CN104923209B - A kind of solid catalyst for acetone self-condensation reaction and its preparation method and application - Google Patents
A kind of solid catalyst for acetone self-condensation reaction and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of solid catalyst for acetone self-condensation reaction and its preparation method and application, belong to for acetone self-condensation reaction catalyst technical field.Coprecipitation prepares magnalium hydrotalcite as catalyst precarsor first, and then catalyst precarsor is well mixed with rare earth component and organic dispersing agent, using wet method kneading extruded moulding, solid catalyst is obtained after roasting.Using continuous fixed bed reaction or continuous device, the catalyst is applied to acetone self-condensation reaction, 100~450 DEG C of reaction temperature, 0.1~2.0MPa of reaction pressure, volume space velocity is 0.1~5h during liquid‑1, acetone conversion per pass 20~50%, wherein effective selectivity (isopropylidene acetone+isophorone) 90%~99%, the selectivity of isophorone>70%.The catalyst surface has a soda acid double activity center, and can flexibly modulation, catalyst activity, good stability.
Description
Technical field
The present invention relates to be used for acetone self-condensation reaction catalyst technical field, and in particular to one kind is self condensed for acetone
Solid catalyst of reaction and its preparation method and application.
Background technology
Acetone is also referred to as dimethyl ketone, is simplest ketone in saturated fat ketone series.- 95 DEG C of fusing point, 56 DEG C of boiling point, nothing
Color liquid, there is special odor, can dissolve acetic acid and cellulose nitrate.It is anti-that the carbonyl of acetone can occur addition with various nucleopilic reagents
Should, such as catalytic hydrogenation generation isopropanol, reduction generation pinacol；With ammonia derivative, hydrogen cyanide, acetylide, organometallic
Compound reaction etc.；Acetone can also carry out the reaction of α-H, for example with halogen occur substitution reaction, itself or with other compounds send out
Reaction of raw similar aldol condensation etc..The self-condensation reaction product of wherein acetone has diacetone alcohol, isopropylidene acetone, different Fo Er
Ketone, trimethylbenzene etc..Acetone self-condensation reaction is consecutive reaction, and its dimerisation products is mainly isopropylidene acetone, and trimerization product is main
It is isophorone.Isopropylidene acetone is important organic synthesis intermediate, is mainly used in medicine, fine chemicals and insecticide
Deng medium-boiling solvent being can serve as, as nitrocellulose and various kinds of resin-especially vinylite and spray painting etc. is molten
Agent.Isophorone is a kind of high boiling solvent of function admirable, while be also important Organic Chemicals, in plastics, gluing
It is widely used in the industries such as agent, medicine and spices.The isophorone as obtained in isophorone gasifies through phosgene again through addition, hydrogenation
Diisocyanate has excellent mechanical property and ageing-resistant performance, can be used as the curing agent of complex solid propellant；It is different
3,3, the 5- cyclonols that phorone is generated through catalytic hydrogenation are a kind of widely used medicine intermediates, with being obtained for it
Cyclandelate be a kind of blood vessel dilatation class medicine, can be used for treat cerebral arteriosclerosis.
Acetone self-condensation reaction belongs to aldol reaction, and aldol condensation refers to two points in the presence of diluted alkaline or diluted acid
The carbonyls containing α-H of son interacts, and the α-H in one of molecule are added to the carbonylic oxygen atom of another molecule
On, remainder is added on carbonylic carbon atom, generates a molecule beta-hydroxy aldehyde or a molecule beta-hydroxy ketone, by aldol condensation,
New carbon-carbon bond can be in the molecule formed, and increases carbochain.
Aldol reaction includes various reactions, and differential responses need different catalyst for different purpose products,
Even same reaction, using same catalyst series, catalyst surface acid-base property is different, and the ratio of products therefrom is also different,
This is primarily due to aldol condensation the different reaction mechanisms mechanism of reaction under the catalyst of different acid or alkalescence, and is directed to purpose product
Thing, can be lived by the preparation method that changes catalyst, the method regulating catalyst surface such as the relative scale soda acid for changing metal
Property center intensity and the ratio of soda acid amount, aldol reaction is reached maximum yield, realize commercial Application higher
Value.
