CN104998648B - A kind of nickel, copper, the mesoporous MnO of zinc load2The preparation method of catalyst and 4,4 dimethyl 1 (4 rubigan) 3 pentanones - Google Patents
A kind of nickel, copper, the mesoporous MnO of zinc load2The preparation method of catalyst and 4,4 dimethyl 1 (4 rubigan) 3 pentanones Download PDFInfo
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- CN104998648B CN104998648B CN201510423831.4A CN201510423831A CN104998648B CN 104998648 B CN104998648 B CN 104998648B CN 201510423831 A CN201510423831 A CN 201510423831A CN 104998648 B CN104998648 B CN 104998648B
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Abstract
The present invention relates to the mesoporous MnO that a kind of nickel, copper, zinc load2Catalyst and 4, the preparation method of 4 dimethyl 1 (4 rubigan) 3 pentanones, catalyst include mesoporous MnO2Carrier and it is supported on described mesoporous MnO2Nickel, copper, zinc on carrier, described nickel, copper, the mol ratio of zinc are 1：0.3~1：0.1 ~ 0.3, described nickel, copper, quality summation and the described mesoporous MnO of zinc2The mass ratio of carrier is 1 ~ 3：10.Catalyst prepared by the present invention has the advantages that high catalytic activity, cost are low, preparation technology is simple, service life is long.In reaction for 4,43 ketone Hydrogenation of dimethyl 1 (4 rubigan) 1 amylene 4,4 dimethyl 1 (4 rubigan) 3 pentanones, yield and purity highest are up to 99%.
Description
Technical field
The present invention relates to the mesoporous MnO that a kind of nickel, copper, zinc load2(4- is to chlorobenzene by catalyst and 4,4- dimethyl -1-
Base)-propione preparation method.
Background technology
Tebuconazole is sterol demethylation inhibitors, is the seed treatment of various crop or the efficient sterilizing of foliage spray
Agent.Developed earliest by Beyer Co., Ltd, English common name tebuconazole, chemical structural formula is：
。
Tebuconazole wide sterilization spectrum, not only activity is high, and the lasting period is grown, and is mainly used in preventing and treating wheat, peanut, vegetables, perfume (or spice)
A variety of fungal diseases on the crops such as any of several broadleaf plants, apple, pears.2014, the global marketing volume of Tebuconazole was more than 800,000,000 dollars, all
Fluoxastrobin is only second in bactericide kind, is come second.
The Tebuconazole production technology of comparative maturity is using 4-chloro-benzaldehyde and pinacoline as raw material at present, is obtained through condensation reaction
To 4,4- dimethyl -1- (4- rubigan) -1- penten-3-ones (intermediate 1), then hydrogenating reduction obtains 4,4- dimethyl -1-
(4- rubigan)-propione (intermediate 2), then through epoxidation and ring-opening reaction synthesizing fungicide tebuconazole.By the hydrogen of intermediate 1
It is a step crucial in synthesis technique to change to intermediate 2, need to be in height frequently with Raney's nickel as hydrogenation catalyst in existing process
Reacted under warm high pressure, severe reaction conditions, be extremely difficult to preferable quality and yield.Cheap, efficient catalyst is found to carrying
High product qualities, to reduce cost significant.
The content of the invention
The technical problems to be solved by the invention be to provide a kind of low cost, the nickel of high activity, copper, zinc load it is mesoporous
MnO2Catalyst, the catalyst can be used in during the hydrogenation synthesis of Tebuconazole.
Another technical problem to be solved by this invention is to provide a kind of using above-mentioned catalyst preparation 4,4- dimethyl -1-
The method of (4- rubigan)-propione.
To solve above technical problem, the present invention adopts the following technical scheme that：
A kind of nickel, copper, the mesoporous MnO of zinc load2Catalyst, described catalyst include mesoporous MnO2Carrier and it is supported on
Described mesoporous MnO2Nickel, copper, zinc on carrier, described nickel, copper, the mol ratio of zinc are 1：0.3~1：0.1 ~ 0.3, it is described
Nickel, copper, quality summation and the described mesoporous MnO of zinc2The mass ratio of carrier is 1 ~ 3：10.
Preferably, described nickel, copper, the mol ratio of zinc are 1：0.4~0.6：0.15~0.25.
