CN102258994A - Method for preparing catalyst used in synthesizing isophorone through acetone multiphase method - Google Patents
Method for preparing catalyst used in synthesizing isophorone through acetone multiphase method Download PDFInfo
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- CN102258994A CN102258994A CN 201110130003 CN201110130003A CN102258994A CN 102258994 A CN102258994 A CN 102258994A CN 201110130003 CN201110130003 CN 201110130003 CN 201110130003 A CN201110130003 A CN 201110130003A CN 102258994 A CN102258994 A CN 102258994A
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Abstract
The invention relates to a method for preparing a catalyst used in synthesizing isophorone through an acetone multiphase method. The method provided by the invention comprises the following steps: weighing and dissolving a certain quantity of magnesium salt, calcium salt, aluminum salt and transition metal salt in distilled water to prepare a mixed salt solution; dropwise adding a precipitator-alkali solution to the mixed salt solution in the stirring course; and aging, filtering, washing, drying and roasting the precipitates to finally obtain the catalyst. Compared with the prior art, the method provided by the invention has the characteristics: (1) the preparation course of the catalyst is simple; (2) the price of the raw materials of the catalyst is low; and (3) the reaction is carried out under gas phase conditions, and the catalyst is a magnesium-calcium-aluminum composite oxide modified by the transition metal. The catalyst provided by the invention has certain acid strength and alkali strength, thereby enabling the catalyst to have higher catalytic activity and stability. In the reaction for preparing the isophorone through acetone condensation, the conversion rate of acetone is about 34%, the selectivity of the isophorone reaches more than 90%, and the one-way running time is larger than 1000 hours.
Description
Technical field
The present invention relates to chemical field, relate in particular to a kind of Preparation of catalysts method that is used for acetone through heterogeneous method synthesis of isophorone.
Background technology
Isophorone is a kind of important fine chemical material, of many uses, both can be used as a kind of senior solvent, also can be used as a kind of organic reaction intermediate, both macromolecular materials such as solubilized nitrocellulose, acrylate, alkyd resins, polyester and epoxy resin, can be used as intermediate raw material again, generate staple products such as alcohol, acid, amine, ester and isocyanates by reaction.
Industrialization process route by synthesis of isophorone from acetone mainly is an acetone condensation method.Acetone condensation method is three molecule acetone self condensation a part isophorones.Present production technology mainly is an acetone pressurization liquid phase condensation method, adopts KOH to make catalyst.The isophorone total recovery that this method obtains is about 60~70%, acetone conversion about 6~10%.The catalyst that this technology is used is simple, easy to operate, and isophorone yield height is suitable for suitability for industrialized production.But in course of reaction, the reactor of employing is a high-tension apparatus, and internal structure is complicated, and acetone conversion is not high, and the waste liquid etching apparatus of generation brings bigger difficulty for separation and post processing, causes environmental pollution simultaneously.Is that advantages such as fixed bed, easy amplification more and more cause people's attention through the process route of heterogeneous catalysis condensation synthesis of isophorone because of its environmental protection, acetone conversion height, reactor by acetone.The condensation of acetone reaction belongs to acid base catalyzed reaction, when catalyst possesses certain soda acid intensity, can reach condensation result preferably.
It is the process that the condensation of acetone of catalyst prepares isophorone with solid sodium ethanol or highly basic that patent 200710021600.6 discloses a kind of.This good catalyst activity, life cycle is long.But highly basic has certain corrosivity to equipment, and environment is had to a certain degree pollution, and therefore more patent is devoted to the exploitation of other solid acid alkali catalytic agent system.
Patent US4535187 discloses a kind of calcium aluminium composite oxide catalyst.Patent US4476324 and EP512843 disclose a kind of magnalium co-precipitated catalyst separately.These catalyst all have catalytic activity preferably.Patent US4970191 utilizes boehmite to be the aluminium source, adopts the sol deposition method to prepare the Mg-Al composite oxide catalyst, and this catalyst activity is higher, and acetone conversion is up to 32.5%, and the isophorone selectivity reaches 74.8%.
The catalyst of present stage generally with magnesium aluminum oxide or calcium aluminum oxide as catalyst system.This system has Acidity of Aikalinity coupling to a certain degree, causes the condensation appropriateness of acetone to be finished.Yet from the result of study of present stage, there are shortcomings such as preparation technology's relative complex, life-span weak point, regeneration difficulty and isophorone selectivity are low in the catalyst of being developed.The main cause of this System Catalyst inactivation is a carbon deposit.
Summary of the invention
The present invention is from improving the Acidity of Aikalinity angle of catalyst, on the basis of former magnalium, calcium aluminium composite oxide, on catalyst, add a small amount of transition metal, and then adjusted the Acidity of Aikalinity of catalyst, with the formation of minimizing carbon deposit, thereby prolong life of catalyst.
