CN104549252B - A kind of catalyst for synthesizing DIBK and preparation method thereof - Google Patents
A kind of catalyst for synthesizing DIBK and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of catalyst for synthesizing DIBK and preparation method thereof, the catalyst is by active component palladium, auxiliary agent neodymium and ZrO2‑Al2O3The part of complex carrier three is constituted, with overall catalyst weight gauge, and active component Pd is 0.05wt%~1.5wt%, and auxiliary agent Nd is 0.2wt%~8wt%, and surplus is ZrO2‑Al2O3Complex carrier, on the basis of complex carrier weight, ZrO2Content be 10wt%~90wt%.Preparation method is as follows：（1）By Al2O3‑ZrO2Complex carrier impregnation process in Nd soluble salt solutions, separation of solid and liquid is dried, roasting；（2）By step（1）Obtained carrier is added in Pd soluble salt solutions, and regulation pH value is 3~4, and impregnation process is dried, and roasting obtains product.Catalyst of the present invention has raw material acetone high conversion rate, the features such as selectivity of product DIBK is good.
Description
Technical field
The present invention relates to catalyst of a kind of acetone through one-step method synthesis DIBK and preparation method thereof.
Background technology
DIBK is a kind of excellent solvent and chemical intermediate.The boiling point of DIBK is high, evaporation rate is fast,
Dissolving power is strong, can improve film levelling, gloss, recoatability, the wettability to plastic bottom material is good, increases sorptive force, can use nitro
The solvent of spray painting, ethenoid resin paint and other synthetic resin coatings, can improve its moisture protection.It also is used as manufacturing organic gas
The refined solvent of dispersant and food and some drugses, the intermediate of insecticide of colloidal sol, be also used in rare metal extraction and
Metallic salt is separated in purification.
At present, about introducing the synthesis DIBK report that is and few.Most of is to introduce synthesizing methyl isobutyl group
The method of ketone coproduction DIBK.Totally see, if using DIBK as purpose product, its yield awaits improving.
Document " Ni, Pd/Al2O3To the performance comparision of acetone hydrogenation one-step synthesis methyl iso-butyl ketone (MIBK) "（Institution of higher education's Science of Chemistry
Report, o. 11th, page 1865 in 1997）Report, during acetone hydrogenation one-step synthesis methyl iso-butyl ketone (MIBK), using Ni-
Ce/Al2O3During catalyst, the conversion ratio of acetone is 81.7%, and the selectivity of DIBK is 50.05%, now DIBK
Yield be up to 40.9%.
CN1566060A discloses the process of a kind of Status of OneStep Synthesis of Methyl isoButyl Ketone from Acetone and DIBK.
This method uses Pd/ZrO2As catalyst, Pd contents are 0.5wt%, normal pressure, fixed bed reactors.Acetone conversion is
When 65.13%, the selectivity of DIBK is up to 61.34%, and now the yield of DIBK is 40.01%.
WO2012080809 describes a kind of using acetone and methyl iso-butyl ketone (MIBK) as mixed material synthesis DIBK
Method, but the selectivity of this method purpose product DIBK only has 14%.And compare with the side that single acetone is charging
Method, cost of material will height.
The content of the invention
In view of the shortcomings of the prior art, it is an object of the invention to provide it is a kind of synthesize DIBK catalyst and its
Preparation method, catalyst of the invention has raw material acetone high conversion rate, and the selectivity of product DIBK is good, i.e., purpose is produced
The features such as high income of thing DIBK.
The catalyst of the synthesis DIBK of the present invention, by active component palladium（Pd）, auxiliary agent neodymium（Nd）And ZrO2-Al2O3
The part of complex carrier three is constituted, with overall catalyst weight gauge, and active component Pd is 0.05wt%~1.5wt%, and preferably 0.1wt%~
0.8wt%, auxiliary agent Nd are 0.2wt%~8wt%, and preferably 0.5wt%~5wt%, surplus is ZrO2-Al2O3Complex carrier, with compound load
On the basis of body weight, ZrO2Content be 10wt%~90wt%, preferably 30wt%~60wt%.
The preparation method of the catalyst of the synthesis DIBK of the present invention, including following content：
（1）By Al2O3-ZrO2Complex carrier impregnation process in Nd soluble salt solutions, separation of solid and liquid is dried, roasting
Burn；
（2）By step（1）Obtained carrier is added in Pd soluble salt solutions, and regulation pH value is 3~4, dipping
Processing, is dried, and roasting obtains product.
