CN110963901B - Preparation method of 3,3,5-trimethylcyclohexanone - Google Patents
Preparation method of 3,3,5-trimethylcyclohexanone Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/62—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by hydrogenation of carbon-to-carbon double or triple bonds
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- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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Abstract
The invention relates to a preparation method of 3,3,5-trimethylcyclohexanone, which is used for preparing 3,3,5-trimethylcyclohexanone by isophorone selective hydrogenation reaction in the presence of hydrogen and a hydrogenation catalyst. The hydrogenation catalyst is selected from supported nickel or supported cobalt modified by alkali metal carbonate or alkali metal bicarbonate. Meanwhile, a certain amount of ammonium oxalate is added into the reaction liquid, ammonia and carbon monoxide are slowly decomposed and released at the hydrogenation reaction temperature, the generation of byproducts can be inhibited while the conversion rate of isophorone is improved, the subsequent separation operation of TMC and the byproducts 3,3,5-trimethylcyclohexanol is avoided, and the continuous preparation of 3,3,5-trimethylcyclohexanone with high selectivity and high yield is realized.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and relates to a preparation method of 3,3,5-trimethylcyclohexanone.
Background
3,3,5-Trimethylcyclohexanone (TMC) is used as an important high-boiling point organic solvent and a medicine synthesis intermediate, is mainly used in the fields of medicines, pesticides, fine chemical engineering and the like, and downstream products of the TMC can be used as vulcanizing agents in rubber industry and the like and polymer monomers in plastic industry.
TMC is mainly prepared by hydrogenation of Isophorone (IP). The isophorone contains one C = C double bond and one C = O double bond in the molecular structure, and the product 3,3,5-trimethylcyclohexanone is obtained by hydrogenating the C = C double bond. Under the action of a common hydrogenation catalyst, not only the C = C double bond is hydrogenated, but also the C = O double bond is very easily hydrogenated, so that the byproduct 3,3,5-trimethylcyclohexanol is formed, the boiling points of the product and the byproduct are similar (the boiling point of TMC is 189 ℃, and the boiling point of 3,3,5-trimethylcyclohexanol is 191 ℃), and therefore great difficulty is brought to the subsequent product separation work.
Patent CN102718641B proposes a method for preparing TMC by selective hydrogenation of isophorone by adopting Pd or Pt catalyst in an autoclave and adding zinc chloride as cocatalyst, the reaction has higher selectivity, however, the cost is higher after precious metal is adopted, and salts such as zinc chloride and the like are required to be adopted as auxiliary agents, the auxiliary agents have strong corrosivity and toxicity, and are batch reaction, the treatment amount is small, and large-scale production is difficult.
CN105061176B adopts a fixed bed reactor, and isophorone is selectively hydrogenated and reduced into 3,3,5-trimethylcyclohexanone by a Cr modified supported Ni-based catalyst at a reaction temperature of 140-300 ℃. The method has low selectivity of trimethyl cyclohexanone, needs heavy metal Cr to be added, is not beneficial to environmental protection, and increases the wastewater treatment cost.
Disclosure of Invention
The invention aims to prepare a cheap catalyst, improve the conversion rate of isophorone and inhibit the generation of byproducts at the same time under a relatively mild condition, and realize the continuous preparation of 3,3,5-trimethylcyclohexanone with high selectivity and high yield, so that the subsequent separation of TMC and the byproduct 3,3,5-trimethylcyclohexanol is avoided, and the energy consumption of the subsequent separation is further reduced.
In order to realize the purpose of the invention, the following technical scheme is adopted:
the invention provides a preparation method of 3,3,5-trimethylcyclohexanone, which is used for preparing 3,3,5-trimethylcyclohexanone by selective hydrogenation of isophorone in the presence of hydrogen and a hydrogenation catalyst.
In the preparation method of the invention, the hydrogenation catalyst is selected from modified supported nickel or modified supported cobalt, preferably modified supported nickel.
Further, the hydrogenation catalyst, the carrier may be at least one of alumina, silica, titania, magnesia and activated carbon, preferably alumina.