Preferably, quality summation and the described mesoporous MnO of described nickel, copper, zinc2The mass ratio of powder is 1.5 ~ 2.5：
10。
Described nickel, copper, the mesoporous MnO of zinc load2Catalyst is prepared via a method which to obtain：
1）Mesoporous MnO2The preparation of carrier：SBA-15 is dissolved in organic solvent, then adding mass percent concentration is
30% ~ 50% Mn (NO3)2 Solution, react 6 ~ 12 hours, after filtered, dry, be calcined 2 ~ 4 hours, obtain at 300 ~ 400 DEG C
To solid, then described solid and alkaline solution are reacted 10 ~ 20 hours, mesoporous MnO is obtained after scrubbed, dry, grinding2
Powder；
2）Nickel, copper, the mesoporous MnO of zinc load2The preparation of catalyst：By described mesoporous MnO2Powder and total concentration are 0.1
~ 0.3mol/L nickel nitrate, copper nitrate and zinc nitrate solution reacts 12 ~ 30 hours, after then being dried at 50 ~ 100 DEG C, in
300 ~ 600 DEG C of 3 ~ 6h of calcining, obtain blocks of solid；After described blocks of solid grinding, at 300 ~ 500 DEG C, hydrogen is added
3 ~ 6h of reduction reaction, obtain described nickel, copper, the mesoporous MnO of zinc load2Catalyst.
Preferably, described organic solvent is n-hexane.
Preferably, described alkaline solution is sodium hydroxide.
Preferably, described SBA-15 is dissolved in described organic solvent, then ultrasonic disperse 1 ~ 3 hour, is added
Described Mn (NO3)2 Solution.
Preferably, step（1）The temperature of middle roasting is 340 ~ 360 DEG C.
Preferably, step（2）The temperature of middle drying is 40 ~ 60 DEG C.
Preferably, step（2）The temperature of middle calcining is 480 ~ 520 DEG C.
Preferably, step（2）The temperature of middle reduction reaction is 380 ~ 420 DEG C.
The preparation method of one kind 4,4- dimethyl -1- (4- rubigan)-propione, by 4,4- dimethyl -1-, (4- is to chlorine
Phenyl) -1- penten-3-ones and hydrogen is anti-at 1.5 ~ 2.5 MPa, 90 ~ 110 DEG C in the presence of organic solvent and catalyst
Answer 10 ~ 20h, be made described 4,4- dimethyl -1- (4- rubigan)-propione, described catalyst include described nickel,
Copper, the mesoporous MnO of zinc load2Catalyst.
Preferably, described 4,4- dimethyl -1- (4- rubigan) -1- penten-3-ones are born with described nickel, copper, zinc
The mesoporous MnO carried2The addition mass ratio of catalyst is 3 ~ 10:1.
Preferably, in the initial period of reaction, described 4,4- dimethyl -1- (4- rubigan) -1- penten-3-ones
Concentration is 0.4 ~ 0.6g/mL.
Preferably, described organic solvent is methanol and/or dimethyl sulfoxide (DMSO).
Preferably, described 4,4- dimethyl -1- (4- rubigan)-propione is prepared to concretely comprise the following steps：By described in
4,4- dimethyl -1- (4- rubigan) -1- penten-3-ones be dissolved in methanol, be separately added into described nickel, copper, zinc and bear
The mesoporous MnO carried2Catalyst and described Raney's nickel, then add dimethyl sulfoxide (DMSO), through being repeatedly flushed with hydrogen gas displacement, are flushed with hydrogen gas and arrive
The MPa of pressure 1.8 ~ 2.2, interior temperature are 95 ~ 105 DEG C, after completion of the reaction, through cooling, release, use N2Extruded after displacement repeatedly anti-
Feed liquid is answered, catalyst solid is filtered out and applies mechanically, concentrating filter liquor obtains described 4,4- dimethyl -1- (4- rubigan) -3-
Pentanone.
Due to the implementation of above technical scheme, the present invention has following advantage compared with prior art：
Catalyst prepared by the present invention has meso-hole structure, there is larger specific surface area, can effectively improve nickel, copper, zinc
Load capacity, nickel, copper, zinc is set to be highly dispersed at carrier surface.The present invention catalyst be used for tebuconazole intermediate 4,4- dimethyl-
In the synthetic reaction of 1- (4- rubigan)-propione, there is higher catalytic reaction activity and good stability, reduce
The production cost of Tebuconazole, improves industrial production efficiency, and further increases the quality of product, so that product
With the higher market competitiveness.