Wherein, step（1）In used volume impregnation method, the impregnation process time is 20~25 hours, and drying condition is：
100~120 DEG C dry 2~4 hours, and roasting condition is：400~500 DEG C are calcined 6~8 hours.Step（2）Using isometric or
Cross volume impregnation method, the impregnation process time is 20~25 hours, drying can volatilize under field conditions (factors) moisture or 100~
120 DEG C dry 2~4 hours, and roasting condition is：300~400 DEG C are calcined 6~8 hours.
In the inventive method, Al2O3-ZrO2Complex carrier is prepared using method well known to those skilled in the art, such as
Dipper precipitation method, alkoxide sol-gel method and coprecipitation etc., preferably dipper precipitation method.
In the inventive method, Al2O3-ZrO2It is bar shaped that complex carrier, which can be actually needed and be prepared into, spherical or cylinder.
Depending on active component content can be according to response situation, typically change the content of active component by reconciling impregnation concentration.
In the inventive method, the soluble-salt of described palladium is the one or more in palladium nitrate, palladium bichloride or palladium sulfate,
It is preferred that palladium nitrate；The soluble salt solutions concentration of palladium is 0.01~0.5mol/L.
In the inventive method, the soluble-salt of described neodymium is one or both of nitrate or chloride, preferably nitre
Hydrochlorate；The soluble salt solutions concentration of neodymium is 0.05~1mol/L.
Catalyst of the present invention is applied to the reaction that acetone through one-step method synthesizes DIBK, and general condition is：Reaction temperature
100~220 DEG C, preferably 130~180 DEG C；Reaction pressure normal pressure；Acetone feed air speed is 0.25~2.5h-1, preferably 0.5 (V)~
2.0h-1(V)；H2/ acetone（V/V）For 300~800, preferably 300~500.
Catalyst of the present invention is loading reactor using preceding, is reduced using reducing process in device.Reducing condition is：Reduction temperature
For 300 DEG C, normal pressure is reduced 5~8 hours, and the catalyst isolation air after reduction is preserved.
Catalyst of the present invention is compared to prior art, with following features：
（1）Using Al2O3-ZrO2Complex carrier so that the acidity of carrier in itself is better than pure γ-Al2O3, the acid of carrier
Property enhancing be conducive to acetone trimerization generate DIBK, improve selectivity of the catalyst to DIBK.And Al2O3-
ZrO2The intensity of complex carrier is better than ZrO2Carrier, is longer than the service life of the catalyst and only uses ZrO2It is used as urging for carrier
Agent.
（2）By introducing neodymium metal in the catalyst, the competitive Adsorption in palladium ion adsorption process on catalyst is changed
State.Make catalyst dehydrating function and hydrogenating function matching it is more preferable, make whole chemical reaction process to being conducive to acetone three
Consor is carried out into the direction of DIBK, improves selectivity of the catalyst to product DIBK.Meanwhile, neodymium metal
Addition can increase the surface area of catalyst, improve anticaking carbon ability, be conducive to improving the stability of catalyst.
Embodiment
The present invention is further described with reference to embodiment.
Embodiment 1
（1）Weigh ZrOCl2·8H2O 145g, are dissolved in 400mL distilled water and are made into the aqueous solution, by 80g Al2O3Powder adds
Enter into the solution, with vigorous stirring with the 10 dilute NH of (v/v) %3·H2O solution is titrated to pH to be stirred for 30 minutes after 9, puts
Precipitation aging in 4 hours is put, no Cl is then washed with distilled water to-Untill.Dry and be calcined 4 hours after 550 DEG C at 110 DEG C,
Obtain Al2O3-ZrO2Complex carrier.ZrO2Content is 40wt%, Al2O3Content is 60wt%.
（2）By 1.6gNd (NO3)3·4H2O is added in 105mL distilled water and is made into the aqueous solution, is impregnated with the solution
100gAl2O3-ZrO2Complex carrier, impregnates 24 hours.Upper strata clear water is removed, is dried 3 hours in 110 DEG C, is roasted in 500 DEG C
Burn 6 hours, the support C -1 containing neodymium is made.
（3）By 0.51gPd (NO3)2·2H2O, which is dissolved in 105mL distilled water, is made into the aqueous solution, and regulation pH value is 3~4.Will
100gC-1 is impregnated into the palladium solution, after after moisture content volatilization, in roasting 8 hours in 400 DEG C.Catalyst A-1 is made.The catalysis
The Nd contents of agent are 0.5wt%, and Pd contents are 0.2wt%.