The object of the present invention is to provide a kind of catalyst that is used for the heterogeneous method synthesis of isophorone of acetone.
Another object of the present invention is to be to provide a kind of above-mentioned Preparation of catalysts method.The catalyst that utilizes this method to obtain has certain acid strength and base strength.
Catalyst provided by the invention is a kind of high activity and high stability, the acid base catalysator that is used for fixing the bed reaction, its preparation process is as follows: claim a certain amount of magnesium salts, calcium salt, aluminium salt and transition metal salt to be dissolved in the distilled water, be mixed with mixing salt solution, under agitation in solution, dropwise add precipitating reagent-aqueous slkali.Sediment finally obtains catalyst through aging, filtration, washing, drying and roasting.
In the method provided by the invention, said magnesium salts, calcium salt, aluminium salt, transition metal salt are nitrate, chlorate or sulfate, preferably nitrate.
In the method provided by the invention, said transition metal is titanium or zirconium, preferred zirconium.
Compare with prior art, be characterized in: (1) catalyst preparation process is simple; (2) the catalyst raw material is cheap; (3) be reflected under the gas phase condition and carry out, catalyst is a kind of magnesium-calcium-aluminium composite oxide of modifying through the transition metal.Catalyst provided by the invention has certain acid strength and base strength, makes this catalyst have higher catalytic activity and stability.Prepare in the reaction of isophorone at condensation of acetone, acetone conversion reaches about 34%, and the isophorone selectivity reaches more than 90%, and one way duration of runs was greater than 1000 hours.
The specific embodiment
As embodiment, when magnesium salts of the present invention, calcium salt, aluminium salt, transition metal salt are selected nitrate for use, when transition metal is elected zirconium as, Preparation of catalysts method of the present invention comprises the following steps: magnesium nitrate, calcium nitrate, aluminum nitrate and zirconium nitrate are dissolved in the distilled water, is mixed with the mixing salt solution of 1-2 molar concentration.Under agitation in mixing salt solution, dropwise add aqueous slkali to pH value to 7-10.Sediment was worn out 3-12 hour in 60-100 ℃ of temperature.Leave standstill cooling and filter after 1-6 hour, then the filter cake that obtains is spent deionised water to neutral.With filter cake in 80-120 ℃ baking oven dry 12 hours, then under air atmosphere 350-700 ℃ roasting 2-7 hour, finally obtain catalyst.
The proportioning of described magnesium nitrate, calcium nitrate, aluminum nitrate and zirconium nitrate is: control Mg/Ca mol ratio is 1-3: 1, and the Mg/A1 mol ratio is 0.1-5: 1, the Mg/Zr mol ratio is 10-30: 1.
Described aqueous slkali is the potassium hydroxide solution of mass concentration 1%.
Prepared catalyst specific surface is 150-300m
2/ g, pore volume are 0.3-0.4cm
3/ g.
It is raw material that catalyst of the present invention is used for acetone, through the reaction of condensation prepared isophorone.Reaction condition is temperature 220-300 ℃, pressure 0.1-1MPa, acetone weight space velocity 1-3h
-1Condition under, described catalyst has high isophorone selectivity, high stability and higher acetone conversion, selectivity reaches as high as 94.6%, acetone conversion is up to 43.5%, stability reached more than 1000 hours, in stability test, acetone conversion can maintain about 34%, and the isophorone selectivity can maintain more than 90%.
Embodiment 1
270 gram magnesium nitrate hexahydrates, 250 gram four water-calcium nitrates, 770 gram nine water aluminum nitrates and 15 grams, five water zirconium nitrates are dissolved in the 2000ml deionized water.The KOH that dropwise adds mass concentration 1%, to PH be 8.5.Wore out 8 hours at 70 ℃ of following constant temperature, leave standstill cooling 2 hours.Filter and spend deionised water filter cake to filtrate and be neutrality.Descended dry 12 hours at 80 ℃ again, made catalyst in 7 hours in 350 ℃ of roastings under the air atmosphere.
Embodiment 2
270 gram magnesium nitrate hexahydrates, 200 gram four water-calcium nitrates, 500 gram nine water aluminum nitrates and 30 grams, five water zirconium nitrates are dissolved in the 3000ml deionized water.The KOH to PH that dropwise adds mass concentration 1% is 7.5.60 ℃ of following constant temperature wore out 12 hours, left standstill cooling 1 hour.Filter and spend deionised water filter cake to filtrate and be neutrality.Drying is 12 hours under 100 ℃, makes catalyst in 5 hours in 400 ℃ of roastings under the air atmosphere.
