CN116621682A - Preparation method of 4-oxo-isophorone - Google Patents
Preparation method of 4-oxo-isophorone Download PDFInfo
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- CN116621682A CN116621682A CN202310596450.0A CN202310596450A CN116621682A CN 116621682 A CN116621682 A CN 116621682A CN 202310596450 A CN202310596450 A CN 202310596450A CN 116621682 A CN116621682 A CN 116621682A
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- phase chamber
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- isophorone
- oxygen
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- AYJXHIDNNLJQDT-UHFFFAOYSA-N 2,6,6-Trimethyl-2-cyclohexene-1,4-dione Chemical compound CC1=CC(=O)CC(C)(C)C1=O AYJXHIDNNLJQDT-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000007789 gas Substances 0.000 claims abstract description 152
- 238000006243 chemical reaction Methods 0.000 claims abstract description 107
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 106
- 239000001301 oxygen Substances 0.000 claims abstract description 106
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 106
- 238000000034 method Methods 0.000 claims abstract description 77
- LKOKKQDYMZUSCG-UHFFFAOYSA-N 3,5,5-Trimethyl-3-cyclohexen-1-one Chemical compound CC1=CC(C)(C)CC(=O)C1 LKOKKQDYMZUSCG-UHFFFAOYSA-N 0.000 claims abstract description 54
- 230000008569 process Effects 0.000 claims abstract description 54
- 230000003197 catalytic effect Effects 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910001868 water Inorganic materials 0.000 claims abstract description 20
- 150000007530 organic bases Chemical class 0.000 claims abstract description 11
- 230000001590 oxidative effect Effects 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 4
- 230000003139 buffering effect Effects 0.000 claims abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 33
- 230000007246 mechanism Effects 0.000 claims description 18
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 17
- 238000010008 shearing Methods 0.000 claims description 17
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 9
- 150000001879 copper Chemical class 0.000 claims description 8
- 150000007522 mineralic acids Chemical class 0.000 claims description 8
- 150000007524 organic acids Chemical class 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims description 4
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 claims description 4
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 4
- PTVDYARBVCBHSL-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu] PTVDYARBVCBHSL-UHFFFAOYSA-N 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- 235000005985 organic acids Nutrition 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 17
- 230000003647 oxidation Effects 0.000 abstract description 10
- 239000012071 phase Substances 0.000 description 83
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 30
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 20
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- 238000002156 mixing Methods 0.000 description 11
- 230000001276 controlling effect Effects 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 150000002978 peroxides Chemical class 0.000 description 4
- 238000005273 aeration Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- -1 pyridine organic bases Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of 4-oxo-isophorone, which comprises the steps of preparing 4-oxo-isophorone by oxidizing beta-isophorone, and respectively providing a reaction phase chamber for accommodating a reaction system, a gas phase chamber for buffering mixed gas and communicated with the reaction phase chamber, and a connecting channel for connecting the lower part of the reaction phase chamber with the gas phase chamber, wherein the gas phase chamber, the connecting channel and the reaction phase chamber form a gas circulation channel; the reaction system comprises organic base, a catalytic system and beta-isophorone, the catalytic system comprises copper ions, acid and water, and the mixed gas comprises oxygen; in the oxidation process, the mixed gas enters a reaction system from the lower part of a reaction phase chamber through a connecting channel, part or all of oxygen participates in the reaction, gas which does not participate in the reaction returns to the gas phase chamber, and new oxygen is supplemented to the gas phase chamber to control the pressure of the gas phase chamber to be at a preset value; the invention has the advantages of no exhaust during the preparation process and simple operation on the basis of higher conversion rate and selectivity.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a preparation method of 4-oxo-isophorone.
Background
4-oxo isophorone (also called tea-ketone, called KIP for short) is an important chemical intermediate. The most commonly used preparation method at present is to take beta-isophorone as a raw material, oxidize the beta-isophorone by oxygen, mixed gas containing oxygen or hydrogen peroxide in the presence of a catalyst to generate 4-oxo-isophorone, and the reaction formula is as follows:
however, the following problems still remain in the above-mentioned processes:
1. when oxygen and a mixed gas containing oxygen are used for oxidation, for example, CN113429271A, CN1865210A, a large amount of oxygen or the mixed gas needs to be continuously introduced, so that a large amount of tail gas is generated, organic substances are easily carried out in the process of exhausting the tail gas, and equipment is corroded or the environment is polluted;
2. when hydrogen peroxide is used for oxidation, for example, CN111777497B, CN108440262B, on one hand, the hydrogen peroxide has obvious safety problems in terms of storage and transportation, and on the other hand, basically, a dropwise adding mode is adopted to add hydrogen peroxide aqueous solution (namely hydrogen peroxide), so that the phenomenon of overhigh local concentration is easy to generate, and the industrialized application is not facilitated;
3. the matched catalyst is not easy to obtain and has complex preparation, such as CN1100075894B, CN111269949B, CN108440262B and the like.