Further, the hydrogenation catalyst, wherein the amount of the active metal component (nickel or cobalt) is 5 to 40% by weight, preferably 10 to 20% by weight, of the support calculated as the oxide thereof.
Because the supported nickel catalyst has strong hydrogenation activity and generally has poor selectivity to carbon-carbon double bonds and carbon-oxygen double bonds, the catalyst of the invention inhibits the hydrogenation of the carbon-oxygen double bonds by adding the modifier, and improves the selectivity of the hydrogenation of the carbon-carbon double bonds.
In addition, the hydrogenation catalyst and the modifier adopt alkali metal carbonate or alkali metal bicarbonate, preferably at least one of sodium bicarbonate, sodium carbonate, potassium carbonate and potassium bicarbonate, and more preferably sodium carbonate. The invention adopts alkali metal carbonate or bicarbonate modified load nickel or cobalt catalyst, can well inhibit hydrogenation of carbon-oxygen double bond in IP, and obtains TMC with high selectivity. The effect of the alkali metal carbonate or bicarbonate modifier added in the present invention may be analyzed as follows: 1) The addition of alkali metal (such as Na ion) promotes Ni and Ni on the surface of the catalyst 2+ Dispersion of ions, increase of isolated Ni 2+ Ion content, ni in reduction with Hydrogen 2+ Ions are more difficult to be completely reduced, the content of ionic Ni in the reduced catalyst is higher, and the reducibility of the catalyst is weakened; 2) The catalyst surface contains alkali metal ions (such as Na) + ) And Ni 2+ Carbon-carbon bis(s) more readily compatible with greater electron densityBonds rather than carbon-oxygen double bonds which are relatively electron deficient adsorb, thereby being more beneficial to hydrogenation with carbon-carbon double bonds; 3) When sodium carbonate is used as a modifier, the sodium carbonate is a strong base and weak acid salt with certain alkalinity, and the sodium carbonate is doped in the catalyst to reduce the surface acidity of the catalyst, accelerate the desorption of TMC and avoid further hydrogenation; and the reduction of the surface acidity of the catalyst is beneficial to avoiding the generation of polymers, thereby reducing the carbon deposition rate and improving the stability of the catalyst.
Further, in the hydrogenation catalyst, the addition amount of the modifier is 1 to 20% by mole, preferably 2 to 8% by mole, calculated as the alkali metal element, relative to the active metal component. The surface area of the catalyst can be obviously reduced and the activity of the catalyst is influenced if the addition amount of the modifier is too large; the addition amount is small, and the effect of improving TMC selectivity is not achieved.
Further, the preparation method of the hydrogenation catalyst, modified supported nickel or modified supported cobalt is not particularly limited, and the hydrogenation catalyst can be prepared by any known method, such as an impregnation method, preferably an equal-volume impregnation method. One preparation method employed in the embodiments of the present invention is: dissolving soluble salt of nickel or cobalt (the soluble salt of nickel or cobalt can be selected from nickel nitrate, nickel chloride, nickel acetate and nickel acetylacetonate, preferably such as nitrate) and modifier in water, preferably, the dosage (calculated by alkali metal) of modifier is 1-20% of mole amount of nickel or cobalt, and the soluble salt of nickel or cobalt is dissolved in water with concentration of 20-50wt%, then adding carrier to impregnate (preferably impregnating in equal volume) for 20-30h, then optionally making operation such as forming, drying and roasting so on to obtain the modified supported nickel or modified supported cobalt catalyst.
Preferably, the particle size range of the formed catalyst is 2-3mm, the shape is not limited, and the catalyst is preferably clover-shaped; the preferable drying temperature is 110-120 ℃, and the time is 1.5-2.0h; the roasting is preferably carried out at the temperature of 550-600 ℃ for 5.5-6.0h.