Embodiment 3
270 gram magnesium nitrate hexahydrates, 150 gram four water-calcium nitrates, 220 gram nine water aluminum nitrates and 25 grams, five water zirconium nitrates are dissolved in the 2000ml deionized water.The KOH to PH that dropwise adds mass concentration 1% is 8.90 ℃ of following constant temperature wore out 4 hours, left standstill cooling 4 hours.Filter and spend deionised water filter cake to filtrate and be neutrality.Drying is 12 hours under 120 ℃, makes catalyst in 4 hours in 550 ℃ of roastings under the air atmosphere.
Embodiment 4
270 gram magnesium nitrate hexahydrates, 100 gram four water-calcium nitrates, 120 gram nine water aluminum nitrates and 35 grams, five water zirconium nitrates are dissolved in the 1000ml deionized water.The KOH to PH that dropwise adds mass concentration 1% is 9.5.100 ℃ of following constant temperature wore out 3 hours, left standstill cooling 6 hours.Filter and spend deionised water filter cake to filtrate and be neutral.Drying is 12 hours under 120 ℃, makes catalyst in 2 hours in 700 ℃ of roastings under the air atmosphere.
Embodiment 5
270 gram magnesium nitrate hexahydrates, 85 gram four water-calcium nitrates, 100 gram nine water aluminum nitrates and 45 grams, five water zirconium nitrates are dissolved in the 1000ml deionized water.The KOH to PH that dropwise adds mass concentration 1% is 10.70 ℃ of following constant temperature wore out 5 hours, left standstill cooling 3 hours.Filter and spend deionised water filter cake to filtrate and be neutral.Drying is 12 hours under 100 ℃, makes catalyst in 3 hours in 600 ℃ of roastings under the air atmosphere.
Embodiment 6
Present embodiment is to use the embodiment of above-mentioned Preparation of Catalyst isophorone.Raw material is an acetone, and catalyst amount is 8-14 purpose catalyst 20g.Concrete experimentation is as follows: experiment is carried out on the fixed bed reactors of continuous-flow, and fresh acetone enters reactor by micro-plunger displacement pump injecting reactor after the preheating vaporization.Experiment is at 220 ℃, and 0.1MPa, acetone weight space velocity are 1h
-1Condition under carry out, the activity experiment of catalyst runs after 24 hours the results are shown in Table 1.
Table 1
Acetone conversion % | Isophorone selectivity % | |
Embodiment 1 | 28.2 | 81.2 |
Embodiment 2 | 30.6 | 80.5 |
Embodiment 3 | 29.5 | 83.2 |
Embodiment 4 | 33.5 | 87.5 |
Embodiment 5 | 30.2 | 84.7 |
Embodiment 7
Present embodiment is to use the embodiment of above-mentioned Preparation of Catalyst isophorone.Raw material is an acetone, and catalyst amount is 8-14 purpose catalyst 20g.Concrete experimentation is as follows: experiment is carried out on the fixed bed reactors of continuous-flow, and fresh acetone enters reactor by micro-plunger displacement pump injecting reactor after the preheating vaporization.Experiment is at 260 ℃, and 0.5MPa, acetone weight space velocity are 2h
-1Condition under carry out, the activity experiment of catalyst runs after 24 hours the results are shown in Table 2.
Table 2
Acetone conversion % | Isophorone selectivity % | |
Embodiment 1 | 32.7 | 79.6 |
Embodiment 2 | 35.1 | 80.1 |
Embodiment 3 | 31.2 | 82.2 |
Embodiment 4 | 38.5 | 86.5 |
Embodiment 5 | 35.7 | 83.5 |
Embodiment 8
Present embodiment is to use the embodiment of above-mentioned Preparation of Catalyst isophorone.Raw material is an acetone, and catalyst amount is 8-14 purpose catalyst 20g.Concrete experimentation is as follows: experiment is carried out on the fixed bed reactors of continuous-flow, and fresh acetone enters reactor by micro-plunger displacement pump injecting reactor after the preheating vaporization.Experiment is at 300 ℃, and 1MPa, acetone weight space velocity are 2h
-1Condition under carry out, the activity experiment of catalyst runs after 24 hours the results are shown in Table 3.
Table 3
Acetone conversion % | Isophorone selectivity % | |
Embodiment 1 | 38.2 | 85.2 |
Embodiment 2 | 40.6 | 90.7 |
Embodiment 3 | 39.5 | 91.0 |
Embodiment 4 | 43.5 | 94.6 |
Embodiment 5 | 40.2 | 89.5 |
Embodiment 9
This example is a research object with embodiment 4 catalyst, has carried out stability test.The evaluating catalyst condition is: 300 ℃, 1MPa, acetone feed weight space velocity are 2h
-1, always last more than 1000 hours.The results are shown in Table 4.From the result as seen, on this catalyst, the acetone initial conversion is up to 43.5%, and steadily the back conversion ratio maintains about 34%, and the isophorone selectivity maintains about 90%, and reaction was gone through 1000 hours, and catalyst does not have inactivation.