At present, acetone carries out self-condensation reaction and has realized industrialized production in liquid phase, and catalyst is potassium hydroxide or hydrogen-oxygen
Change sodium solution, but liquid phase reactor equipment is autoclave, and acetone conversion is not high, and product is difficult to be separated, and waste liquid etching apparatus,
Pollution environment.Acetone is set to carry out the green syt work that self-condensation reaction is focus development in recent years in gas phase using fixed bed
Skill route, reaction condition is relatively mild, and catalyst preparation and product separation process are without waste discharge, and fixed bed reaction
Device can realize continuous production, easily expand the scale of production.Such as：Patent US5849957 discloses a kind of magnalium double oxide catalysis
Agent, for powdered, reaction is carried out catalyst in autoclave, and in 200 DEG C of temperature, under the conditions of pressure 25bar, acetone conversion is
38%, the selectivity to isophorone is 51%.Patent EP0640387A1 discloses one kind by aluminum carbonate basic hydrate and carbon
Sour magnesium hydrate is the precursor magnalium mixed oxide catalyst that obtains of roasting, in 290 DEG C of temperature, under the conditions of pressure 40psig,
Liquid air speed 2hr-1, acetone conversion is 31.34%, and the selectivity to isophorone is 16.4%.Patent CN101050168A
Disclose what one kind was made up of solid sodium ethanol (sodium methoxide or caustic alcohol) and highly basic (potassium hydroxide, NaOH or calcium hydroxide)
Solid catalyst, it is batch (-type) to react, and acetone is heated to 180~210 DEG C, is passed through in reactor, 3 minutes reaction time, acetone
Conversion ratio is 40.8%, and the selectivity to isophorone is 33.5%.CN102188967A discloses one kind by co-precipitation legal system
Standby carrier is that magnesia, silica, aluminum oxide and calcium carbonate and active component are cerium or the solid catalyst of caesium, and catalyst is
10-20 mesh powder, 290 DEG C of reaction temperature, pressure 0.7Mpa, liquid air speed 1.0hr-1, ketone：Nitrogen ratio is 1:10, acetone conversion
It is 16.4%, the selectivity to isophorone is 78.2%, isopropylidene acetone is selectively 16.4%.CN102258994A is disclosed
A kind of magnesium-aluminum-calcium zirconium mixed oxide solid catalyst prepared by coprecipitation, catalyst is 8-14 mesh powder, reaction temperature
300 DEG C of degree, pressure 1MPa, liquid air speed 2.0hr-1, reacting 24 hours, acetone conversion is 43.5%, to isophorone and different
The overall selectivity of propylidene acetone is 94.6%.
Acetone gas phase self-condensation reaction needs soda acid double activity center solid catalyst, the key of its technology be high activity,
The selection of high-selectivity catalyst active component and the shaping technology of preparing of catalyst.And above-mentioned recent researches report is more
Method for preparing catalyst is generally powder catalyst prepared by coprecipitation, and catalyst strength is poor, and due to co-precipitation legal system
Standby condition is harsh, prepares the repeated poor of catalyst, the requirement therefore, it is difficult to meet large-scale industry device application.
To sum up, a kind of preparation condition is researched and developed gently, catalyst reuse ability is high, disclosure satisfy that large-scale industry device
The solid catalyst of the requirement of application is problem demanding prompt solution then.
The content of the invention
For the weak point that above-mentioned present technology is present, self condensed instead for acetone it is an object of the invention to provide one kind
Solid catalyst answered and its preparation method and application, is prepared for acetone by co-precipitation-wet method kneading group technology
The solid catalyst of self-condensation reaction, preparation condition is gentle, and catalyst has active component is uniformly dispersed, side pressure strength is high etc. concurrently
Advantage.