Embodiment
The present invention is described in further details below in conjunction with specific embodiment.It should be understood that these embodiments are to be used to say
The bright basic principles, principal features and advantages of the present invention, and the present invention is not limited by the following examples.Used in embodiment
Implementation condition can do further adjustment according to specific requirement, and unreceipted implementation condition is usually the condition in normal experiment.
Embodiment 1
1）Take SBA-15 wiring solution-formings in n-hexane, ultrasonic disperse 2 hours.Mn (the NO of the lower dropwise addition 30% of stirring3)2
Solution, then continue stirring 8 hours at room temperature, filter, be calcined 4 hours at 300 times after vacuum drying.Obtained solid as
Stirred 10 hours in sodium hydroxide solution, mesoporous MnO is obtained after scrubbed, dry, grinding2Powder.
2）By nickel nitrate, copper nitrate and zinc nitrate deionized water dissolving, the gold that total concentration is 0.1mol/L is made into
Belong to salting liquid, then with the step 1）Manganese dioxide powder mixing is obtained, is stirred at room temperature 12 hours, obtained maceration extract
Dried under the conditions of 80 DEG C, calcine 3h in 300 DEG C, obtain blocks of solid；By ground 100 mesh sieve of gained blocks of solid, 300
At DEG C, after leading to H2 reduction reactions 3h in tube furnace, nickel, copper, the mesoporous MnO of zinc load are obtained2Catalyst.Wherein nickel, copper,
The mol ratio of zinc is 1:0.3:0.1, nickel, copper, the quality of zinc are total and the mass ratio of carrier manganese dioxide is 1:10.
Embodiment 2
1）Take SBA-15 wiring solution-formings in n-hexane, ultrasonic disperse 2 hours.Mn (the NO of the lower dropwise addition 50% of stirring3)2
Solution, then continue stirring 12 hours at room temperature, filter, be calcined 4 hours at 400 DEG C after vacuum drying.Obtained solid
Stirred 20 hours as in sodium hydroxide solution, mesoporous MnO is obtained after scrubbed, dry, grinding2Powder.
2）By nickel nitrate, copper nitrate and zinc nitrate deionized water dissolving, the gold that total concentration is 0.3mol/L is made into
Belong to salting liquid, then with the step 1）Manganese dioxide powder mixing is obtained, is stirred at room temperature 30 hours, obtained maceration extract
Dried under the conditions of 100 DEG C, 600 DEG C of calcining 6h, obtain blocks of solid；By ground 100 mesh sieve of gained blocks of solid, 500
At DEG C, after leading to H2 reduction reactions 6h in tube furnace, nickel, copper, the mesoporous MnO of zinc load are obtained2Catalyst.Wherein nickel, copper,
The mol ratio of zinc is 1:1:0.3, nickel, copper, the quality of zinc are total and the mass ratio of carrier manganese dioxide is 3:10.
Embodiment 3
1）Take SBA-15 wiring solution-formings in n-hexane, ultrasonic disperse 3 hours.Mn (the NO of the lower dropwise addition 40% of stirring3)2
Solution, then continue stirring 8 hours at room temperature, filter, be calcined 3 hours at 350 DEG C after vacuum drying.Obtained solid is extremely
Stirred 15 hours in sodium hydroxide solution, mesoporous MnO is obtained after scrubbed, dry, grinding2Powder.
2）By nickel nitrate, copper nitrate and zinc nitrate deionized water dissolving, the gold that total concentration is 0.2mol/L is made into
Belong to salting liquid, then with the step 1）Manganese dioxide powder mixing is obtained, is stirred at room temperature 20 hours, obtained maceration extract
Dried under the conditions of 50 DEG C, calcine 4h in 500 DEG C, obtain blocks of solid；By ground 100 mesh sieve of gained blocks of solid, 400
At DEG C, after leading to H2 reduction reactions 4h in tube furnace, nickel, copper, the mesoporous MnO of zinc load are obtained2Catalyst.Wherein nickel, copper,
The mol ratio of zinc is 1:0.5:0.2, nickel, copper, the quality of zinc are total and the mass ratio of carrier manganese dioxide is 1:5.