Disclosure of Invention
The invention aims to overcome one or more defects in the prior art and provide an improved preparation method of 4-oxo-isophorone with higher conversion rate and selectivity and without exhaust in the preparation process.
In order to achieve the above purpose, the invention adopts the following technical scheme: a process for the preparation of 4-oxoisophorone by oxidation of β -isophorone, wherein:
the method comprises the steps of respectively providing a reaction phase chamber for accommodating a reaction system, a gas phase chamber for buffering mixed gas and communicated with the reaction phase chamber, and a connecting channel for connecting the lower part of the reaction phase chamber with the gas phase chamber;
the reaction system comprises an organic base, a catalytic system and beta-isophorone, wherein the catalytic system comprises copper ions, acid and water;
the mixed gas contains oxygen; the content of oxygen in the mixed gas is 2-15% by volume percent;
in the process of oxidizing beta-isophorone, the mixed gas enters the reaction system from the lower part of the reaction phase chamber through the connecting channel, part or all of oxygen participates in the reaction, gas which does not participate in the reaction returns to the gas phase chamber, and new oxygen is supplemented to the gas phase chamber to control the pressure in the gas phase chamber to be at a pressure preset value.
In some embodiments of the invention, the gas mixture further comprises a blend gas, which may be nitrogen, argon, or the like.
In some embodiments of the invention, the gas phase chamber, the connecting channel and the reaction phase chamber constitute a gas circulation channel.
According to some preferred and specific aspects of the invention, the catalytic system is formed by dispersing copper salts, organic acids and/or inorganic acids in water.
According to some preferred aspects of the invention, the copper salt is a combination of one or more selected from copper acetate, copper nitrate, copper sulfate, copper chloride.
According to some preferred aspects of the invention, the organic acid and/or inorganic acid is one or a combination of more selected from acetic acid, sulfuric acid, hydrochloric acid, nitric acid.
According to a particular aspect of the invention, the catalytic system comprises copper acetate, acetic acid and water.
According to a particular aspect of the invention, the catalytic system comprises copper acetate, nitric acid and water.
According to a particular aspect of the invention, the catalytic system comprises copper acetate, hydrochloric acid and water.
According to a particular aspect of the invention, the catalytic system comprises copper sulphate, acetic acid and water.
According to some preferred aspects of the present invention, the copper salt is present in the catalytic system in an amount of 0.1% to 2.0% and the organic acid and/or inorganic acid is present in an amount of 10% to 50% by mass.
In some embodiments of the present invention, the copper salt may be included in the catalytic system in an amount of, but not limited to, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.8%, 1.0%, 1.2%, 1.4%, 1.5%, 1.6%, 1.8%, 2.0%, etc., by mass percent.
In some embodiments of the present invention, the content of the organic acid and/or inorganic acid in the catalytic system, in mass percent, includes, but is not limited to, may be 10%, 12%, 15%, 16%, 18%, 20%, 21%, 22%, 24%, 25%, 26%, 28%, 30%, 32%, 33%, 35%, 36%, 38%, 40%, 41%, 42%, 43%, 45%, 48%, 50%, etc.
In some embodiments of the present invention, the copper salt is present in the catalytic system in an amount of 0.4% to 1.2% and the organic and/or inorganic acid is present in an amount of 12% to 35% by mass.
According to some preferred aspects of the invention, the ratio of the catalytic system to the charged mass of beta-isophorone is 0.01-0.05:1.
According to some preferred aspects of the present invention, both ends of the connection passage are respectively communicated with a bottom of a lower portion of the reaction phase chamber, an upper portion of the gas phase chamber.
According to some preferred aspects of the invention, an oxygen inlet is arranged at the upper part of the gas-phase chamber, and the oxygen inlet and the connection part of the gas-phase chamber communicated with the connecting channel are respectively positioned at two opposite sides of the gas-phase chamber.
According to some preferred aspects of the invention, the process of oxidizing β -isophorone is achieved by means of a reaction vessel formed with a cavity, the reaction phase chamber, the gas phase chamber being integrally formed to form the cavity.