Embodiment 2
（1）Al2O3-ZrO2The step of preparation be the same as Example 1 of complex carrier（1）.
（2）By 4.8gNd (NO3)3·4H2O is added in 105mL distilled water and is made into the aqueous solution, is impregnated with the solution
100gAl2O3-ZrO2Complex carrier impregnates 24 hours.Upper strata clear water is removed, is dried 3 hours in 110 DEG C, is calcined in 500 DEG C
6 hours, the support C -2 containing neodymium is made.
（3）By 1.02gPd (NO3)2·2H2O, which is dissolved in 105mL distilled water, is made into the aqueous solution, and regulation pH value is 3~4.Will
100gC-2 is impregnated into the palladium solution, after after moisture content volatilization, in roasting 8 hours in 400 DEG C.Catalyst A-2 is made.The catalysis
The Nd contents of agent are 1.5wt%, and Pd contents are 0.4 wt%.
Embodiment 3
（1）Al2O3-ZrO2The step of preparation be the same as Example 1 of complex carrier（1）.
（2）By 9.6gNd (NO3)3·4H2O is added in 105mL distilled water and is made into the aqueous solution, is impregnated with the solution
100gAl2O3-ZrO2Complex carrier, impregnates 24 hours.Upper strata clear water is removed, is dried 3 hours in 110 DEG C, is roasted in 500 DEG C
Burn 6 hours, the support C -3 containing neodymium is made.
（3）By 1.51gPd (NO3)2·2H2O, which is dissolved in 105mL distilled water, is made into the aqueous solution, and regulation pH value is 3~4.Will
100gC-3 is impregnated into the palladium solution, after after moisture content volatilization, in roasting 8 hours in 400 DEG C.Catalyst A-3 is made.The catalysis
The Nd contents of agent are 3wt%, and Pd contents are 0.6wt%.
Embodiment 4
（1）Al2O3-ZrO2The step of preparation be the same as Example 1 of complex carrier（1）.
（2）The step of preparation be the same as Example 2 of the carrier containing neodymium（2）.
（3）By 2.02gPd (NO3)2·2H2O, which is dissolved in 105mL distilled water, is made into the aqueous solution, and regulation pH value is 3~4.Will
100gC-2 is impregnated into the palladium solution, after after moisture content volatilization, in roasting 8 hours in 400 DEG C.Catalyst A-4 is made.The catalysis
The Nd contents of agent are 1.5wt%, and Pd is 0.8 wt%.
Embodiment 5
（1）Al2O3-ZrO2The step of preparation be the same as Example 1 of complex carrier（1）.
（2）By 16.0gNd (NO3)3·4H2O is added in 105mL distilled water and is made into the aqueous solution, is impregnated with the solution
100gAl2O3-ZrO2Complex carrier, impregnates 24 hours.Upper strata clear water is removed, is dried 3 hours in 110 DEG C, is roasted in 500 DEG C
Burn 6 hours, the support C -5 containing neodymium is made.
（3）By 2.02gPd (NO3)2·2H2O, which is dissolved in 105mL distilled water, is made into the aqueous solution, and regulation pH value is 3~4.Will
100gC-5 is impregnated into the palladium solution, after after moisture content volatilization, in roasting 8 hours in 400 DEG C.Catalyst A-5 is made.The catalysis
The Nd contents of agent are 5wt%, and Pd contents are 0.8 wt%.
Embodiment 6
（1）Weigh ZrOCl2·8H2O60g, is dissolved in 400mL distilled water and is made into the aqueous solution, by 90gAl2O3Powder is added
Into the solution, with vigorous stirring with the 10 dilute NH of (v/v) %3·H2O solution, which is titrated to behind pH=9, to be stirred for 30 minutes.Place 4
Hour precipitation aging, is then washed with distilled water to no Cl-Untill.Dry and be calcined 4 hours after 550 DEG C at 110 DEG C, obtained
Al2O3-ZrO2Complex carrier.ZrO2Content is 20wt%, Al2O3Content is 80wt%.
（2）The step of preparation be the same as Example 2 of the carrier containing neodymium（2）.
（3）Catalyst carries the step of palladium process be the same as Example 2（3）.Catalyst A-6 is obtained, the Nd contents of the catalyst are 1.5%
Wt, Pd content are 0.4 wt%.