To achieve the above object, the technical solution adopted in the present invention is as follows：
A kind of preparation method of solid catalyst for acetone self-condensation reaction, is using co-precipitation-wet method kneading group
Conjunction method prepares solid catalyst, specifically includes following steps：
(1) prepared as the magnalium hydrotalcite of catalyst precarsor, Mg elements in gained magnalium hydrotalcite using coprecipitation
It is (1-5) with the molar ratio of Al elements:(1-2)；
(2) wet method kneading prepares the solid catalyst：
The well mixed acquisition mixture of magnalium hydrotalcite, active rare-earth component and organic dispersing agent prepared by step (1)
Material, addition accounts for the nitric acid of 1~5wt.% of mixed material as binding agent, by wet method kneading extruded moulding after being well mixed, into
Pattern product are dried 6~12 hours at a temperature of 100~130 DEG C, then are calcined 4~8 hours at 300~800 DEG C, that is, be molded
Solid catalyst.In the step, it is the nitric acid of 3wt% to use concentration as the nitric acid of binding agent.
In above-mentioned steps (1), use coprecipitation prepare the process of magnalium hydrotalcite for：Magnesium salts and aluminium salt are mixed and molten
Solution is configured to mixing salt solution in deionized water；Precipitating reagent is dissolved in deionized water again aqueous slkali is obtained；Gained is mixed
Salting liquid and aqueous slkali are added in reaction vessel using cocurrent mode, then temperature be 30-90 DEG C, pH be 9-12 under the conditions of instead
Answer 10-100 minutes, then it is aging 6-36 hours after, by gained washing of precipitate to neutrality, magnalium hydrotalcite is obtained after drying.
Mg in the mixing salt solution2+With Al3+Molar ratio according to the magnalium in the magnalium hydrotalcite of required preparation
Ratio is chosen.In the mixing salt solution of preparation, Mg2+With Al3+Molar concentration rate be (1~2.5)：1.
The magnesium salts is magnesium nitrate, magnesium acetate or magnesium sulfate, preferably magnesium nitrate；The aluminium salt is aluminum nitrate, aluminum acetate
Or aluminum sulfate, preferably aluminum nitrate；The precipitating reagent be potassium hydroxide, potassium carbonate, NaOH and sodium carbonate in one kind or
Several, preferably NaOH and sodium carbonate is used in mixed way.
In above-mentioned steps (2), the part by weight of the magnalium hydrotalcite and active rare-earth component is (90~98)：(0.1~
10)；The weight of the organic dispersing agent is the 2~50% of magnalium hydrotalcite and active rare-earth component weight.
In above-mentioned steps (2), the active rare-earth component is the oxide or its hydroxide of rare earth element, the rare earth
Element is lanthanum, yttrium or cerium；The organic dispersing agent is ethanol, ethylene glycol, polyethylene glycol, propane diols, ethylenediamine, monoethanolamine, two
Monoethanolamine or triethanolamine.
Using the above method prepare the solid catalyst for acetone self-condensation reaction, its specific surface area be 100~
300m2/ g, 0.3~1.0cm of pore volume3/ g, 10~50nm of aperture, side pressure strength 50-150Ncm-1。
It is continuously anti-using fixed bed when the solid catalyst is applied into acetone gas phase self-condensation reaction production isophorone
Answering device carries out acetone gas phase self-condensation reaction, and process conditions are：100~450 DEG C of reaction temperature, 0.1~2.0MPa of pressure, liquid
When air speed 0.1~5h-1。
Advantages of the present invention and have the beneficial effect that：
1st, catalyst preparation technology of the present invention by the acidity on rare earth component and organic dispersing agent regulating catalyst surface and
Alkaline bit density and pore size distribution, can effectively improve activity and selectivity of the catalyst for target product isophorone.Pass through
The active bit density of catalyst prepared by co-precipitation-wet method kneading combined method is high, while have larger specific surface area and
Granule strength higher, therefore catalyst has long lifespan, and can repeatedly regenerate and use.
2nd, the active rare-earth component that the present invention chooses is the oxide or hydroxide of Rare Earth Lanthanum (or yttrium or cerium), and purpose exists
In solid catalyst surface alkalescence bit density and intensity is improved, improve catalyst surface basic sites and acid site density ratio to carry
Selectivity of the high catalyst for target product isophorone.
3rd, organic dispersing agent selection ethylene glycol or diethanol amine of the present invention etc., it is therefore intended that increase catalyst precarsor with activity
The decentralization of component.