According to some preferred aspects of the present invention, there is provided a shearing mechanism partially disposed at the bottom of the interior of the reaction phase chamber, the center line of the shearing mechanism being coincident with the center line of the reaction phase chamber, an inlet port for introducing the mixture gas on the reaction phase chamber being opposed to the shearing mechanism. The device can ensure that the mixed gas can be dispersed strongly by the shearing mechanism along with the reaction system when entering the reaction system, can be thrown to all directions under the high-speed drive of the shearing mechanism and generate mutual collision dispersion, so as to achieve the aim of dispersing liquid flow and air flow together, and the aim of dispersing the oxygen in the liquid phase rapidly and uniformly is realized because the flow of the liquid flow of the reaction system is far greater than the flow of the oxygen in the mixed gas just introduced.
In some embodiments of the present invention, the shearing mechanism preferably adopts a mechanism with strong dispersing and mixing capability, for example, a stator-rotor shearing mechanism and the like.
According to some preferred aspects of the invention, a controller for controlling the flow of the mixed gas is arranged on the connecting channel, and the controller comprises, but is not limited to, a pressure fan, and the variable frequency motor of the pressure fan can control the gas quantity of the mixed gas in the gas phase chamber entering the reaction phase chamber through the connecting channel, so that the means for controlling the reaction speed is increased; when the volume of the reaction phase chamber is large, the air quantity can be adjusted to the most suitable state for reaction by adjusting the air quantity of the pressure fan. Of course, in other embodiments, other control components capable of actively regulating the flow of the mixture may be selected.
According to some preferred aspects of the invention, the pressure preset value is 100-3000Pa gauge pressure.
According to some preferred aspects of the invention, the organic base is a combination of one or more selected from pyridine, 2-picoline, 3-picoline, 4-picoline. The pyridine organic bases can provide a proper alkaline environment, and are beneficial to the reaction.
According to some preferred aspects of the invention, the feeding mass ratio of the organic base to the beta-isophorone is 0.5-2.5:1, so that the oxidation reaction is ensured to be suitable for alkaline environment, the concentration of the beta-isophorone can be reduced, and the quantity of beta-isophorone polymolecular binding byproducts is reduced.
According to some preferred aspects of the present invention, the reaction temperature is controlled to be 30-50 ℃ during the oxidation of beta-isophorone.
The invention is different from the prior art that oxygen or air is directly introduced into a reaction system, new oxygen is introduced into a gas phase chamber and residual gas (only a small amount of oxygen, even no oxygen, and other mixed gas such as nitrogen) in a space to obtain an 'lean oxygen' type mixed gas, the 'lean oxygen' type mixed gas enters the reaction system from the lower part of the reaction phase chamber through the connecting channel, and the residual gas of the 'lean oxygen' type mixed gas which consumes part or all of the oxygen is enriched into the gas phase chamber again, so that firstly, the purpose of lean oxygen oxidation can be achieved without supplementing the mixed gas such as nitrogen from the outside; secondly, without discharging the accumulated mixed gas, when the accumulated gas is discharged from the reaction system, part of substances are easily carried out of the reaction system, so that the reaction process becomes unstable; thirdly, the operation is convenient, and in the reaction process, a proper amount of oxygen is timely supplemented according to the pressure value change until the preset pressure value is reached, so that the reaction process is not needed to be interfered excessively.
According to the invention, practice shows that (1) in the presence of organic alkali, acid and copper ions, water and oxygen can form trace hydrogen peroxide (peroxide values can be detected by an instrument, in the experimental process, the pyridine, the copper acetate, the acetic acid and the water are added into a flask, the mixture is sampled after uniform stirring, and then the reaction flask is continuously filled with an oxygen-deficient mixed gas with the oxygen content of 15% for several hours, and then the peroxide values are detected together with a sample before aeration, so that the sample peroxide value before aeration is 0, the sample peroxide value after aeration can reach 0.17, the unit is the milligrams of 0.01mol/L sodium thiosulfate solution consumed by each gram of sample, and the hydrogen peroxide can oxidize beta-isophorone to prepare 4-oxo-isophorone, and then is converted into water, so that dynamic balance is formed, and the hydrogen peroxide is generated, and meanwhile, the water quantity in the system is basically stable; in addition, by means of the synchronous formation and consumption of the hydrogen peroxide, the defect that the concentration gradient is easily formed in the system to cause the increase of the selectivity of byproducts due to the formation and addition of hydrogen peroxide in single time, batch (such as dropwise addition) and the like in the prior art is avoided;
(2) The acid can be combined with organic base to form salt, which has obvious effect on controlling the alkalinity or nucleophilicity of the reaction system.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
the method solves the problem of generating a large amount of tail gas when oxidizing gas is introduced to oxidize beta-isophorone to prepare 4-oxo-isophorone in the prior art, simultaneously reduces system fluctuation caused by loss of substances in a reaction system along with the characteristic that the system basically does not need to discharge tail gas to the outside, so that the concentration of each substance directly or indirectly playing roles in catalytic oxidation and the like in the reaction process is basically stable, and the condition that the concentration gradient of each component in the reaction system is caused by the entry and the exit of the substances is avoided, thereby being beneficial to suppressing side reaction and improving the selectivity of target products; in addition, the method is simple to operate, the oxygen content of the reaction system can be always in a controllable range, and the safety is high.
