CN103285847B - Dehydrogenation catalyst, preparation method and application thereof, and method for preparing cyclohexanone by cyclohexanol dehydrogenation - Google Patents
Dehydrogenation catalyst, preparation method and application thereof, and method for preparing cyclohexanone by cyclohexanol dehydrogenation Download PDFInfo
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- CN103285847B CN103285847B CN201210050539.9A CN201210050539A CN103285847B CN 103285847 B CN103285847 B CN 103285847B CN 201210050539 A CN201210050539 A CN 201210050539A CN 103285847 B CN103285847 B CN 103285847B
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Abstract
The invention provides a dehydrogenation catalyst, and a preparation method and application thereof. The method comprises the following steps: under coprecipitation conditions, contacting a soluble salt of a dehydrogenation active component with a cationic precipitant capable of precipitating the soluble salt in water, filtering to obtain a solid precipitate, and drying and roasting the solid precipitate or directly roasting the solid precipitate, wherein the dehydrogenation active component contains Zn, Ca and Ba in a mol ratio of (3-1000):(5-50):1, and the contacting is carried out in the presence of an organic compound containing hydroxy functional group. The invention also provides a method for preparing cyclohexanone by cyclohexanol dehydrogenation. The dehydrogenation catalyst provided by the invention has higher catalytic activity in dehydrogenation reaction, can implement catalytic dehydrogenation at higher vapor-phase temperature, can keep high selectivity for the target product, and can achieve higher conversion rate and higher selectivity for cyclohexanone at higher vapor-phase dehydrogenation temperature especially in dehydrogenation reaction of cyclohexanol for preparing cyclohexanone.
Description
Technical field
The present invention relates to a kind of preparation method of dehydrogenation, and the dehydrogenation prepared by the preparation method of dehydrogenation of the present invention and the application in dehydrogenation reaction thereof, and the method for cyclohexanone is prepared in a kind of cyclohexanol dehydrogenation.
Background technology
The catalytic dehydrogenation reaction of secondary alcohol is widely used for industrial quarters to manufacture ketone compounds, such as manufacture cyclohexanone (concrete visible K.Weissermel from cyclohexanol dehydrogenation, H.-J.Arpe, IndustrielleOrganische Chemie, 4th edition, Verlag Chemie, Weinheim, 1994, the 274th page).The reaction that dehydrogenation reaction prepares cyclohexanone as cyclohexanol dehydrogenation is the endothermic reaction (see following formula), therefore dehydrogenation
reaction generally comprises at relatively high temperatures, generally at 200 DEG C, make alcohol or alcohol/alcohol/ketone mixtures by a kind of copper catalyst, it is important in this that must be noted that alcohols catalyst is dehydrogenated to ketone is reversible reaction, equilbrium position can offset towards starting material when the temperature decreases.And balancing speed is very slow at low temperatures, except low-conversion, make it generally cannot reach balance, on the contrary, if carry out at relatively high temperatures, such as higher than 400 DEG C, easily cause other side reactions as two polymerisations of product ketone, that can cause valuable product is lower selective.
For the particularity of dehydrogenation reaction, the existing more research about dehydrogenation reaction, and major part research is all optimize dehydrogenating technology by improving dehydrogenation, such as CN1106372C discloses a kind of process for dehydrogenating secondary cyclic alcohols, under being included in the catalyst existence comprising the zinc oxide of 30-60wt% and the calcium carbonate of 40-70wt%, to secondary cyclic alcohol gas-phase dehydrogenation at 200-500 DEG C of temperature.And it is pointed out in the description further, when using cyclohexanol as initial compounds, temperature is within the scope of 350-400 DEG C.
CN100455556C discloses has 3-25 carbon atom and at least one can the method for optically-active aldehydes or ketones of racemic stereocenter a kind of preparation, described method is included under the existence comprising the zinc of oxide form and/or its carbonate form and the catalyst of calcium in the gas phase by corresponding optically-active primary alconol or secondary alcohol catalytic dehydrogenation, desorption temperature is 250-600 DEG C, (temperature range of specific, concrete selection should make the conversion ratio of alcohol be 20-60% to be preferably 300-450 DEG C, preferred 35-50%), and point out when citronellol is as initial compounds, desorption temperature is preferably 350-450 DEG C, point out that controlling sintering temperature in the preparation process of catalyst is no more than 600 DEG C simultaneously, preferred sintering temperature is 300-600 DEG C, especially preferably sintering temperature be 400-475 DEG C with the formation avoiding the too high roasting of temperature to cause the aragonite variant of calcium carbonate.