4th, the present invention uses wet method kneading by fine catalyst precursor and active component extruded moulding, wherein catalyst precarsor
With active rare-earth component (with La2O3、CeO2And Y2O3Meter) part by weight be (90~98)：(0.1~10), organic dispersing agent is
The 2~50% of solid masses.The key problem in technology of catalyst preparation of the present invention is：A () catalyst precarsor is multiple for magnalium hydrotalcite class
Compound；B () uses wet method kneading by fine catalyst precursor and active component extruded moulding；C () adds organic dispersing agent；(d)
Catalyst surface acid-base property density is adjusted using active rare earth component.
5th, the solid catalyst that the present invention is prepared using co-precipitation-wet method kneading group technology, on the one hand increased activity
The decentralization of component, on the other hand promotes the bonding action of catalyst precarsor and active component, catalyst is had activearm concurrently
Be uniformly dispersed, the advantages of side pressure strength is high.
6th, solid catalyst prepared by the present invention is applied to acetone gas phase self-condensation reaction, and acetone conversion per pass 20~
36%, effective selectivity (isopropylidene acetone+isophorone) 90%~97%, the selectivity of wherein isophorone reaches>70%.
Device was operated by more than 2000 hours, catalyst catalytic performance stabilization.
Figure of description
Fig. 1 is solid catalyst preparation technology flow chart of the present invention.
Fig. 2 is magnalium hydrotalcite XRD spectra prepared by embodiment 1.
Fig. 3 is solid catalyst XRD spectra prepared by embodiment 1.
Specific embodiment
Below in conjunction with drawings and Examples in detail the present invention is described in detail.
Embodiment 1
The present embodiment is to prepare catalyst precarsor using coprecipitation, then prepares solid catalyst by wet method kneading,
As shown in figure 1, the preparation method detailed process is as follows：
1st, the preparation of mixing salt solution：
666.7g Mg (NO are weighed respectively3)2·6H2O and 322.2g Al (NO3)3·9H2O crystal, adds deionized water,
Stirring is completely dissolved salt, is configured to 1000ml mixing salt solutions；
2nd, the preparation of aqueous slkali：
A certain amount of NaOH is weighed, is dissolved in deionized water, be configured to the NaOH solution that concentration is 3.8mol/L, then
A certain amount of sodium carbonate is weighed, is dissolved in deionized water, compound concentration is the Na of 1.0mol/L2CO3Solution.
3rd, the preparation of magnalium hydrotalcite：
By in 500ml deionized waters addition reactor, after being heated to 60 DEG C, by mixing salt solution and aqueous slkali, (NaOH is molten
Liquid and Na2CO3Solution) during cocurrent adds reactor, 60 DEG C of reaction temperature, pH controls are reacted 30 minutes in 9-10, and aging 12 is small
When, to after neutrality, 120 DEG C of dryings 6 hours obtain magnalium hydrotalcite, as catalyst precarsor for washing.
Fig. 2 show prepared magnalium hydrotalcite XRD spectra, it can be seen that the typical lamellar magnalium water of the product of synthesis
Talcum diffraction maximum, the crystallinity of product is relatively good.
4th, wet method kneading dispensing：
Take the catalyst precarsor 48.1g of above-mentioned preparation, active rare-earth component La2O3It is 4.3g, organic dispersing agent ethylene glycol is
3.8g weighs each component respectively.
5th, wet method kneading prepares solid catalyst：
After catalyst precarsor is well mixed with organic dispersing agent ethylene glycol, addition accounts for catalyst precarsor weight 3~5%
Salpeter solution carries out kneading, and salpeter solution concentration is 3wt..%.Active rare-earth component is added and accounts for catalyst precarsor weight 5%
Salpeter solution stir into pasty state.Kneading 3 on banded extruder by the catalyst precarsor of preliminary kneading and pasty state active rare-earth component
~4 times, then extruded moulding.Molded samples are dried 6 hours at 110 DEG C, in being calcined 4 hours at 550 DEG C, obtain 1# shapings solid
Body catalyst.
Fig. 3 is solid catalyst XRD spectra manufactured in the present embodiment, it can be seen that without obvious rare earth oxygen
The diffraction maximum of compound or hydroxide, illustrate add rare earth component catalyst Dispersion on surface it is relatively good, be conducive to carrying
High catalyst surface alkalinty bit density and intensity, improve catalyst surface basic sites and acid site density ratio to improve catalyst
For the selectivity of target product isophorone.