Drawings
FIG. 1 is a schematic structural view of a reaction vessel employed in an embodiment of the present invention;
in the reference numerals, 1, a reaction phase chamber; 2. a gas phase chamber; 3. a connection channel; 4. an oxygen inlet pipe; 5. a shearing mechanism; 6. a beta-isophorone feed tube; 7. an organic base feed tube; 8. a catalytic system feed tube; 9. a jacket;
FIG. 2 is a gas chromatograph of the product obtained in example 1 of the present invention.
Detailed Description
As shown in fig. 1, the present invention can perform an oxidation reaction using the reaction vessel shown in fig. 1, which comprises a body having a cavity, a connecting channel 3, an oxygen inlet pipe 4, a shearing mechanism 5, a beta-isophorone inlet pipe 6, an organic base inlet pipe 7, a catalytic system inlet pipe 8, a jacket 9, a blending gas inlet pipe (not shown), a pressure fan (not shown), and an evacuation valve (not shown);
the material can fall into the reaction phase chamber 1 from the gas phase chamber 2 during feeding, an oxygen inlet is formed in the body and is communicated with an oxygen inlet pipe 4, and the connection parts of the oxygen inlet and the gas phase chamber 2 communicated with the connecting channel 3 are respectively positioned at two opposite sides of the gas phase chamber 2; the beta-isophorone feed pipe 6 and the organic base feed pipe 7 are respectively communicated with the upper part of the body, further, two ends of the connecting channel 3 are respectively communicated with the bottom of the lower part of the reaction phase chamber 2 and the upper part of the gas phase chamber 2, the connecting channel 3 and the reaction phase chamber 1 form a gas circulation channel, the connecting channel 3 and the catalytic system feed pipe 8 share a section of pipeline to be communicated with the body, and a pressure fan (not shown) is arranged on the connecting channel 3 to control the flow of the mixed gas; the mixing gas input pipe and the exhaust valve are respectively communicated with the upper part of the gas phase chamber 2, and the exhaust valve can be used for exhausting internal gas or exhausting gas to be replaced when the gas is replaced;
the shearing mechanism 5 is provided with a part extending into the reaction phase chamber 1, an air inlet for introducing mixed gas on the reaction phase chamber 1 is opposite to the part structure of the shearing mechanism 5, the part structure can enable the mixed gas to be dispersed strongly along with the reaction system when entering the reaction system, the mixed gas can be thrown to all directions under the high-speed driving of the shearing mechanism and mutually collided and dispersed, the purpose of rapidly and uniformly dispersing liquid flow and air flow together is achieved, and the purpose of rapidly and uniformly dispersing oxygen in the liquid phase is achieved because the flow amount of the liquid flow of the reaction system is far greater than the flow amount of oxygen in the mixed gas which is just introduced;
the jacket 9 is arranged outside the body and is used for controlling the temperature inside, for example, heating and cooling are respectively realized by introducing a heat source or a cold source.