As can be seen here, dehydrogenation is carried out under the catalyst of prior art exists, all need to control certain desorption temperature (being generally 300-450 DEG C) in gas-phase dehydrogenation process to realize, under the condition ensureing certain conversion ratio, making the selective relatively high of target product.
But due to desorption temperature lower, make reaction rate comparatively slow undoubtedly, thus make to obtain higher conversion ratio and need the longer time, be therefore unfavorable for industrial applications.
Summary of the invention
The object of the present invention is to provide a kind of alcohol can at a relatively high temperature Oxidative Dehydrogenation for the method for ketone, especially by selecting suitable dehydrogenation active component, and the organic compound introduced containing functional group's hydroxyl carries out the preparation of catalyst in the preparation process of dehydrogenation, adopt the catalyst for preparing of the method can dehydrogenation at a higher temperature, and almost there is no the generation of other side reactions, namely can obtain the selective of higher conversion ratio and target product within the relatively short time.
To achieve these goals, the invention provides a kind of preparation method of dehydrogenation, the method comprises: under Coprecipitation, filters after the soluble-salt of dehydrogenation active component and the cationic precipitating reagent that can precipitate described soluble-salt are contacted in water and obtains solid sediment, by described solid sediment drying or moist after carry out roasting; Wherein, containing Zn element, Ca element and Ba element in described dehydrogenation active component, and the mol ratio of Zn element, Ca element and Ba element is 3-1000: 5-50: 1, and described contact is carried out under the organic compound containing functional group's hydroxyl exists.
The invention provides a kind of dehydrogenation prepared by the preparation method of dehydrogenation of the present invention.
The invention provides the application of a kind of dehydrogenation prepared by the preparation method of dehydrogenation of the present invention in dehydrogenation reaction.
The invention provides a kind of method that cyclohexanone is prepared in cyclohexanol dehydrogenation, the method comprises: at dehydrogenation condition, by cyclohexanol and catalyst exposure, wherein, described catalyst is dehydrogenation of the present invention or is suppressed the formed body obtained by dehydrogenation of the present invention.
The dehydrogenation adopting the preparation method of dehydrogenation of the present invention to prepare has higher catalytic activity in dehydrogenation reaction, it can catalytic dehydrogenation and can keep the selective of higher target product under higher gas phase temperature, particularly being applied to cyclohexanol dehydrogenation prepares in the dehydrogenation reaction of cyclohexanone, can at higher gas-phase dehydrogenation temperature, reach higher conversion ratio in the short period and cyclohexanone selective higher.And as can be seen from the data of comparative example 1, comparative example 2, comparative example 3, the organic compound containing functional group's hydroxyl, compared to the composition of active component, has larger impact to the activity of the dehydrogenation that preparation method of the present invention prepares.
Other features and advantages of the present invention are described in detail in detailed description of the invention part subsequently.
Detailed description of the invention
Below the specific embodiment of the present invention is described in detail.Should be understood that, detailed description of the invention described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of preparation method of dehydrogenation, the method comprises: under Coprecipitation, filters after the soluble-salt of dehydrogenation active component and the cationic precipitating reagent that can precipitate described soluble-salt are contacted in water and obtains solid sediment, by described solid sediment drying or moist after carry out roasting; Wherein, containing Zn element, Ca element and Ba element in described dehydrogenation active component, and the mol ratio of Zn element, Ca element and Ba element is 3-1000: 5-50: 1, and described contact is carried out under the organic compound containing functional group's hydroxyl exists.
According to the preparation method of dehydrogenation of the present invention, as long as the mol ratio of Zn element, Ca element and Ba element is 3-1000: 5-50: 1 in guarantee dehydrogenation active component, and described contact is carried out realizing object of the present invention under the organic compound containing functional group's hydroxyl exists, and the present inventor finds better to realize object of the present invention when the mol ratio of described Zn element, Ca element and Ba element is 5-500: 10-20: 1, therefore, the mol ratio of the preferred Zn element of the present invention, Ca element and Ba element is 5-500: 10-20: 1.
In the present invention, the cation of described soluble-salt refers to the cation of the active metallic element in active component, such as, containing Zn element, Ca element and Ba element in active component of the present invention, then the cation of soluble-salt generally refers to zinc ion and (is generally Zn
2+), calcium ion (is generally Ca
2+), barium ions (Ba
2+).To this, those skilled in the art all can know, this is no longer going to repeat them.