Embodiment 2
The present embodiment is to prepare catalyst precarsor using coprecipitation, then prepares solid catalyst by wet method kneading,
Detailed process is as follows：
1st, the preparation of mixing salt solution：
650.5g Mg (NO are weighed respectively3)2·6H2O and 310.2g Al (NO3)3·9H2O crystal, adds deionized water,
Stirring is completely dissolved salt, is configured to 1000ml mixing salt solutions；
2nd, the preparation of aqueous slkali：
A certain amount of NaOH is weighed, is dissolved in deionized water, be configured to the NaOH solution that concentration is 3.8mol/L, then
A certain amount of sodium carbonate is weighed, is dissolved in deionized water, compound concentration is the Na of 1.0mol/L2CO3Solution.
3rd, the preparation of magnalium hydrotalcite：
By in 500ml deionized waters addition reactor, after being heated to 65 DEG C, by mixing salt solution and aqueous slkali, (NaOH is molten
Liquid and Na2CO3Solution) during cocurrent adds reactor, 65 DEG C of reaction temperature, pH controls are reacted 40 minutes in 9-10, and aging 15 is small
When, to after neutrality, 120 DEG C of dryings 6 hours obtain magnalium hydrotalcite, as catalyst precarsor for washing.
4th, wet method kneading dispensing：
Take the catalyst precarsor 48g of above-mentioned preparation, active rare-earth component Y2O3It is 4.5g, organic dispersing agent ethylene glycol is 5g,
Each component is weighed respectively.
5th, wet method kneading prepares solid catalyst：
After catalyst precarsor is well mixed with organic dispersing agent ethylene glycol, addition accounts for the nitre of catalyst precarsor weight 3%
Acid solution carries out kneading, and salpeter solution concentration is 3wt.%.Active rare-earth component is added the nitre for accounting for catalyst precarsor weight 6%
Acid solution stirs into pasty state.Kneading 3~4 on banded extruder by the catalyst precarsor of preliminary kneading and pasty state active rare-earth component
Time, then extruded moulding.Molded samples are dried 8 hours at 120 DEG C, in being calcined 5 hours at 600 DEG C, obtain 2# formation solids
Catalyst.
Embodiment 3
The present embodiment is to prepare catalyst precarsor using coprecipitation, then prepares solid catalyst by wet method kneading,
Detailed process is as follows：
1st, the preparation of mixing salt solution：
700.4g Mg (NO are weighed respectively3)2·6H2O and 352.1g Al (NO3)3·9H2O crystal, adds deionized water,
Stirring is completely dissolved salt, is configured to 1000ml mixing salt solutions；
2nd, the preparation of aqueous slkali：
A certain amount of NaOH is weighed, is dissolved in deionized water, be configured to the NaOH solution that concentration is 3.8mol/L, then
A certain amount of sodium carbonate is weighed, is dissolved in deionized water, compound concentration is the Na of 1.0mol/L2CO3Solution.
3rd, the preparation of magnalium hydrotalcite：
By in 500ml deionized waters addition reactor, after being heated to 50 DEG C, by mixing salt solution and aqueous slkali, (NaOH is molten
Liquid and Na2CO3Solution) during cocurrent adds reactor, 50 DEG C of reaction temperature, pH controls are reacted 35 minutes 9.5, and aging 17 is small
When, to after neutrality, 120 DEG C of dryings 6 hours obtain magnalium hydrotalcite, as catalyst precarsor for washing.
4th, wet method kneading dispensing：
Take the catalyst precarsor 47.8g of above-mentioned preparation, active rare-earth component CeO2It is 4.16g, organic dispersing agent ethylene glycol
It is 6.7g, each component is weighed respectively.
5th, wet method kneading prepares solid catalyst：
After catalyst precarsor is well mixed with organic dispersing agent ethylene glycol, addition accounts for the nitre of catalyst precarsor weight 5%
Acid solution carries out kneading, and salpeter solution concentration is 3wt.%.Active rare-earth component is added the nitre for accounting for catalyst precarsor weight 5%
Acid solution stirs into pasty state.Kneading 3~4 on banded extruder by the catalyst precarsor of preliminary kneading and pasty state active rare-earth component
Time, then extruded moulding.Molded samples are dried 8 hours at 115 DEG C, in being calcined 4 hours at 650 DEG C, obtain 3# formation solids
Catalyst.
