CN109438199A - A kind of method that continuous high-efficient oxidation prepares 2,6,6- trimethyl -2- cyclohexene -1,4- diketone - Google Patents
A kind of method that continuous high-efficient oxidation prepares 2,6,6- trimethyl -2- cyclohexene -1,4- diketone Download PDFInfo
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- 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
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- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
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Abstract
The invention discloses a kind of continuous high-efficients to aoxidize preparation 2,6,6- trimethyl -2- cyclohexene-Isosorbide-5-Nitrae-diketone method, comprising: (1) reacts material liquid in a manner of spraying mixing with oxygen-containing gas, obtain reaction solution；(2) reaction solution is subjected to gas-liquid separation, then adjusts the temperature of liquid phase, then reacted to obtain reaction solution in a manner of spraying mixing with oxygen-containing gas；Oxygen-containing gas in step (2) is the obtained gas phase of gas-liquid separation or the gas newly prepared；(3) process of step (2) is repeated to fully reacting, obtains 2,6,6- trimethyl -2- cyclohexene-Isosorbide-5-Nitrae-diketone product liquid.The material liquid includes catalyst, reaction raw materials and solvent.The present invention is sprayed by gas-liquid mixed, so that reaction solution and gas and catalyst mixed effect are significantly better than mechanically stirred reactor, bubble disperses more evenly, and contact is more abundant, reaches ideal mass transfer effect, improves reaction speed.
Description
Technical field
The present invention relates to 2,6,6- trimethyl -2- cyclohexene-Isosorbide-5-Nitrae-diketone synthesis fields, and in particular to a kind of continuous oxygen
Change the method that 3,5,5- trimethyl -3- cyclohexene -1- ketone prepares 2,6,6- trimethyl -2- cyclohexene -1,4- diketone.
Background technique
2,6,6- trimethyl -2- cyclohexene-Isosorbide-5-Nitrae-diketone is a kind of important chemical and medicine industry intermediate, can be used as food additive
Add the flavoring agent or fragrance in agent, it can also be used to synthesize cosmetics, 2,6,6- trimethyl -2- cyclohexene-Isosorbide-5-Nitrae-diketone is still made
The important intermediate of standby vitamin and carotenoid.
Due to 2,6,6- trimethyl -2- cyclohexene-importance of the Isosorbide-5-Nitrae-diketone in the fields such as chemical and medicine industry, for a long time with
Come, by 3,5,5- trimethyl -2- cyclohexene -1- ketone or 3,5,5- trimethyl -3- cyclohexene -1- oxidation of ketones are at 2,6,6- front threes
Base -2- cyclohexene-Isosorbide-5-Nitrae-diketone is always a hot spot of chemical field research, especially for 3,5,5- trimethyls -
The oxidation of 3- cyclohexene -1- ketone, at present it has been reported that patent and document it is very much.Generally speaking, at present to 3,5,5- trimethyls-
On the document and patent of 3- cyclohexene -1- oxidation of ketones all concentrate on solvent or screening of catalyst mostly or improve.Such as:
Described in US4046813, CN1923782 and US4970347 in the presence of an organic base, using lead, vanadium, chromium,
The acetyl acetone complex of manganese, iron, cobalt etc. or its ionic liquid composites are catalyst, catalysis oxidation 3,5,5- trimethyl-
3- cyclohexene -1- ketone prepares 2,6,6- trimethyl -2- cyclohexene-Isosorbide-5-Nitrae-diketone method, same although this method high conversion rate
When be also easy to make 3,5,5- trimethyl -3- cyclohexene -1- ketone that isomerization occurs to 3,5,5- trimethyl -2- cyclohexene -1- ketone, and
The by-product that height easy to form gathers again in reaction, so that reaction selectivity declines.
In US6297404, US6300521, CN1865210, CN100999453, US6166261 and CN 1281844,
It describes in the presence of the organic bases such as DMF or DMA and tripropyl amine (TPA), uses 3,5,5- front three of different type schiff bases catalysis oxidation
Base -3- cyclohexene -1- ketone prepares 2,6,6- trimethyl -2- cyclohexene-Isosorbide-5-Nitrae-diketone method, one maximum disadvantage of this method
It is that reaction is easy to produce 3,5,5- trimethyl-cyclohex-2-en -4- hydroxyl -1- ketone, 2,2,6- trimethyl-cyclohexanes-Isosorbide-5-Nitrae-diketone
Equal by-products, since the various aspects such as these byproduct molecules amounts and property are similar to product, and 2,6,6- trimethyl -2- rings
The separation of hexene -1,4- diketone is extremely difficult.