According to the preparation method of dehydrogenation of the present invention, as long as Zn element in guarantee dehydrogenation active component, the mol ratio of Ca element and Ba element is 3-1000: 5-50: 1, and described contact is carried out realizing object of the present invention under the organic compound containing functional group's hydroxyl exists, and the present inventor finds better to realize object of the present invention when the described organic compound containing functional group's hydroxyl is alcohol, and the catalyst prepared has higher stability, gas-phase dehydrogenation can be carried out at a higher temperature thus, and carry out gas-phase dehydrogenation in the presence of a catalyst of the invention and can obtain the selective of higher target product.
Therefore, the present invention preferably described organic compound containing functional group's hydroxyl is substituted or unsubstituted alcohol, is more preferably the substituted or unsubstituted alcohol of C1-C10, is more preferably the substituted or unsubstituted alcohol of C2-C6.For the alcohol replaced, the alcohol preferably replaced by amino, be particularly preferably the hydramine of C2-C6, as being monoethanolamine, diethanol amine, triethanolamine, 3-Propanolamine (also title normal propyl alcohol amine), monoisopropanolamine, diisopropanolamine (DIPA), triisopropanolamine, N, one or more in N-dimethylethanolamine and N, N-diethyl ethylene diamine.
According to the preparation method of dehydrogenation of the present invention, as long as ensure that described contact is carried out realizing object of the present invention under the organic compound containing functional group's hydroxyl exists, the range of choices of the consumption of the described organic compound containing functional group's hydroxyl is wider, for the present invention, in order to optimize the performance of dehydrogenation of the present invention further, preferably relative to the soluble-salt of every gram of dehydrogenation active component, the consumption of the described organic compound containing functional group's hydroxyl is 0.1-800mg, is preferably 10-500mg.
According to the preparation method of dehydrogenation of the present invention, the range of choices of the kind of the soluble-salt of described dehydrogenation active component is wider, conventional soluble-salt all can be used for the present invention, can be such as one or more in acetate, sulfate and nitrate, be preferably nitrate, specifically, when described active component contains Zn element, Ca element and Ba element, described soluble zinc salt can be one or more in zinc nitrate, zinc sulfate, zinc acetate and zinc chloride, is preferably zinc nitrate; Described soluble calcium salt can be one or more in calcium nitrate, calcium sulfate, calcium acetate and calcium chloride, is preferably calcium nitrate; Described soluble barium salt can be one or more in barium nitrate, barium acetate and barium chloride, is preferably barium nitrate.
In the present invention, the range of choices of the kind of described precipitating reagent is wider, the cationic precipitating reagent that can precipitate soluble-salt of the present invention of prior art all can realize object of the present invention, can be generally such as soluble carbonate salt (being preferably the carbonate of alkalescence), be preferably one or more in sodium carbonate, potash, sodium acid carbonate, saleratus, ammonium carbonate and carbonic hydroammonium.
In the present invention, the condition of described co-precipitation can be selected according to prior art, and the temperature that the present inventor finds reasonably to control co-precipitation can improve the selective of catalyst further, therefore, for the present invention, preferred described Coprecipitation comprises: temperature is 10-100 DEG C, is preferably 50-70 DEG C.
In the present invention, the range of choices of the temperature of described roasting is wider, and for the present invention, the temperature of preferred described roasting is 300-800 DEG C.
The invention provides a kind of dehydrogenation prepared by the preparation method of dehydrogenation of the present invention.
The invention provides the application of a kind of dehydrogenation prepared by the preparation method of dehydrogenation of the present invention in dehydrogenation reaction.
The dehydrogenation adopting the preparation method of dehydrogenation of the present invention to prepare has higher catalytic activity in dehydrogenation reaction, and it can catalytic dehydrogenation and can keep the selective of higher target product under higher gas phase temperature
The invention provides a kind of method that cyclohexanone is prepared in cyclohexanol dehydrogenation, the method comprises: at dehydrogenation condition, by cyclohexanol and catalyst exposure, wherein, described catalyst is dehydrogenation of the present invention or is suppressed the formed body obtained by dehydrogenation of the present invention.
Dehydrogenation of the present invention is applied to cyclohexanol dehydrogenation and prepares in the dehydrogenation reaction of cyclohexanone, can at higher gas-phase dehydrogenation temperature, reaches higher conversion ratio and cyclohexanone selective higher in the short period.