Embodiment 4
1）Take SBA-15 wiring solution-formings in n-hexane, ultrasonic disperse 3 hours.Mn (the NO of the lower dropwise addition 40% of stirring3)2
Solution, then continue stirring 10 hours at room temperature, filter, be calcined 3 hours at 350 DEG C after vacuum drying.Obtained solid
Stirred 15 hours as in sodium hydroxide solution, mesoporous MnO is obtained after scrubbed, dry, grinding2Powder.
2）By nickel nitrate, copper nitrate and zinc nitrate deionized water dissolving, the gold that total concentration is 0.2mol/L is made into
Belong to salting liquid, then with the step 1）Manganese dioxide powder mixing is obtained, is stirred at room temperature 20 hours, obtained maceration extract
Dried under the conditions of 60 DEG C, calcine 5h in 400 DEG C, obtain blocks of solid；By ground 100 mesh sieve of gained blocks of solid, 400
At DEG C, after leading to H2 reduction reactions 5h in tube furnace, nickel, copper, the mesoporous MnO of zinc load are obtained2Catalyst.Wherein nickel, copper,
The mol ratio of zinc is 1:0.6:0.1, nickel, copper, the quality of zinc are total and the mass ratio of carrier manganese dioxide is 3:20.
Embodiment 5 to 8
100 g 4,4- dimethyl -1- (4- rubigan) -1- penten-3-ones, first are put into 500 mL autoclaves
The mL of alcohol 200, the catalyst 20g prepared in embodiment 1-4 is separately added into, adds the mL of dimethyl sulfoxide (DMSO) 0.05.Gas is flushed with hydrogen to put
3 times (0.3 MPa/ times) are changed, gas is flushed with hydrogen to the MPa of pressure 2.0, interior 100 DEG C of temperature, reacts 15 h.Reaction finishes, and cooling, will react
Kettle release, uses N2Displacement 3 times (0.3 MPa/ times) extrudes reaction material liquid afterwards, filters out catalyst solid and applies mechanically, filtrate is concentrated to give
To faint yellow solid, through vapor detection target product 4,4- dimethyl -1- (4- rubigan)-propione（Intermediate 2）Yield
And content, as a result as shown in table 1.
Comparative example 1
The preparation method of this comparative example and embodiment 5 to 8 are essentially identical, and difference is to replace implementing using 20g Raney's nickels
The catalyst prepared in example 1 to 4.
Table 1
| Catalyst | Reaction temperature（℃） | Reaction pressure（MPa） | The yield of intermediate 2 | The content of intermediate 2 |
| Embodiment 5 | 100 | 2.0 | 98% | 97% |
| Embodiment 6 | 100 | 2.0 | 97% | 98% |
| Embodiment 7 | 100 | 2.0 | 99% | 99% |
| Embodiment 8 | 100 | 2.0 | 99% | 97% |
| Comparative example 1 | 100 | 2.0 | 92% | 95% |
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art
Scholar can understand present disclosure and implement according to this, and it is not intended to limit the scope of the present invention, all according to the present invention
The equivalent change or modification that Spirit Essence is made, it should all be included within the scope of the present invention.
Claims (9)
- A kind of 1. mesoporous MnO of nickel, copper, zinc load2Catalyst, it is characterised in that：Described catalyst includes mesoporous MnO2Carry Body and it is supported on described mesoporous MnO2Nickel, copper, zinc on carrier, described nickel, copper, the mol ratio of zinc are 1：0.3~1：0.1~ 0.3, described nickel, copper, quality summation and the described mesoporous MnO of zinc2The mass ratio of carrier is 1 ~ 3：10, wherein, it is described Mesoporous MnO2The preparation method of carrier is：SBA-15 is dissolved in organic solvent, then add mass percent concentration be 30% ~ 50% Mn (NO3)2 Solution, react 6 ~ 12 hours, after filtered, dry, be calcined 2 ~ 4 hours at 300 ~ 400 DEG C, consolidate Body, then described solid and alkaline solution are reacted 10 ~ 20 hours, mesoporous MnO is obtained after scrubbed, dry, grinding2Powder End.