In US4898985, one kind is described in the presence of triethylamine and glycol dimethyl ether, uses iron, cobalt, ketone, manganese
Porphyrin or phthalocyanine complex be catalyst, catalysis oxidation 3,5,5- trimethyl -3- cyclohexene -1- ketone prepare 2,6,6- front threes
Base -2- cyclohexene-Isosorbide-5-Nitrae-diketone method, although this method has very high yield, the transition-metal catalyst of porphyrin
It is fairly expensive, and be also easy to be corrupted such that the high process cost in the reaction.Furthermore glycol dimethyl ether combines triethylamine
The alkaline environment of formation is abnormally dangerous in oxidation operation, because the burning point of the mixture is very low, for security reasons, to the greatest extent
Pipe this method has very high yield, can must just implement at industrial scale under very safe precautionary measures.
In CN102329202 and CN1271031, CN101417935B, describe with n-Hydroxyphthalimide
And metal salt, or [CnMin] [X] ionic liquid and transition metal halide composition binary catalyst system, be catalyzed oxygen
Change the method that 3,5,5- trimethyl -2- cyclohexene -1- ketone obtains highly selective 2,6,6- trimethyl -2- cyclohexene -1,4- diketone.
The reaction carries out in ventilatory response kettle.This method synthetic route is simple, and reaction condition is mild, and reaction conversion ratio, selectivity are high.
But catalyst post-processing has difficulties after the reaction was completed.
In CN101182288, the transition gold with the modified active porous inorganic carrier support of nitrogenous compound is described
Category salt is catalyst, aoxidizes 3,5,5- trimethyl -3- cyclohexene -1- ketogenesis, 2,6,6- trimethyl -2- cyclohexene-Isosorbide-5-Nitrae-diketone
Method.This method reaction condition is mild, and catalyst can be easily separated and control, and two cluster by-products are less.In CN1923783
In, it describes using immobilized transition metal salt as catalyst, heterocatalysis oxidation generates 2,6,6- trimethyls-at -30-150 DEG C
The method of 2- cyclohexene -1,4- diketone.This method is greatly improved compared to general different-phase catalyst reactivity and selectivity, phase
Than in homogeneous catalyst, reaction condition is mild, two cluster by-products are few, and catalyst is easily isolated and controls, and is conducive to catalyst
It recycles.But heterogeneous catalysis is used, reaction efficiency and selectivity are all not so good as homogeneous catalytic oxidation.
In US6410797, a kind of production 2,6,6- trimethyl -2- cyclohexene-Isosorbide-5-Nitrae-diketone and its derivative are described
Method and one kind be stirred to react kettle device.This method is in having solvent existing for organic carboxyl acid, with N, bis- salicylidene two of N'-
The transient metal complex of amine is catalyst, and cyclic base is co-catalyst, catalysis oxidation 3,5,5- trimethyl -3- cyclohexene -1-
Ketogenesis 2,6,6- trimethyl -2- cyclohexene -1,4- diketone.The process units is comprising being stirred to react unit and isolating and purifying list
Member.In US6346651, a kind of 2,6,6- trimethyl -2- cyclohexene-Isosorbide-5-Nitrae-diketone production process and device is described.It should
Process units includes 3,5,5- trimethyl -2- cyclohexene -1- ketone isomerization reaction units, 3,5,5- trimethyl -3- cyclohexene -1- ketone
Oxidation reaction unit, low boiling impurity/solvent rectification cell, high boiling compound rectification cell and 2,6,6- trimethyl -2- cyclohexene -
1,4- diketone rectification cell.Oxidation reaction unit uses mechanic whirl-nett reaction kettle.The technique joins isomerization reaction and oxidation reaction
It is combined, there is high conversion ratio and selectivity, and the device avoids the poisoning and deactivations of oxidation catalyst.