The method of cyclohexanone is prepared in cyclohexanol dehydrogenation according to the present invention, the range of choices of described dehydrogenation condition is wider, the dehydrogenation condition of prior art all can realize object of the present invention, for the present invention, preferred described dehydrogenation condition is gas-phase dehydrogenation condition, the temperature of described dehydrogenation is 200-700 DEG C, is more preferably 400-600 DEG C, is particularly preferably 460-530 DEG C.
More preferably in situation, described gas-phase dehydrogenation condition of the present invention also comprises: pressure is 0.05-8MPa, is preferably 0.1-2MPa.Aforementioned pressure is generally pressure spontaneous in reactor, also can Additional pressurizations, and the pressure in embodiments of the invention is pressure spontaneous in reactor.Dehydrogenation of the present invention can be carried out under hydrogen presence or absence, all can know these those skilled in the art.In order to improve the selective of target product, the present invention preferably carries out in presence of hydrogen.
The present invention without particular/special requirement to the time of described dehydrogenation, can carry out with reference to prior art, be generally 1-10 hour, is preferably 2-8 hour, is more preferably 2-4 hour.
Dehydrogenation of the present invention has good stability, can keep good activity after dehydrogenation reaction carries out 200-2000 hour continuously.
Preparation embodiment 1
Configuration 2L concentration is the barium nitrate of 30 % by weight, the mixed aqueous solution (wherein Zn-ef ficiency: calcium constituent: the mol ratio of barium element is 5: 20: 1) of calcium nitrate and zinc nitrate;
The mixed aqueous solution that 6g monoethanolamine obtains containing hydramine is added in aforementioned mixed aqueous solution;
Under 70 DEG C of conditions, the aqueous sodium carbonate being 2mol/L by the aforementioned mixed aqueous solution containing hydramine and concentration contacts 2h, wherein, the consumption controlling sodium carbonate makes barium ions, calcium ion and zinc ion all precipitated, then sediment is leached and carry out washing and (wash to having can't detect nitrate, use FeSO
4solution and concentrated sulfuric acid test, this test is called nitrate ring test), then at 610 DEG C, roasting obtains C1 in 5 hours.
Preparation embodiment 2-8
Dehydrogenation C2-C8 is prepared according to the method preparing embodiment 1, unlike, in preparation process, the temperature of active component, co-precipitation and sintering temperature etc. change to some extent (specifically in table 1, wherein identical with preparation embodiment 1 condition is no longer listed).
Preparation comparative example 1-3
Dehydrogenation D1-D3 is prepared according to the method preparing embodiment 1, unlike, in preparation process, active component is different, or the organic compound (specifically in table 1, wherein identical with preparation embodiment 1 condition is no longer listed) do not added in preparation process containing functional group's hydroxyl.
Embodiment 1
Catalyst C1 is carried out mixing rear compacting according to mass ratio 98: 2 with graphite, obtains the tablet of the catalyst C1 after the compacting of 5 × 5mm;
The tablet getting the catalyst C1 after 920g compacting is inserted in the tubular reactor of long 0.6m, internal diameter 0.05m.Through vaporizer, in a gaseous form 640ml/h Breakup of Liquid Ring hexanol is fed in tubular reactor.The countercurrent direction of autoreactor pumps into 7l/h hydrogen to measuring pump.The temperature keeping reactant mixture in reaction zone is 480 DEG C.At this temperature, the conversion ratio of cyclohexanol after 900 hours, cyclohexanone selective in table 2.
Embodiment 2-11
Carry out dehydrogenation according to the method for embodiment 1, change unlike catalyst and/or desorption temperature change, specifically in table 2, the conversion ratio of cyclohexanol after 900 hours, cyclohexanone selective in table 2.
Comparative example 1-3
Carrying out dehydrogenation according to the method for embodiment 1, is D1-D3 unlike catalyst, the conversion ratio of cyclohexanol after 900 hours, cyclohexanone selective in table 2.
Table 1
Table 2
Cyclohexanone selective (%)=(molal quantity of the cyclohexanol consumed in the molal quantity/reaction of the cyclohexanone of generation) × 100%,
The conversion ratio (%) of cyclohexanol=(molal quantity of the molal quantity of the cyclohexanol consumed in reaction/the be provided to raw material cyclohexanol in reaction) × 100%.
As can be seen from data in table, the dehydrogenation adopting the preparation method of dehydrogenation of the present invention to prepare has higher catalytic activity in dehydrogenation reaction, it can catalytic dehydrogenation and can keep the selective of higher target product under higher gas phase temperature, particularly being applied to cyclohexanol dehydrogenation prepares in the dehydrogenation reaction of cyclohexanone, can at higher gas-phase dehydrogenation temperature, reach higher conversion ratio in the short period and cyclohexanone selective higher.And as can be seen from the data of comparative example 1, comparative example 2, comparative example 3, the organic compound containing functional group's hydroxyl, compared to the composition of active component, has larger impact to the activity of the dehydrogenation that preparation method of the present invention prepares.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned detailed description of the invention, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible combination.