Embodiment 4
The present embodiment is to prepare catalyst precarsor using coprecipitation, then prepares solid catalyst by wet method kneading,
Difference from Example 1 is：
Wet method kneading each component dispensing is：Catalyst precarsor 45.4g, active rare-earth component is La2O3With the mixture of CeO,
Wherein：La2O3It is 4.26g, CeO2It is 5.1g, organic dispersing agent ethylene glycol is 4.2g.4# solid catalysts are obtained.
Embodiment 5
The present embodiment is to prepare catalyst precarsor using coprecipitation, then prepares solid catalyst by wet method kneading,
Difference from Example 1 is：
Wet method kneading each component dispensing is：Catalyst precarsor 46.1g, active rare-earth component is Y2O3And CeO2Mixture,
Wherein：Y2O3It is 4.3g, CeO2It is 6.1g, organic dispersing agent ethylene glycol is 6.7g.5# solid catalysts are obtained.
Each solid catalyst raw material composition transitivity data prepared by above-described embodiment 1-5 are listed in the table below in 1.S in tableBET
Represent the specific surface area of prepared solid catalyst.
As can be seen from Table 1, in preparation process of the present invention, due to increased the decentralization of active component, and promote
The bonding action of catalyst precarsor and active component is entered, the solid catalyst for preparing is had big specific surface area and side concurrently
The advantages of Compressive Strength is high.
The composition and physical parameter of formation solid catalyst prepared by table 1
| Catalyst is numbered | 1# | 2# | 3# | 4# | 5# |
| Catalyst precarsor/g | 48.1 | 48 | 47.8 | 45.4 | 46.1 |
| 4.3 | -- | -- | 4.26 | -- | |
| -- | 4.5 | -- | -- | 4.3 | |
| -- | -- | 4.16 | 5.1 | 6.1 | |
| Ethylene glycol/g | 3.8 | 5 | 6.7 | 4.2 | 4.9 |
| 246 | 229 | 225 | 220 | 221 | |
| 0.50 | 0.45 | 0.48 | 0.52 | 0.55 | |
| Aperture/nm | 20 | 22 | 25 | 23 | 22 |
| 117 | 118 | 118 | 118 | 111 |
Embodiment 6
The present embodiment is that the formation solid catalyst is applied into acetone gas phase self-condensation reaction.
Each solid catalyst prepared by embodiment 1-5 is applied to acetone self-condensation reaction, on fixed-bed reactor
Carry out activity rating, catalyst amount 20mL, appreciation condition：300 DEG C of temperature, pressure 0.2MPa, liquid hourly space velocity (LHSV) 2hr-1, negating should
Sample is analyzed within 48 hours.Analysis instrument：The type chromatographics of Agilent 6820, fid detector, chromatogram column type
Number：HP-5(30m,0.32mm,0.5μm).
The data result of each catalyst activity evaluation is listed in Table 2 below, total effective selectivity therein be isopropylidene acetone and
The summation of isophorone selectivity.As can be seen from Table 2, the solid catalyst that prepared by the present invention is applied to acetone and self condenses
During reaction, isopropylidene acetone and the total effective selectivity of isophorone are more than 90%, the wherein selectivity of isophorone>70%.
The Activity evaluation of formation solid catalyst prepared by table 2
| Catalyst is numbered | 1# | 2# | 3# | 4# | 5# |
| Acetone conversion % | 36.1 | 28.2 | 29.6 | 29.3 | 32.6 |
| Total effective selectivity % | 91.8 | 89.6 | 94.5 | 97.1 | 91.4 |
| Isophorone selectivity % | 80.2 | 82 | 87.6 | 84.1 | 85.3 |
Embodiment 7
Solid catalyst of the present invention is applied to the estimation of stability of acetone gas phase self-condensation reaction
4# catalyst prepared by the present invention carries out activity stability evaluation.Condition：300 DEG C of temperature, pressure 0.2MPa, liquid
When air speed 2hr-1.After reaction time 5030h, acetone conversion, effective selectivity and the selectivity to isophorone are listed in table 3
In.