In the preparation method, in the hydrogenation reaction, an auxiliary agent ammonium oxalate is also added into a reaction system. In the hydrogenation reaction, in order to further improve the TMC selectivity, ammonium oxalate is added into the reaction liquid. Ammonium oxalate can be slowly decomposed at the hydrogenation reaction temperature to release ammonia and carbon monoxide, wherein the ammonia can form a complex with nickel ions, the surface acidity of the catalyst is reduced, the desorption of TMC is accelerated, and the excessive hydrogenation byproducts are further reduced. The generated carbon monoxide and active metal nickel generate a complex, so that the hydrogenation activity of the catalyst is reduced, and the TMC selectivity is improved. Compared with the method of directly introducing gases such as carbon monoxide into a reaction system, the carbon monoxide is added from the outside and can preferentially react with the active metal nickel of the catalyst at the front end of the catalyst bed layer, so that the catalyst is gradually inactivated from front to back. The ammonium oxalate adopted by the invention is mixed and slowly decomposed in a reaction system, and the released gas can be uniformly distributed in a catalyst bed layer, so that the catalyst modification effect is more uniform, and the local inactivation of the catalyst can not be caused.
Furthermore, the addition amount of the ammonium oxalate in the reaction system is 10-5000ppm, preferably 100-1000ppm. The excessive addition of ammonium oxalate can cause the remarkable reduction of the activity of the catalyst due to the excessive amount of generated carbon monoxide, and the excessive addition of ammonium oxalate cannot improve the TMC selectivity.
Preferably, the ammonium oxalate is water, methanol or ethanol solution of ammonium oxalate, preferably ethanol solution of ammonium oxalate, and more preferably the concentration of the ammonium oxalate is 0.05-0.5wt%.
In the preparation method, the hydrogenation reaction pressure is 0.1-5MPa (gauge pressure), preferably 1-2MPa (gauge pressure); the reaction temperature is 70 to 150 ℃ and preferably 95 to 110 ℃. The space velocity is 0.05-4h -1 Preferably 0.2 to 1h -1 . The reaction temperature is required to be controlled in the reaction process, the reaction temperature is not too high, the reaction temperature is high, the hydrogenation reduction of carbon-oxygen double bonds is easy to cause, and the TMC selectivity is reduced; the reaction temperature is low, the catalytic hydrogenation activity is low, and IP is difficult to effectively convert.
Preferably, the method also comprises the operation of reducing and activating the catalyst before the hydrogenation reaction, and specifically adopts hydrogen reduction and activation, wherein the reduction conditions are as follows: the temperature is 260-275 ℃, the pressure is 1-2MPa (gauge pressure), and the time is 7-8h; most preferably 2MPa (gauge pressure) and 270 ℃ for 8h.
In the preparation method of the invention, the hydrogenation reaction can be carried out in a batch or continuous mode, and is preferably a continuous reaction; the hydrogenation reactor is selected from a reaction kettle, a fixed bed or a slurry bed, and preferably a fixed bed.
According to the preparation method, the conversion rate of isophorone can reach more than 99.9%, the selectivity of 3,3,5-trimethylcyclohexanone is more than 99.5%, the selectivity of a by-product 3,3,5-trimethylcyclohexanol is lower than 0.3%, the subsequent separation operation of TMC and the by-product 3,3,5-trimethylcyclohexanol can be avoided, and the energy consumption of subsequent separation is saved.
The technical scheme of the invention has the beneficial effects that: the hydrogenation catalyst is modified by adopting carbonate or bicarbonate of alkali metal, wherein the reducibility of the catalyst can be weakened by alkali metal ions, the carbonate group is used for regulating the acidity of the surface of the catalyst, a certain amount of ammonium oxalate is added into reaction liquid, ammonia and carbon monoxide are slowly decomposed and released at the hydrogenation reaction temperature, the generation of a byproduct can be inhibited while the conversion rate of isophorone is improved, the subsequent separation operation of TMC and the byproduct 3,3,5-trimethylcyclohexanol is avoided, and the continuous preparation of 3,3,5-trimethylcyclohexanone with high selectivity and high yield is realized.