In addition, also can be combined between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (14)
1. the preparation method of a cyclohexanol dehydrogenation dehydrogenation, the method comprises: under Coprecipitation, filters after the soluble-salt of dehydrogenation active component and the cationic precipitating reagent that can precipitate described soluble-salt are contacted in water and obtains solid sediment, by described solid sediment drying or moist after carry out roasting; It is characterized in that, containing Zn element, Ca element and Ba element in described dehydrogenation active component, and the mol ratio of Zn element, Ca element and Ba element is 3-1000:5-50:1, and described contact is carried out under the organic compound containing functional group's hydroxyl exists; The described organic compound containing functional group's hydroxyl is the hydramine of C2-C6, and relative to the soluble-salt of every gram of dehydrogenation active component, the consumption of the described organic compound containing functional group's hydroxyl is 0.1-800mg; Described precipitating reagent is soluble carbonate salt.
2. preparation method according to claim 1, wherein, the consumption of the described organic compound containing functional group's hydroxyl is 10-500mg.
3. preparation method according to claim 1, wherein, the soluble-salt of described dehydrogenation active component is one or more in acetate, sulfate and nitrate; Described precipitating reagent is one or more in sodium carbonate, potash, sodium acid carbonate, saleratus, ammonium carbonate and carbonic hydroammonium.
4. preparation method according to claim 3, wherein, the soluble-salt of described dehydrogenation active component is nitrate.
5. preparation method according to claim 1, wherein, described Coprecipitation comprises: temperature is 10-100 DEG C; The temperature of described roasting is 300-800 DEG C.
6. preparation method according to claim 5, wherein, described Coprecipitation comprises: temperature is 50-70 DEG C.
7. the cyclohexanol dehydrogenation dehydrogenation prepared by the preparation method in claim 1-6 described in any one.
8. the application of dehydrogenation according to claim 7 in cyclohexanol dehydrogenation reaction.
9. the method for cyclohexanone is prepared in a cyclohexanol dehydrogenation, the method comprises: under dehydrogenation condition, by cyclohexanol and catalyst exposure, it is characterized in that, described catalyst is cyclohexanol dehydrogenation dehydrogenation according to claim 7 or is suppressed the formed body obtained by cyclohexanol dehydrogenation dehydrogenation according to claim 7.
10. method according to claim 9, wherein, described dehydrogenation condition is gas-phase dehydrogenation condition, and the temperature of described dehydrogenation is 200-700 DEG C.
11. methods according to claim 10, wherein, the temperature of described dehydrogenation is 400-600 DEG C.
12. methods according to claim 11, wherein, the temperature of described dehydrogenation is 460-530 DEG C.
13. according to the method in claim 10-12 described in any one, and wherein, described gas-phase dehydrogenation condition also comprises: pressure is 0.05-8MPa.
14. methods according to claim 13, wherein, described gas-phase dehydrogenation condition also comprises: pressure is 0.1-2MPa.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1056067A (en) * | 1990-04-29 | 1991-11-13 | 王炳炎 | Multi component cyclohexanol dehydrogenation catalyst |
| CN1184705A (en) * | 1996-09-25 | 1998-06-17 | 中国科学院兰州化学物理研究所 | Iron group catalyst for producing butadiene by oxidative dehydrogenation of bytylene |
| CA2701089A1 (en) * | 2010-03-31 | 2011-09-30 | Nova Chemicals Corporation | Pulsed oxidative dehydrogenation process |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080166274A1 (en) * | 2007-01-08 | 2008-07-10 | Fina Technology, Inc. | Oxidative dehydrogenation of alkyl aromatic hydrocarbons |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1056067A (en) * | 1990-04-29 | 1991-11-13 | 王炳炎 | Multi component cyclohexanol dehydrogenation catalyst |
| CN1184705A (en) * | 1996-09-25 | 1998-06-17 | 中国科学院兰州化学物理研究所 | Iron group catalyst for producing butadiene by oxidative dehydrogenation of bytylene |
| CA2701089A1 (en) * | 2010-03-31 | 2011-09-30 | Nova Chemicals Corporation | Pulsed oxidative dehydrogenation process |
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