Embodiment 7
（1）Weigh ZrOCl2·8H2O200g, is dissolved in 400mL distilled water and is made into the aqueous solution, by 50gAl2O3Powder is added
Into the solution, with vigorous stirring with the 10 dilute NH of (v/v) %3·H2O solution, which is titrated to behind pH=9, to be stirred for 30 minutes.Place 4
Hour precipitation aging, is then washed with distilled water to no Cl-Untill.Dry and be calcined 4 hours after 550 DEG C at 110 DEG C, obtained
Al2O3-ZrO2Complex carrier.ZrO2Content is 60wt%, Al2O3Content is 40wt%.
（2）The step of preparation be the same as Example 2 of the carrier containing neodymium（2）.
（3）Catalyst carries the step of palladium process be the same as Example 2（3）.Catalyst A-7 is made, the Nd contents of the catalyst are
1.5wt%, Pd content are 0.4wt%.
Comparative example 1
Weigh ZrOCl2·8H2O 265g, are dissolved in 400mL distilled water and are made into the aqueous solution, with vigorous stirring with 10 (v/
V) the dilute NH of %3·H2O solution is titrated to pH to be stirred for 30 minutes after 9, places precipitation aging in 4 hours, then with distillation water washing
To without Cl-Untill.Dry and be calcined 4 hours after 550 DEG C at 110 DEG C, obtain ZrO2Multiple carrier.
By 0.51gPd (NO3)2·2H2O, which is dissolved in 105mL distilled water, is made into the aqueous solution, and regulation pH value is 3~4.It is molten with this
Immersion stain 100g Zirconia carriers, after after moisture content volatilization, in roasting 8 hours in 400 DEG C.Catalyst B-1 is made.The catalyst
Pd contents are 0.2 wt%.
Comparative example 2
Weigh ZrOCl2·8H2O 265g, are dissolved in 400mL distilled water and are made into the aqueous solution, with vigorous stirring with 10 (v/
V) the dilute NH of %3·H2O solution is titrated to pH to be stirred for 30 minutes after 9, places precipitation aging in 4 hours, then with distillation water washing
To without Cl-Untill.Dry and be calcined 4 hours after 550 DEG C at 110 DEG C, obtain ZrO2Multiple carrier.
（2）By 1.6gNd (NO3)3·4H2O is added in 105mL distilled water and is made into the aqueous solution, is impregnated with the solution
100gZrO2Carrier, impregnates 24 hours.Upper strata clear water is removed, in 110 DEG C of drying, is calcined 6 hours in 500 DEG C, is made and contains
Neodymium 0.5wt% ZrO2Carrier.
（3）By 0.51gPd (NO3)2·2H2O, which is dissolved in 105mL distilled water, is made into the aqueous solution, and regulation pH value is 3~4.Will
100g 0.5wt% containing neodymium ZrO2Carrier impregnation is into the palladium solution, after after moisture content volatilization, in roasting 8 hours in 400 DEG C.It is made
Catalyst B-2.The Nd contents of the catalyst are 0.5wt%, and Pd contents are 0.2wt%.
Comparative example 3
By 0.51gPd (NO3)2·2H2O, which is dissolved in 105mL distilled water, is made into the aqueous solution, and regulation pH value is 3~4.By 100g
Al2O3Carrier impregnation is into the palladium solution, after after moisture content volatilization, in roasting 8 hours in 400 DEG C.Catalyst B-3 is made.The catalysis
The Pd contents of agent are 0.2wt%.
Comparative example 4
（1）By 1.6gNd (NO3)3·4H2O is added in 105mL distilled water and is made into the aqueous solution, and 100g is impregnated with the solution
Al2O3Carrier, impregnates 24 hours.Upper strata clear water is removed, in 110 DEG C of drying, is calcined 6 hours, is made containing neodymium in 500 DEG C
0.5wt% Al2O3Carrier.
（3）By 0.51gPd (NO3)2·2H2O, which is dissolved in 105mL distilled water, is made into the aqueous solution, and regulation pH value is 3~4.Will
100g 0.5wt% containing neodymium Al2O3Carrier impregnation is into the palladium solution, after after moisture content volatilization, in roasting 8 hours in 400 DEG C.It is made
Catalyst B-4.The Nd contents of the catalyst are 0.5wt%, and Pd contents are 0.2wt%.
Comparative example 5
（1）Weigh ZrOCl2·8H2O 145g, are dissolved in 400mL distilled water and are made into the aqueous solution, by 80g Al2O3Powder adds
Enter into the solution, with vigorous stirring with the 10 dilute NH of (v/v) %3·H2O solution is titrated to pH to be stirred for 30 minutes after 9, puts
Precipitation aging in 4 hours is put, no Cl is then washed with distilled water to-Untill.Dry and be calcined 4 hours after 550 DEG C at 110 DEG C,
Obtain Al2O3-ZrO2Complex carrier.ZrO2Content is 40wt%, Al2O3Content is 60wt%.
