embodiment 7】
Take appropriate copper nitrate, nickel nitrate, 40%Wt% Ludox and urea by Cu:Ni=3：1, SiO2：Ni=8：1, urine
Element：(Cu+Ni)=8：1 (molar ratio) is configured to the mixed material of 1.5M.Mixed material is placed in three mouthfuls with condensing reflux pipe
In flask, under oil bath heating, reflux digestion for 24 hours, reaction solution is centrifuged, is washed, is dry under the conditions of 65 DEG C, consolidate
Body sediment rises to 500 DEG C by 1 DEG C/min heating rates, roasts 3h, obtain metal oxide precursor.Weigh 0.20g metals
Oxide precursor is fitted into reduction tube, in H2It is restored under atmosphere, reducing condition is：500 are risen to by 1 DEG C/min heating rates
DEG C, restore 3h, H2Flow velocity 20ml/min obtains CuNi base catalyst after reduction, wherein the CuNi base catalyst includes
CuOWt%：38.3%, NiOWt%：9.6%, SiO2Wt%：52.1%.
CuNi base catalyst 0.2g after above-mentioned reduction is fitted into autoclave, 3.5g DMA methanol solutions are added, from
Air inlet 3MPa H2Air in kettle is replaced, is operated 3 times repeatedly.Then 1：1 pours CO2And H2To pressure 8MPa, close
Stirring in kettle is reached 500 revs/min, rises to 180 DEG C with 1 DEG C/min heating rates, react 4h by air intake valve.After reaction
It is cooled to room temperature, is detached catalyst and product liquid using high speed centrifugation, and to liquid product into chromatography.Reaction result
It is shown in Table 1.
【Embodiment 8】
Take appropriate copper nitrate, nickel nitrate, 40%Wt% Ludox and urea by Cu:Ni=3：1, SiO2：Ni=8：1, urine
Element：(Cu+Ni)=8：1 (molar ratio) is configured to the mixed material of 1.5M.Mixed material is placed in three mouthfuls with condensing reflux pipe
In flask, under oil bath heating, reflux digestion for 24 hours, reaction solution is centrifuged, is washed, is dry under the conditions of 65 DEG C, consolidate
Body sediment rises to 500 DEG C by 1 DEG C/min heating rates, roasts 3h, obtain metal oxide precursor.Weigh 0.20g metals
Oxide precursor is fitted into reduction tube, in H2It is restored under atmosphere, reducing condition is：500 are risen to by 1 DEG C/min heating rates
DEG C, restore 3h, H2Flow velocity 20ml/min obtains CuNi base catalyst after reduction, wherein the CuNi base catalyst includes
CuOWt%：38.3%, NiOWt%：9.6%, SiO2Wt%：52.1%.
CuNi base catalyst 0.2g after above-mentioned reduction is fitted into autoclave, 3.5g DMA methanol solutions are added, from
Air inlet 3MPa H2Air in kettle is replaced, is operated 3 times repeatedly.Then 1：1 pours CO2And H2To pressure 10MPa, close
Stirring in kettle is reached 500 revs/min, rises to 120 DEG C with 1 DEG C/min heating rates, react 6h by air intake valve.After reaction
It is cooled to room temperature, is detached catalyst and product liquid using high speed centrifugation, and to liquid product into chromatography.Reaction result
It is shown in Table 1.
1 embodiment catalyst reaction result of table
| Embodiment | DMA conversion ratios (%) | DMF yields (%) |
| 1 | 44.9 | 32.12 |
| 2 | 90.1 | 50.60 |
| 3 | 69.8 | 40.73 |
| 4 | 65.9 | 39.58 |
| 5 | 93.2 | 72.82 |
| 6 | 89.9 | 72.16 |
| 7 | 94.8 | 79.28 |
| 8 | 96.5 | 86.76 |
Table 1 gives the reaction result data table of each embodiment catalyst, and the result listed by the table 1 finds out that the CuNi bases are urged
There is agent higher DMA conversion ratios and DMF yields, simultaneous reactions to terminate to collect product liquid to be colourless transparent liquid, show
It can prepare that catalytic performance is excellent while its stable structure using the preparation method of the present invention, the CuNi bases that active component is not lost in
Catalyst.