Detailed Description
In order to better understand the technical solution of the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
In the following examples, the chemical composition was determined by gas phase analysis of Shimadzu GC-2010 plus. The conditions for gas chromatography were: a chromatographic column: 30m DB-WAX, ID 0.32mm, FD 0.25 μm;50-230 ℃,3 ℃/min, nitrogen flow rate: 30mL/min, hydrogen flow rate: 40mL/min, air flow rate: 400mL/min; sample introduction amount: 0.2. Mu.L. Conversion and selectivity were calculated using area normalization.
Preparation of hydrogenation catalyst
Example 1
38.9gNi (NO) was prepared by an isovolumetric impregnation method 3 ) 2 ·6H 2 Adding O and 0.14g of sodium carbonate into water under stirring, adding water until the volume of the solution is 100ml after all the salt is dissolved, stirring, adding 100g of alumina serving as a carrier in batches, soaking at room temperature for 24 hours, forming into a 2-3mm clover shape, and drying at 120 ℃ for 2 hours; then roasting for 6h at 600 ℃ to obtain the catalystAgent 1. The loading amount of Ni is 10wt% of the carrier calculated by NiO, and the content of the modifier sodium carbonate calculated by Na element is 2% of the molar amount of Ni.
Example 2
By adopting an equal volume impregnation method, 77.8gNi (NO) is added 3 ) 2 ·6H 2 Adding O and 1.14g of sodium carbonate into water under stirring, adding water until the volume of the solution is 100ml after all the salt is dissolved, stirring, adding 100g of alumina serving as a carrier in batches, soaking at room temperature for 24 hours, forming into a 2-3mm clover shape, and drying at 120 ℃ for 2 hours; then roasting for 6h at 600 ℃ to obtain the catalyst 2. The loading amount of Ni is 20wt% of the carrier calculated by NiO, and the amount of the modifier sodium carbonate calculated by Na element is 8% of the molar amount of Ni.
Example 3
58.4gNi (NO) was prepared by an isovolumetric impregnation method 3 ) 2 ·6H 2 Adding O and 0.53g of sodium carbonate into water under stirring, adding water until the volume of the solution is 100ml after all the salt is dissolved, stirring, adding 100g of alumina serving as a carrier in batches, soaking at room temperature for 24 hours, forming into a 2-3mm clover shape, and drying at 120 ℃ for 2 hours; then roasting for 6h at 600 ℃ to obtain the catalyst 3. The loading amount of Ni is 15wt% of the carrier calculated by NiO, and the amount of the modifier sodium carbonate calculated by Na element is 5% of the molar amount of Ni.
Example 4
Catalyst 4 was obtained in the same manner as in example 3 except that 0.84g of sodium bicarbonate was used instead of 0.53g of sodium carbonate. The loading amount of Ni is 15wt% of the carrier calculated by NiO, and the amount of the modifier sodium carbonate calculated by Na element is 5% of the molar amount of Ni.
Example 5
Only 58.5g gCo (NO) were used 3 ) 2 ·6H 2 O instead of 58.4gNi (NO) 3 ) 2 ·6H 2 Otherwise, catalyst 5 was obtained in the same manner as in example 3. The loading of Co is 15wt% of the carrier calculated by CoO, and the amount of the modifier sodium carbonate calculated by Na element is 5% of the molar amount of Ni.
Example 6
The same procedure as in example 3 was repeated except for using 0.66g of potassium carbonate alone in place of 0.53g of sodium carbonate to obtain catalyst 6. The load of Ni is 15wt% of the carrier calculated by NiO, and the amount of the modifier potassium carbonate calculated by K element is 5% of the molar amount of Ni.
Example 7
Catalyst 7 was obtained by reducing the amount of sodium carbonate to 0.11g only, and the same procedure as in example 3 was repeated. The loading amount of Ni calculated by NiO is 15wt% of the carrier, and the amount of the modifier sodium carbonate calculated by Na element is 1% of the molar amount of Ni.
Example 8
Catalyst 8 was obtained in the same manner as in example 3 except that the amount of sodium carbonate used was adjusted to 2.12 g. The loading amount of Ni calculated by NiO is 15wt% of the carrier, and the amount of the modifier sodium carbonate calculated by Na element is 20% of the molar amount of Ni.