- 2. the mesoporous MnO of nickel according to claim 1, copper, zinc load2Catalyst, it is characterised in that：Described nickel, copper, The mesoporous MnO of zinc load2Catalyst is prepared via a method which to obtain：1）Mesoporous MnO2The preparation of carrier：SBA-15 is dissolved in organic solvent, then add mass percent concentration be 30% ~ 50% Mn (NO3)2 Solution, react 6 ~ 12 hours, after filtered, dry, be calcined 2 ~ 4 hours at 300 ~ 400 DEG C, consolidate Body, then described solid and alkaline solution are reacted 10 ~ 20 hours, mesoporous MnO is obtained after scrubbed, dry, grinding2Powder End；2）Nickel, copper, the mesoporous MnO of zinc load2The preparation of catalyst：By described mesoporous MnO2Powder and total concentration be 0.1 ~ 0.3mol/L nickel nitrate, copper nitrate and zinc nitrate solution reacts 12 ~ 30 hours, after then being dried at 50 ~ 100 DEG C, in 300 ~ 600 DEG C of 3 ~ 6h of calcining, obtain blocks of solid；After described blocks of solid grinding, at 300 ~ 500 DEG C, hydrogen reducing is added 3 ~ 6h is reacted, obtains described nickel, copper, the mesoporous MnO of zinc load2Catalyst.
- 3. the mesoporous MnO of nickel according to claim 2, copper, zinc load2Catalyst, it is characterised in that：Described is organic molten Agent is n-hexane.
- 4. the mesoporous MnO of nickel according to claim 2, copper, zinc load2Catalyst, it is characterised in that：Described is alkaline molten Liquid is sodium hydroxide.
- 5. the mesoporous MnO of nickel according to claim 2, copper, zinc load2Catalyst, it is characterised in that：By described SBA- 15 are dissolved in described organic solvent, then ultrasonic disperse 1 ~ 3 hour, add described Mn (NO3)2 Solution.
- 6. one kind 4, the preparation method of 4- dimethyl -1- (4- rubigan)-propione, it is characterised in that：By 4,4- diformazans Base -1- (4- rubigan) -1- penten-3-ones and hydrogen in the presence of organic solvent and catalyst, 1.5 ~ 2.5 MPa, 10 ~ 20h is reacted at 90 ~ 110 DEG C, described 4,4- dimethyl -1- (4- rubigan)-propione, described catalyst is made Nickel, copper, the mesoporous MnO of zinc load any one of claim 1 to 52Catalyst;Described 4,4- dimethyl -1- The mesoporous MnO that (4- rubigan) -1- penten-3-ones load with described nickel, copper, zinc2The addition mass ratio of catalyst be 3 ~ 10:1。
- 7. the preparation method of 4,4- dimethyl -1- (4- rubigan)-propione according to claim 6, its feature exist In：Described organic solvent is methanol and/or dimethyl sulfoxide (DMSO).
- 8. the preparation method of 4,4- dimethyl -1- (4- rubigan)-propione according to claim 6, its feature exist In：In the initial period of reaction, the concentration of described 4,4- dimethyl -1- (4- rubigan) -1- penten-3-ones for 0.4 ~ 0.6g/mL。
- 9. the preparation method of 4,4- dimethyl -1- (4- rubigan)-propione according to claim 6, its feature exist In：Described 4,4- dimethyl -1- (4- rubigan)-propione is prepared to concretely comprise the following steps：By described 4,4- dimethyl- 1- (4- rubigan) -1- penten-3-ones are dissolved in methanol, add described nickel, copper, the mesoporous MnO of zinc load2Catalysis Agent, dimethyl sulfoxide (DMSO) is then added, through being repeatedly flushed with hydrogen gas displacement, be flushed with hydrogen gas to the MPa of pressure 1.8 ~ 2.2, interior temperature is 95 ~ 105 DEG C, after completion of the reaction, through cooling, release, use N2Reaction material liquid is extruded after displacement repeatedly, is filtered out under catalyst solid is used for The preparation of one batch materials, concentrating filter liquor obtain described 4,4- dimethyl -1- (4- rubigan)-propione.
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| CN112062662A (en) * | 2020-09-11 | 2020-12-11 | 安达市多森新材料科技有限公司 | Preparation method of 1- (4-chlorphenyl) -4, 4-dimethyl-3-pentanone |
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