The above, only presently preferred embodiments of the present invention, not to the present invention in any form with substantial limitation,
It should be pointed out that for those skilled in the art, under the premise of not departing from the method for the present invention, can also make
Several improvement and supplement, these are improved and supplement also should be regarded as protection scope of the present invention.All those skilled in the art,
Without departing from the spirit and scope of the present invention, when made using disclosed above technology contents it is a little more
Dynamic, modification and the equivalent variations developed, are the equivalent embodiment of the present invention；Meanwhile all substantial technologicals pair according to the present invention
The variation, modification and evolution of any equivalent variations made by above-described embodiment, still fall within the range of technical scheme of the present invention
It is interior.
Claims (13)
1. a kind of CuNi bases catalyst, which is characterized in that the mass percent of each component is in the catalyst：CuO：30~
50%；NiO：5~25%；Carrier or auxiliary agent：30~60%.
2. CuNi bases catalyst according to claim 1, it is characterised in that：The carrier is gas phase SiO2、Al2O3Microballoon
Or zirconia ball, the auxiliary agent are Ludox, aluminum nitrate or zirconyl nitrate.
3. a kind of preparation method of CuNi bases catalyst as claimed in claim 1 or 2, which is characterized in that the preparation method
It includes at least：
1) it by urea or the mixed liquor of concentrated ammonia liquor or urea and concentrated ammonia liquor, is mixed with mantoquita and nickel salt, mixed solution is made；
2) carrier or auxiliary agent are added in the mixed solution, material to be aging is made；
3) material to be aging is poured into reflux oil bath reaction kettle, sediment is generated by ammonia still process back flow reaction；
4) sediment is prepared after centrifugation, washing, drying, roasting, reduction to CuNi base catalyst successively.
4. the preparation method of CuNi bases catalyst according to claim 3, it is characterised in that：It is described in the step 1)
Mantoquita be copper nitrate, copper chloride or basic copper carbonate, the nickel salt be nickel nitrate or nickel chloride.
5. the preparation method of CuNi bases catalyst according to claim 3, it is characterised in that：In the step 1), mantoquita
And the molar ratio of the Cu and Ni of nickel salt are (0.5~6)：1.
6. the preparation method of CuNi bases catalyst according to claim 3, it is characterised in that：In the step 1), urea,
Or the NH that concentrated ammonia liquor or the mixed liquor of urea and concentrated ammonia liquor are provided4 +Mole and Cu and Ni integral molar quantity ratios be (20~
8)：1.
7. the preparation method of CuNi bases catalyst according to claim 3, it is characterised in that：It is described in the step 1)
A concentration of 0.5~3M of mixed solution.
8. the preparation method of CuNi bases catalyst according to claim 3, it is characterised in that：It is described in the step 2)
Carrier is gas phase SiO2、Al2O3Microballoon or zirconia ball, the auxiliary agent are Ludox, aluminum nitrate or zirconyl nitrate.
9. the preparation method of CuNi bases catalyst according to claim 3, it is characterised in that：The carrier or auxiliary agent and Ni
Molar ratio be (2~15)：1.
10. the preparation method of CuNi bases catalyst according to claim 3, it is characterised in that：In the step 3), by institute
State material to be aging pour into reflux oil bath reaction kettle in reflux digestion, reflux temperature be 50~150 DEG C, ageing time be 6~
24h。
11. the preparation method of CuNi bases catalyst according to claim 3, it is characterised in that：It is described in the step 4)
The condition of roasting is 400~600 DEG C, and constant temperature time is 2~8h.
12. the preparation method of CuNi bases catalyst according to claim 3, it is characterised in that：It is described in the step 4)
The condition of reduction is that 400~600 DEG C are warming up in restoring atmosphere, and the recovery time is 2~8h.
13. a kind of application of CuNi bases catalyst as claimed in claim 1 or 2, which is characterized in that be used for CO2With HN (CH3)2
Hydrogenation reaction synthesizes in DMF reactions, and using autoclave, reaction condition is for the reaction：Reaction pressure is 2~10MPa, instead
It is 100~200 DEG C to answer temperature, the reaction time 2~for 24 hours, and H2/CO2Molar ratio is 1：1.
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| CN115245826A (en) * | 2021-12-24 | 2022-10-28 | 浙江科技学院 | Preparation method and equipment of nickel-based catalyst for methane reforming reaction |
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