The activity stability evaluation result of 4# solid catalysts prepared by table 3
| Reaction time/h | Acetone conversion % | Total effective selectivity % | Isophorone selectivity % |
| 5030 | 31.2 | 94.8 | 77.9 |
Embodiment 8
Solid catalyst of the present invention is applied to the estimation of stability of acetone gas phase self-condensation reaction
1# catalyst prepared by the present invention carries out activity stability evaluation.Condition：300 DEG C of temperature, pressure 0.2MPa, liquid
When air speed 2hr-1.After reaction time 5030h, acetone conversion, effective selectivity and the selectivity to isophorone are listed in table 4
In.
The activity stability evaluation result of 1# solid catalysts prepared by table 4
| Reaction time/h | Acetone conversion % | Total effective selectivity % | Isophorone selectivity % |
| 5030 | 30.1 | 92.5 | 78.4 |
Solid catalyst long lifespan of the present invention is can be seen that by data in embodiment 7-8 tables, and can repeatedly be regenerated and used,
And catalyst catalytic performance stabilization.
For the ordinary skill in the art, specific embodiment is that the present invention is exemplarily described,
The obvious present invention is implemented and is not subject to the restrictions described above, as long as employ method of the present invention design entering with technical scheme
The improvement of capable various unsubstantialities, or it is not improved by it is of the invention design and technical scheme directly apply to other occasions
, within protection scope of the present invention.
Claims (9)
1. the preparation method of a kind of solid catalyst for acetone self-condensation reaction, it is characterised in that：The solid catalyst is adopted
Prepared with co-precipitation-wet method kneading combined method, specifically include following steps：
(1) prepared as the magnalium hydrotalcite of catalyst precarsor, Mg elements and Al in gained magnalium hydrotalcite using coprecipitation
The molar ratio of element is (1-5):(1-2)；
(2) wet method kneading prepares the solid catalyst：
The well mixed acquisition mixed material of magnalium hydrotalcite, active rare-earth component and organic dispersing agent prepared by step (1), plus
Enter to account for the nitric acid of 1~5wt.% of mixed material as binding agent, by wet method kneading extruded moulding after being well mixed, molded samples
Dried 6~12 hours at a temperature of 100~130 DEG C, then be calcined 4~8 hours at 300~800 DEG C, that is, obtained formation solid and urge
Agent；
In step (2), the part by weight of the magnalium hydrotalcite and active rare-earth component is (90~98)：(0.1~10)；It is described
The weight of organic dispersing agent is the 2~50% of magnalium hydrotalcite and active rare-earth component weight；The active rare-earth component is
The oxide of rare earth element or its hydroxide, the rare earth element are lanthanum, yttrium or cerium.
2. the preparation method of the solid catalyst for acetone self-condensation reaction according to claim 1, it is characterised in that：
In step (1), use coprecipitation prepare the process of magnalium hydrotalcite for：Magnesium salts and aluminium salt are mixed and deionized water is dissolved in
In be configured to mixing salt solution；Precipitating reagent is dissolved in deionized water again aqueous slkali is obtained；By gained mixing salt solution and alkali soluble
Liquid is added in reaction vessel using cocurrent mode, then temperature be 30-90 DEG C, pH be 9-12 under the conditions of react 10-100 point
Clock, then it is aging 6-36 hours after, by gained washing of precipitate to neutrality, magnalium hydrotalcite is obtained after drying.
3. the preparation method of the solid catalyst for acetone self-condensation reaction according to claim 2, it is characterised in that：
Mg in the mixing salt solution2+With Al3+Molar ratio carried out according to the magnalium ratio in the magnalium hydrotalcite of required preparation
Choose.
4. the preparation method of the solid catalyst for acetone self-condensation reaction according to claim 2, it is characterised in that：
The magnesium salts is magnesium nitrate, magnesium acetate or magnesium sulfate；The aluminium salt is aluminum nitrate, aluminum acetate or aluminum sulfate；The precipitating reagent is
One or more in potassium hydroxide, potassium carbonate, NaOH and sodium carbonate.