（2）By 0.51gPd (NO3)2·2H2O, which is dissolved in 105mL distilled water, is made into the aqueous solution, and regulation pH value is 3~4.Will
100g ZrO2Content is 40wt%, Al2O3Content is 60wt%.Carrier impregnation is into the palladium solution, after after moisture content volatilization, in 400
It is calcined 8 hours in DEG C.Catalyst B-5 is made.The Pd contents of the catalyst are 0.2wt%.
Embodiment 8
Catalyst A-1 is loaded into reactor, reduced using reducing process in device.Reducing condition is：Reduction temperature is 300 DEG C,
Normal pressure is reduced 5 hours, and hydrogen gas space velocity is 120h during reduction-1.190 DEG C of reaction temperature, reaction pressure normal pressure, acetone feed air speed is
1.5, H2/ acetone（V/V）For 500.
Raw material acetone enters after reactor reaction, and product is through cooling and gas-liquid separation, and vapor phase hydrogen is vented or recycled,
Liquid-phase reaction product gas chromatographic analysis.
Evaluated respectively with the method for embodiment 8 catalyst A-2, A-3, A-4, A-5, A-6, A-7, B-1, B-2, B-3, B-4,
B-5.Compare the performance of different catalysts, the results are shown in Table 1.
The catalyst performance evaluation of table 1.
As can be seen from the table, by the yield of the work of obtained catalyst of the invention, selectivity and DIBK
There is raising by a relatively large margin compared with prior art.
Claims (10)
1. a kind of catalyst for synthesizing DIBK, it is characterised in that：By active component palladium, auxiliary agent neodymium and ZrO2-Al2O3It is multiple
The part of carrier three composition is closed, with overall catalyst weight gauge, active component Pd is 0.05wt%~1.5wt%, and auxiliary agent Nd is 0.2wt%
~8wt%, surplus is ZrO2-Al2O3Complex carrier.
2. according to the catalyst described in claim 1, it is characterised in that：With overall catalyst weight gauge, active component Pd is
0.1wt%~0.8wt%, auxiliary agent Nd 0.5wt%~5wt%, surplus is ZrO2-Al2O3Complex carrier.
3. according to the catalyst described in claim 1 or 2, it is characterised in that：With ZrO2-Al2O3On the basis of complex carrier weight,
ZrO2Content be 10wt%~90wt%.
4. according to the catalyst described in claim 1 or 2, it is characterised in that：With ZrO2-Al2O3On the basis of complex carrier weight,
ZrO2Content be 30wt%~60wt%.
5. the preparation method of the catalyst of the synthesis DIBK described in claim 1, it is characterised in that including following content：
（1）By Al2O3-ZrO2Complex carrier impregnation process in Nd soluble salt solutions, separation of solid and liquid is dried, and roasting is carried on a shoulder pole
Nd Al is carried2O3-ZrO2Complex carrier；（2）By step（1）Obtained carrier is added in Pd soluble salt solutions, regulation
PH value is 3~4, and impregnation process is dried, and roasting obtains product.
6. in accordance with the method for claim 5, it is characterised in that：Step（1）In used volume impregnation, impregnation process time
For 20~25 hours, drying condition was：100~120 DEG C dry 2~4 hours, and roasting condition is：400~500 DEG C of roastings 6~8
Hour.
7. in accordance with the method for claim 5, it is characterised in that：Step（2）Using isometric or cross at volume impregnation, dipping
The reason time is 20~25 hours.
8. in accordance with the method for claim 5, it is characterised in that：The soluble-salt of described palladium be palladium nitrate, palladium bichloride or
One or more in palladium sulfate, the soluble salt solutions concentration of palladium is 0.01~0.5mol/L.
9. in accordance with the method for claim 5, it is characterised in that：The soluble-salt of described neodymium is in nitrate or chloride
One or two, the soluble salt solutions concentration of neodymium is 0.05~1mol/L.
10. the catalyst described in claim 1 or 2 is applied to the reaction that acetone through one-step method synthesizes DIBK, reaction condition
For：100~220 DEG C of reaction temperature, reaction pressure normal pressure, acetone feed air speed is 0.25~2.5h-1(V), H2/ acetone（V/V）
For 300~800.
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