Table 4
Reaction time (hour) | Acetone conversion % | Isophorone selectivity % |
24 | 43.5 | 94.6 |
96 | 41.3 | 92.8 |
147 | 41.9 | 93.7 |
214 | 40 | 90.6 |
287 | 40.7 | 95.9 |
358 | 36.9 | 93.4 |
405 | 39 | 94.9 |
501 | 35.4 | 93.4 |
549 | 33.4 | 93.1 |
597 | 35.2 | 96.9 |
645 | 37.9 | 94.6 |
717 | 35.2 | 93.6 |
765 | 34.2 | 92.8 |
818 | 33.7 | 96 |
866 | 33.4 | 93.9 |
909 | 34.2 | 92.8 |
957 | 33.7 | 93.4 |
1010 | 35.9 | 93.6 |
Claims (6)
1. Preparation of catalysts method that is used for the heterogeneous method synthesis of isophorone of acetone, its preparation process is as follows: claim a certain amount of magnesium salts, calcium salt, aluminium salt and transition metal salt to be dissolved in the distilled water, be mixed with mixing salt solution, under agitation in solution, dropwise add precipitating reagent-aqueous slkali, sediment finally obtains catalyst through aging, filtration, washing, drying and roasting;
Described magnesium salts, calcium salt, aluminium salt, transition metal salt are nitrate, chlorate or sulfate;
Described transition metal is titanium or zirconium.
2. Preparation of catalysts method according to claim 1, when described magnesium salts, calcium salt, aluminium salt, transition metal salt nitrate, when transition metal is zirconium, the preparation method comprises the following steps: magnesium nitrate, calcium nitrate, aluminum nitrate and zirconium nitrate are dissolved in the distilled water, be mixed with the mixing salt solution of 1-2 molar concentration, under agitation in mixing salt solution, dropwise add aqueous slkali to pH value to 7-10; Sediment was worn out 3-12 hour in 60-100 ℃ of temperature, leave standstill cooling and filter after 1-6 hour, then the filter cake that obtains is spent deionised water to neutral; With filter cake in 80-120 ℃ baking oven dry 12 hours, then under air atmosphere 350-700 ℃ roasting 2-7 hour, finally obtain catalyst.
3. according to claim 1,2 described Preparation of catalysts methods, it is characterized in that: the proportioning of described magnesium nitrate, calcium nitrate, aluminum nitrate and zirconium nitrate is: control Mg/Ca mol ratio is 1-3: 1, the Mg/Al mol ratio is 0.1-5: 1, and the Mg/Zr mol ratio is 10-30: 1.
4. according to claim 2,3 described Preparation of catalysts methods, it is characterized in that: described aqueous slkali is the potassium hydroxide solution of mass concentration 1%.
5. according to the described Preparation of Catalyst of claim 4, it is characterized in that: prepared catalyst specific surface is 150-300m
2/ g, pore volume are 0.3-0.4cm
3/ g.
6. the described Application of Catalyst of claim 5, it is characterized in that: in reaction temperature is 220-300 ℃, and reaction pressure is 0.1-1.0MPa, and the reaction liquid weight space velocity is 1-2h
-1Condition under, described catalyst selectivity reaches as high as 94.6%, acetone conversion is up to 43.5%, stability reached more than 1000 hours.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN105268422A (en) * | 2014-07-11 | 2016-01-27 | 中国石油化工股份有限公司 | Preparation method of isophorone catalyst |
CN109926040A (en) * | 2017-12-15 | 2019-06-25 | 中国科学院大连化学物理研究所 | A kind of heterogeneous catalyst preparing isophorone and its preparation and application |
KR20220055782A (en) * | 2020-10-27 | 2022-05-04 | 금호석유화학 주식회사 | Molded catalyst, method of preparing the catalyst, and method for producing cyclic ketone using the same |
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105268422A (en) * | 2014-07-11 | 2016-01-27 | 中国石油化工股份有限公司 | Preparation method of isophorone catalyst |
CN109926040A (en) * | 2017-12-15 | 2019-06-25 | 中国科学院大连化学物理研究所 | A kind of heterogeneous catalyst preparing isophorone and its preparation and application |
CN109926040B (en) * | 2017-12-15 | 2021-08-17 | 中国科学院大连化学物理研究所 | Heterogeneous catalyst for preparing isophorone and preparation and application thereof |
KR20220055782A (en) * | 2020-10-27 | 2022-05-04 | 금호석유화학 주식회사 | Molded catalyst, method of preparing the catalyst, and method for producing cyclic ketone using the same |
WO2022092457A1 (en) * | 2020-10-27 | 2022-05-05 | 금호석유화학 주식회사 | Molded catalyst, production method for same, and method for producing cyclic ketone using same |
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 |
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