5. the preparation method of the solid catalyst for acetone self-condensation reaction according to claim 1, it is characterised in that：
In step (2), the organic dispersing agent is ethanol, ethylene glycol, polyethylene glycol, propane diols, ethylenediamine, monoethanolamine, diethanol amine
Or triethanolamine.
6. it is a kind of utilize claim 1 methods described prepare the solid catalyst for acetone self-condensation reaction.
7. the solid catalyst for acetone self-condensation reaction according to claim 6, it is characterised in that：The solid is urged
The specific surface area of agent is 100~300m2/ g, 0.3~1.0cm of pore volume3/ g, 10~50nm of aperture, side pressure strength 50-150N
cm-1。
8. the application of the solid catalyst for acetone self-condensation reaction according to claim 6, it is characterised in that：This is consolidated
Body catalyst is applied to acetone gas phase self-condensation reaction production isophorone.
9. the application of the solid catalyst for acetone self-condensation reaction according to claim 8, it is characterised in that：Using
Continuous fixed bed reaction or continuous device carries out acetone gas phase self-condensation reaction, and process conditions are：100~450 DEG C of reaction temperature, pressure
0.1~2.0MPa, 0.1~5h of liquid hourly space velocity (LHSV)-1。
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| CN106366009A (en) * | 2016-08-26 | 2017-02-01 | 安徽金邦医药化工有限公司 | Preparation method of chemical intermediate benzocaine |
| CN106380384A (en) * | 2016-08-28 | 2017-02-08 | 安徽金邦医药化工有限公司 | Preparation method of mesityl oxide |
| CN107794370B (en) * | 2017-09-06 | 2019-04-19 | 德庆兴邦稀土新材料有限公司 | A kind of Efficient extraction method of high purity lanthanum oxide |
| CN111097397A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Method for synthesizing mesityl oxide and isophorone |
| CN109513436B (en) * | 2018-11-21 | 2021-10-26 | 浙江工业大学 | Catalyst for preparing acetone from acetic acid and preparation method and application thereof |
| CN114425318A (en) * | 2020-10-13 | 2022-05-03 | 中国石油化工股份有限公司 | Composite oxide, preparation method and application thereof |
| KR102477904B1 (en) * | 2020-10-27 | 2022-12-15 | 금호석유화학 주식회사 | Molded catalyst, method of preparing the catalyst, and method for producing cyclic ketone using the same |
| CN115254199A (en) * | 2022-07-11 | 2022-11-01 | 山东工业陶瓷研究设计院有限公司 | Low-cost denitration catalyst slurry and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6387033B1 (en) * | 2000-11-22 | 2002-05-14 | Council Of Scientific And Industrial Research | Preparation of new layered double hydroxides exchanged with osmate for asymmetric dihydroxylation of olefins to vicinal diols |
| CN102773097A (en) * | 2011-05-13 | 2012-11-14 | 华东理工大学 | Preparation of loaded bimetallic nano-catalyst |
| CN103691416A (en) * | 2013-12-31 | 2014-04-02 | 张锦碧 | Catalyst for synthesizing isophorone |
-
2015
- 2015-05-08 CN CN201510232323.8A patent/CN104923209B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6387033B1 (en) * | 2000-11-22 | 2002-05-14 | Council Of Scientific And Industrial Research | Preparation of new layered double hydroxides exchanged with osmate for asymmetric dihydroxylation of olefins to vicinal diols |
| CN102773097A (en) * | 2011-05-13 | 2012-11-14 | 华东理工大学 | Preparation of loaded bimetallic nano-catalyst |
| CN103691416A (en) * | 2013-12-31 | 2014-04-02 | 张锦碧 | Catalyst for synthesizing isophorone |
Non-Patent Citations (3)
| Title |
|---|
| MgO/γ-Al2O3固体碱的混捏法制备、表征及应用;王芳珠 等;《中国石油大学学报（自然科学版）》;20070630;第31卷(第3期);第128-129页 * |
| Synthesis of a,b-unsaturated ketones over thermally activated Mg–Al hydrotalcites;J.I. Di Cosimo等;《Applied Clay Science》;19981130;第13卷(第5-6期);第433-449页 * |
| 钇掺杂焙烧镁铝水滑石的制备及其催化丙酮合成异佛尔酮;刘艳;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20120515;正文第16-17、33页 * |
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