When actually operated, the operation procedure is as follows: the method comprises the steps of preparing a catalytic system for standby, adding beta-isophorone and organic base into a reaction phase chamber of a reaction container, adding the prepared catalytic system, controlling the internal temperature of the reaction container to be a preset temperature (30-50 ℃) by introducing hot water into a jacket, starting a shearing mechanism, and setting the rotating speed (1000-2900 rpm);
when the reaction starts, adding blending gas such as nitrogen through a blending gas input pipe when the air existing in the gas phase chamber is not replaced, controlling the adding amount of the nitrogen and the air quantity of a pressure fan to control the pressure in the gas phase chamber to be a pressure preset value (gauge pressure 100-3000 Pa), enabling the pressure fan to drive mixed gas to circulate from a reaction system, enabling oxygen to be partially or completely consumed, enabling the rest gas to return to the gas phase chamber and be mixed with newly added nitrogen for recirculation, stopping adding the nitrogen and opening an oxygen inlet pipe when the oxygen concentration in the gas phase chamber is detected to be reduced to 2-15% by volume, continuing to enable the mixed gas to circulate from the reaction system through the pressure fan, and repeating the process, wherein the oxygen input value of the oxygen inlet pipe and the air quantity of the pressure fan are respectively controlled to control the pressure in the gas phase chamber to be the pressure preset value (gauge pressure 100-3000 Pa); or alternatively, the process may be performed,
(mode 2) when the reaction starts, air exists in the gas-phase chamber, part of air in the gas-phase chamber can be replaced through the mixed gas input pipe (the replaced part of air can be discharged through the exhaust valve, the exhaust valve can be closed after the replacement is finished) until the oxygen content is detected to be reduced to 2-15% by volume, the nitrogen is stopped to be introduced and the oxygen inlet pipe is opened, the pressure fan is started to enable the mixed gas in the gas-phase chamber to start flowing in the reaction system, the oxygen is partially or completely consumed, the rest gas returns to the gas-phase chamber and is mixed with the oxygen fed in from the oxygen inlet pipe, and the process is circulated, wherein the oxygen input value of the oxygen inlet pipe and the air quantity of the pressure fan are respectively controlled in the process to control the pressure in the gas-phase chamber to be a pressure preset value (gauge pressure is 100-3000 Pa); or alternatively, the process may be performed,
(mode 3) when the reaction starts, air exists in the gas-phase chamber, a mixed gas (the combination of oxygen and a mixing gas such as nitrogen, the volume percentage of the oxygen is 2% -15%) pipe is adopted to replace the air in the gas-phase chamber (the replaced air can be discharged through an exhaust valve, the exhaust valve can be closed after the replacement is finished), after the replacement is carried out for a plurality of times, the mixed gas is stopped, an oxygen inlet pipe is opened, a pressure fan is started to enable the mixed gas in the gas-phase chamber to start flowing in a reaction system, the oxygen is partially or completely consumed, the residual gas returns to the gas-phase chamber and is mixed with the oxygen fed in from the oxygen inlet pipe, the process is circulated, and in the process, the oxygen input value of the oxygen inlet pipe and the air volume of the pressure fan are respectively controlled to control the pressure in the gas-phase chamber to be a pressure preset value (gauge pressure is 100-3000 Pa);
controlling the oxidation time, transferring the oxidation reaction liquid into a recovery kettle after the oxidation reaction is finished, recovering the organic alkali under reduced pressure, and conveying concentrated solution of the recovery kettle into a wiped film evaporator for removing the weight to obtain the 4-oxo-isophorone after the weight is removed after the recovery of the organic alkali is finished.
In the implementation process of the invention, the total pressure is certain according to the Dalton partial pressure law and the Amagate division volume law, and the volume ratio is equal to the pressure ratio. Because the reaction does not consume the mixed gas such as nitrogen and the like, when the total pressure is unchanged, the amount of oxygen is supplemented by the amount of oxygen which is reacted, and the content of oxygen in the mixed gas can be controlled.
The above-described aspects are further described below in conjunction with specific embodiments; it should be understood that these embodiments are provided to illustrate the basic principles, main features and advantages of the present invention, and that the present invention is not limited by the scope of the following embodiments; the implementation conditions employed in the examples may be further adjusted according to specific requirements, and the implementation conditions not specified are generally those in routine experiments.
All starting materials are commercially available or prepared by methods conventional in the art, not specifically described in the examples below.
In each of the following examples 1 to 10, the operation was performed in the above-described manner 3: when the reaction starts, air exists in the gas phase chamber, a mixed gas (the combination of oxygen and a blending gas such as nitrogen, the volume percentage of the oxygen is 8%) pipe is adopted to replace the air in the gas phase chamber (the replaced air can be discharged through an exhaust valve, the exhaust valve can be closed after replacement is finished), after the replacement is carried out for a plurality of times, the mixed gas is stopped, an oxygen inlet pipe is opened, a pressure fan is started to enable the mixed gas in the gas phase chamber to start flowing in a reaction system, the oxygen is partially or completely consumed, the rest gas returns to the gas phase chamber and is mixed with the oxygen fed in from the oxygen inlet pipe, the process is circulated, and the oxygen input value of the oxygen inlet pipe and the air volume of the pressure fan are respectively controlled in the process so as to control the pressure in the gas phase chamber to be a pressure preset value (gauge pressure is 100-3000 Pa).