Examples 9 to 20
The catalysts prepared in examples 1 to 8 were loaded in a fixed bed reactor and activated by reduction with hydrogen before hydrogenation, under the following reduction conditions: reducing for 8h at 2MPa (gauge pressure) and 270 ℃ by using hydrogen. Cooling to reaction temperature, reaction pressure of 1-2MPa (gauge pressure), continuously pumping in IP, adding a certain amount of ammonium oxalate ethanol solution into IP, ensuring that the addition amount of ammonium oxalate is a set value and the airspeed of IP is 0.2-1h -1 The reaction outlet material was analyzed with a hydrogen-to-oil ratio of 30. The reaction results are shown in table 1 below:
TABLE 1 EXAMPLES 9-20 reaction conditions and analysis of results
Comparative example 1
Comparative catalyst 1 was obtained as in example 3 except that no sodium carbonate was added. The loading of Ni is 15wt% of the carrier based on NiO.
Otherwise, as in example 9, the catalyst was changed to comparative catalyst 1, with an IP conversion of 99.9% and a TMC selectivity of 88.5%.
Comparative example 2
Otherwise, as in example 11, the reaction temperature was raised only to 130 ℃, the IP conversion was 99.9% and the TMC selectivity was 86.7%.
Claims (15)
1. A3,3,5-trimethyl cyclohexanone preparation method, in the presence of hydrogen and hydrogenation catalyst, isophorone selective hydrogenation reaction prepares 3,3,5-trimethyl cyclohexanone, its characteristic is: the hydrogenation catalyst is selected from modified supported nickel or modified supported cobalt, and the modifier is selected from at least one of sodium bicarbonate, sodium carbonate, potassium carbonate and potassium bicarbonate;
ammonium oxalate is added in the reaction system of the hydrogenation reaction as an auxiliary agent.
2. The method of claim 1, wherein: the hydrogenation catalyst is modified supported nickel.
3. The method of claim 1, wherein: the hydrogenation catalyst has carrier selected from at least one of alumina, silica, titania, magnesia and active carbon.
4. The method of claim 1, wherein: the hydrogenation catalyst has the active metal component accounting for 5-40wt% of the carrier.
5. The method of claim 4, wherein: the hydrogenation catalyst, wherein the amount of active metal component is 10-20% by weight of the carrier, calculated as its oxide.
6. The method of claim 1, wherein: the addition amount of the modifier of the hydrogenation catalyst is 1 to 20 percent relative to the molar weight of the active metal component calculated by alkali metal elements.
7. The method of claim 6, wherein: the addition amount of the modifier of the hydrogenation catalyst is 2-8% relative to the molar weight of the active metal component calculated by alkali metal elements.
8. The method of claim 1, wherein: the preparation method of the hydrogenation catalyst comprises the steps of dissolving soluble salt of nickel or cobalt and a modifier in water, then adding a carrier for impregnation, and then optionally carrying out molding, drying and roasting operations to obtain the modified supported nickel or modified supported cobalt catalyst.
9. The method of claim 1, wherein: the addition amount of the ammonium oxalate in the reaction system is 10-5000ppm.
10. The method of claim 9, wherein: the addition amount of the ammonium oxalate in the reaction system is 100-1000ppm.
11. The method of claim 1, wherein: the ammonium oxalate is water, methanol or ethanol solution of ammonium oxalate.
12. The method of claim 11, wherein: the concentration of the ammonium oxalate is 0.05-0.5wt% by adopting a water, methanol or ethanol solution of the ammonium oxalate.
13. The method of claim 1, wherein: the hydrogenation reaction pressure is 0.1-5MPa, the reaction temperature is 70-150 ℃, and the space velocity is 0.05-4h -1 。
14. The method of claim 13, wherein: the reaction pressure is 0.5-2MPa, the reaction temperature is 95-110 ℃, and the airspeed is 0.2-1h -1 。
15. The method of claim 1, wherein: the hydrogenation reaction is carried out in an intermittent or continuous mode, and the adopted hydrogenation reactor is selected from a reaction kettle, a fixed bed or a slurry bed.
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