In example 11 below, the procedure described in mode 3 was followed: when the reaction starts, air exists in the gas phase chamber, a mixed gas (the combination of oxygen and a blending gas such as nitrogen, the volume percentage of the oxygen is 4%) pipe is adopted to replace the air in the gas phase chamber (the replaced air can be discharged through an exhaust valve, the exhaust valve can be closed after replacement is finished), after the replacement is carried out for a plurality of times, the mixed gas is stopped, an oxygen inlet pipe is opened, a pressure fan is started to enable the mixed gas in the gas phase chamber to start flowing in a reaction system, the oxygen is partially or completely consumed, the rest gas returns to the gas phase chamber and is mixed with the oxygen fed in from the oxygen inlet pipe, the process is circulated, and the oxygen input value of the oxygen inlet pipe and the air volume of the pressure fan are respectively controlled in the process so as to control the pressure in the gas phase chamber to be a pressure preset value (gauge pressure is 100-3000 Pa).
In example 12 below, the procedure described in mode 3 was followed: when the reaction starts, air exists in the gas phase chamber, a mixed gas (the combination of oxygen and a blending gas such as nitrogen, the volume percentage of the oxygen is 12%) pipe is adopted to replace the air in the gas phase chamber (the replaced air can be discharged through an exhaust valve, the exhaust valve can be closed after replacement is finished), after the replacement is carried out for a plurality of times, the mixed gas is stopped, an oxygen inlet pipe is opened, a pressure fan is started to enable the mixed gas in the gas phase chamber to start flowing in a reaction system, the oxygen is partially or completely consumed, the rest gas returns to the gas phase chamber and is mixed with the oxygen fed in from the oxygen inlet pipe, the process is circulated, and the oxygen input value of the oxygen inlet pipe and the air volume of the pressure fan are respectively controlled in the process so as to control the pressure in the gas phase chamber to be a pressure preset value (gauge pressure is 100-3000 Pa).
Example 1
The present example provides a process for the preparation of 4-oxoisophorone using the reaction vessel and the process described above in FIG. 1, wherein:
catalytic system configuration: copper acetate was charged into a 5L three-necked flask with thermometer and stirrer: 0.012kg, deionized water: 1.0kg, acetic acid: 0.45kg, stirring and dissolving, and keeping for later use.
The reaction vessel: 500L, add beta-isophorone: 85.0kg (content: 98.9 wt%), pyridine: 100kg, hot water is introduced into the jacket of the reaction vessel to control the internal temperature at 45 ℃, and the rotating speed of the shearing mechanism is controlled: 1450r/min; controlling the pressure in the gas phase chamber to be 2000Pa, and continuing the oxidation reaction for 30 hours;
after the oxidation reaction is completed, transferring the oxidation reaction liquid into a recovery kettle, and recovering pyridine under reduced pressure. And after pyridine is recovered, conveying the concentrated solution of the recovery kettle into a wiped film evaporator for weight removal.
After the weight is removed, 4-oxo isophorone is obtained: 90.7kg (4-oxoisophorone content: 97.1% by weight), yield: 95.1 percent and the gas chromatographic spectrum is shown in figure 2.
Example 2
The procedure and process parameters of example 2 were substantially the same as in example 1 except that pyridine was charged into a 500L reaction vessel: 42.5kg.
After the weight is removed, 4-oxo isophorone is obtained: 90.1kg (4-oxoisophorone content: 96.9% by weight), yield: 94.3%.
Example 3
The procedure and process parameters of example 3 were substantially the same as in example 1 except that pyridine was charged into a 500L reaction vessel: 212.5kg.
After the weight is removed, 4-oxo isophorone is obtained: 91.8kg (4-oxoisophorone content: 97.5 wt.%) yield: 96.7%.
Example 4
The procedure and process parameters of example 4 were substantially identical to those of example 1, except that copper acetate was charged into a 5L three-necked flask with thermometer and stirrer during the preparation of the catalytic system: 0.007kg of deionized water: 0.58kg, acetic acid: 0.26kg, and stirring to dissolve.
After the weight is removed, 4-oxo isophorone is obtained: 92.2kg (4-oxoisophorone content: 97.6 wt.%) yield: 97.2%.
Example 5
The procedure and process parameters of example 5 were substantially identical to those of example 1, except that copper acetate was charged into a 5L three-necked flask with thermometer and stirrer during the preparation of the catalytic system: 0.035kg of deionized water: 2.9kg, acetic acid: 1.30kg, and stirring to dissolve.
After the weight is removed, 4-oxo isophorone is obtained: 89.4kg (4-oxoisophorone content: 97.1 wt%), yield: 93.8%.
Example 6
The procedure and process parameters of example 6 were substantially the same as in example 1 except that the internal temperature of the oxidation vessel was controlled at 30℃by introducing cooling water into the jacket of the reaction vessel.
After the weight is removed, 4-oxo isophorone is obtained: 92.3kg (4-oxoisophorone content: 97.6 wt.%) yield: 97.3%.
Example 7
The procedure and process parameters of example 7 were substantially the same as in example 1 except that the internal temperature of the oxidation vessel was controlled at 50℃by introducing hot water into the jacket of the reaction vessel.
After the weight is removed, 4-oxo isophorone is obtained: 90.3kg (4-oxoisophorone content: 96.7% by weight), yield: 94.3%.
Example 8
The procedure and process parameters of example 8 were substantially identical to those of example 1, except that copper acetate was charged into a 5L three-necked flask with thermometer and stirrer during the preparation of the catalytic system: 0.012kg, deionized water: 1.0kg of nitric acid aqueous solution 0.45kg, content: 67.5wt% and dissolved with stirring.
After the weight is removed, 4-oxo isophorone is obtained: 89.3kg (4-oxoisophorone content: 96.8 wt.%) yield: 93.4%.
Example 9
The procedure and process parameters of example 9 were substantially the same as in example 1 except that copper acetate was charged into a 5L three-necked flask with thermometer and stirrer during the preparation of the catalytic system: 0.012kg, deionized water: 1.0kg of hydrochloric acid (aqueous hydrogen chloride): 0.45kg, content: 35.6wt% and dissolved with stirring.
After the weight is removed, 4-oxo isophorone is obtained: 89.2kg (4-oxoisophorone content: 96.9 wt.%) yield: 93.4%.
Example 10
The procedure and process parameters of example 10 were substantially the same as in example 1 except that copper sulfate was charged into a 5L three-necked flask with thermometer and stirrer during the preparation of the catalytic system: 0.012kg, deionized water: 1.0kg, acetic acid: 0.45kg, and stirring to dissolve.
After the weight is removed, 4-oxo isophorone is obtained: 89.0kg (4-oxoisophorone content: 97.3 wt%), yield: 93.5%.
Example 11
The procedure and process parameters of example 11 were substantially identical to those of example 1, except that the procedure was carried out in the manner described above in 3: when the reaction starts, air exists in the gas-phase chamber, a mixed gas (the combination of oxygen and a mixing gas such as nitrogen, the volume percentage of the oxygen is 4%) pipe is adopted to replace the air in the gas-phase chamber (the replaced air can be discharged through an exhaust valve, the exhaust valve can be closed after the replacement is finished), after the replacement is carried out for a plurality of times, the mixed gas is stopped, an oxygen inlet pipe is opened, a pressure fan is started to enable the mixed gas in the gas-phase chamber to start flowing in a reaction system, the oxygen is partially or completely consumed, the rest gas returns to the gas-phase chamber and is mixed with the oxygen fed in from the oxygen inlet pipe, the process is circulated, and the oxygen input value of the oxygen inlet pipe and the air volume of the pressure fan are respectively controlled in the process so as to control the pressure in the gas-phase chamber to be a pressure preset value (gauge pressure 1500 Pa).
After the weight is removed, 4-oxo isophorone is obtained: 90.8kg (4-oxoisophorone content: 97.1% by weight), yield: 95.2%.
Example 12
The procedure and process parameters of example 12 were substantially identical to those of example 1, except that the procedure was carried out in the manner described above in 3: when the reaction starts, air exists in the gas-phase chamber, a mixed gas (the combination of oxygen and a mixing gas such as nitrogen, the volume percentage of the oxygen is 12%) pipe is adopted to replace the air in the gas-phase chamber (the replaced air can be discharged through an exhaust valve, the exhaust valve can be closed after the replacement is finished), after the replacement is carried out for a plurality of times, the mixed gas is stopped, an oxygen inlet pipe is opened, a pressure fan is started to enable the mixed gas in the gas-phase chamber to start flowing in a reaction system, the oxygen is partially or completely consumed, the rest gas returns to the gas-phase chamber and is mixed with the oxygen fed in from the oxygen inlet pipe, the process is circulated, and the oxygen input value of the oxygen inlet pipe and the air volume of the pressure fan are respectively controlled in the process so as to control the pressure in the gas-phase chamber to be a pressure preset value (gauge pressure 1500 Pa).
After the weight is removed, 4-oxo isophorone is obtained: 89.8kg (4-oxoisophorone content: 97.0 wt%), yield: 94.1%.
Comparative example 1
The process and process parameters of comparative example 1 were substantially identical to those of example 1, except that air was continuously introduced from the bottom of the reaction phase chamber and the remaining unreacted air was discharged from the evacuation valve of the gas phase chamber.
After the weight is removed, 4-oxo isophorone is obtained: 83.9kg (4-oxoisophorone content: 96.6% by weight), yield: 87.5%.
Comparative example 2
The procedure and process parameters of comparative example 2 were substantially identical to those of example 1, except that copper acetate was charged into a 5L three-necked flask with thermometer and stirrer during the preparation of the catalytic system: 0.012kg, deionized water: 1.0kg, and stirring to dissolve.
After the weight is removed, 4-oxo isophorone is obtained: 85.3kg (4-oxoisophorone content: 96.8 wt.%) yield: 89.2%.
The above embodiments are provided to illustrate the technical concept and features of the present invention and are intended to enable those skilled in the art to understand the content of the present invention and implement the same, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
Claims (10)
1. A process for producing 4-oxoisophorone by oxidizing β -isophorone, characterized in that:
the method comprises the steps of respectively providing a reaction phase chamber for accommodating a reaction system, a gas phase chamber for buffering mixed gas and communicated with the reaction phase chamber, and a connecting channel for connecting the lower part of the reaction phase chamber with the gas phase chamber;
the reaction system comprises an organic base, a catalytic system and beta-isophorone, wherein the catalytic system comprises copper ions, acid and water;
the mixed gas contains oxygen; the content of oxygen in the mixed gas is 2-15% by volume percent;
in the process of oxidizing beta-isophorone, the mixed gas enters the reaction system from the lower part of the reaction phase chamber through the connecting channel, part or all of oxygen participates in the reaction, gas which does not participate in the reaction returns to the gas phase chamber, and new oxygen is supplemented to the gas phase chamber to control the pressure in the gas phase chamber to be at a pressure preset value.
2. The process for the preparation of 4-oxoisophorone according to claim 1, wherein: the catalytic system is formed by dispersing copper salts, organic acids and/or inorganic acids in water.
3. The process for the preparation of 4-oxoisophorone according to claim 2, wherein: the copper salt is one or a combination of more selected from copper acetate, copper nitrate, copper sulfate and copper chloride; and/or the organic acid and/or the inorganic acid is one or a combination of more selected from acetic acid, sulfuric acid, hydrochloric acid and nitric acid.
4. A process for the preparation of 4-oxo-isophorone according to claim 3, wherein: the catalytic system comprises copper acetate, acetic acid and water; or, the catalytic system comprises copper acetate, nitric acid and water; or, the catalytic system comprises copper acetate, hydrochloric acid and water; alternatively, the catalytic system comprises copper sulfate, acetic acid, and water.
5. The process for the preparation of 4-oxoisophorone according to any one of claims 2 to 4, wherein: the content of the copper salt in the catalytic system is 0.1-2.0% and the content of the organic acid and/or the inorganic acid is 10-50% by mass percent.
6. The process for the preparation of 4-oxoisophorone according to any one of claims 1 to 4, wherein: the mass ratio of the catalytic system to the beta-isophorone is 0.01-0.05:1.
7. The process for the preparation of 4-oxoisophorone according to claim 1, wherein: two ends of the connecting channel are respectively communicated with the bottom of the lower part of the reaction phase chamber and the upper part of the gas phase chamber;
and/or the upper part of the gas phase chamber is provided with an oxygen inlet, and the oxygen inlet and the connection part of the gas phase chamber communicated with the connecting channel are respectively positioned at two opposite sides of the gas phase chamber;
and/or the process of oxidizing the beta-isophorone is realized by means of a reaction vessel with a cavity, and the reaction phase cavity and the gas phase cavity are integrally formed to form the cavity.
8. The process for the preparation of 4-oxoisophorone according to claim 1, wherein: providing a shearing mechanism partially arranged at the bottom of the inside of the reaction phase chamber, wherein the central line of the shearing mechanism is overlapped with the central line of the reaction phase chamber, and an air inlet for introducing the mixed gas on the reaction phase chamber is opposite to the shearing mechanism; and/or a controller for controlling the flow of the mixed gas is arranged on the connecting channel, and the controller comprises a pressure fan.
9. The process for the preparation of 4-oxoisophorone according to claim 1, wherein: the preset pressure value is 100-3000Pa; and/or, in the process of oxidizing beta-isophorone, controlling the reaction temperature to be 30-50 ℃.
10. The process for the preparation of 4-oxoisophorone according to claim 1, wherein: the organic base is one or a combination of more selected from pyridine, 2-picoline, 3-picoline and 4-picoline; and/or the feeding mass ratio of the organic alkali to the beta-isophorone is 0.5-2.5:1.
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