From the point of view of the case where above-mentioned patent is summarized, these patents are mainly to 3,5,5- trimethyl -2- cyclohexene -1- ketone oxygen
The improvement and optimization that the catalyst or solvent (auxiliary agent) for changing reaction carry out, but reaction is substantially in mechanic whirl-nett reaction kettle
It carries out.By the study found that for 2,6,6- trimethyl -3- cyclohexene-Isosorbide-5-Nitrae-diketone oxidation reaction, in addition to catalyst and
The factor of auxiliary agent, mass transfer and heat transfer also have extremely important influence to reaction.And it is deposited using traditional mechanic whirl-nett reaction kettle
Low whipping speed is unhappy, has certain limitation to the gas-liquid mixed degree in reactor, mass transfer effect is general；Simultaneously for tradition
Belt stirrer reaction kettle, internal heat transfer surface area is limited, and not prompt enough to the removal of oxidation reaction heat, this is side reaction
The major reason of generation；Moreover exist to sealing performance and centainly restrict comprising agitation part in stirred autoclave, it is anti-to be not suitable for high pressure
It answers；It is long there is also the reaction time in actual production, there is the problems such as tail gas formation and solvent entrainment loss.
It opens (Zhejiang chemical industry, 2014,5,17-19) such as qins and has studied 3,5,5- trimethyl -3- cyclohexene -1- of isomer
The oxidation reaction of ketone is studied catalyst amount, temperature and oxygen content etc., instead by the way of spraying oxidation reaction
Should have good mass transfer and heat-transfer effect, but because yield is lower than 80%, 2,6,6- trimethyl -2- are synthesized using the method
Industrialized requirement is not achieved in cyclohexene -1,4- diketone.
Summary of the invention
For above-mentioned 2,6,6- trimethyl -2- cyclohexene of oxidative synthesis-Isosorbide-5-Nitrae-diketone there are the problem of, the present invention provides
A kind of new method of continuous high-efficient oxidation production 2,6,6- trimethyl -2- cyclohexene -1,4- diketone.
Technical scheme is as follows:
A kind of continuous high-efficient preparation 2,6,6- trimethyl -2- cyclohexene-Isosorbide-5-Nitrae-diketone method, comprising:
(1) material liquid is reacted in a manner of spraying mixing with oxygen-containing gas, obtains reaction solution；
(2) reaction solution is subjected to gas-liquid separation, then adjusts the temperature of liquid phase, then with oxygen-containing gas to spray the side mixed
Formula is reacted to obtain reaction solution；
Oxygen-containing gas in step (2) is the obtained gas phase of gas-liquid separation or the gas newly prepared；
(3) process of step (2) is repeated to fully reacting, obtains 2,6,6- trimethyl -2- cyclohexene-Isosorbide-5-Nitrae-diketone products
Liquid；
The material liquid includes catalyst, reaction raw materials (3,5,5- trimethyl -2- cyclohexene -1- ketone) and solvent.
For the oxidation of 3,5,5- trimethyl -2- cyclohexene -1- ketone, find this reaction be it is mass transfer limited, how to improve
Mass transfer effect is one of the key point of reaction.The present invention is by gas-liquid mixed spray regime, so that reaction solution and gas and urging
Agent mixed effect is significantly better than mechanically stirred reactor, and bubble disperses more evenly, and contact is more abundant, reaches ideal mass transfer effect
Fruit, from the point of view of reaction process, reaction speed is obviously improved.
Preferably, injection is blended in the injection reactor of two-stage series connection and carries out, reaction in the first stage reactor of control
When condition and residence time to conversion ratio reach 85%-90%, it is transferred to the second stage reactor and is reacted；
Control reaction condition and residence time to conversion ratio in the second stage reactor and reach 99.5% or more, judgement react into
Row is complete.
Preferably, reaction carries out under conditions of continuous steady state operation；
Gas-liquid separation, gas are carried out after the feed inlet continuous supplementation material liquid and oxygen-containing gas of the first stage reactor, reaction
The feed inlet for mutually returning to the first stage reactor is recycled, and liquid phase a part returns to the charging of the first stage reactor after cooling
Mouth circulation enters the feed inlet of second level reactor after another part cooling；
In the second level, the feed inlet of reaction solution supplements oxygen-containing gas, and gas-liquid separation is carried out after reaction, and gas phase returns to the second level
The feed inlet of reactor is recycled, and liquid phase a part returns to the feed inlet circulation of the second stage reactor after cooling, another
Part is continuously exported as product liquid.
Preferably, reaction solution residence time in first set reactor is 5-6h；When being stopped in second set of reactor
Between be 3-4h.
Preferably, the reactor injector outlet liquid stream speed is 5-15m/s, preferably 8-12m/s.
Since 3,5,5- trimethyl -2- cyclohexene -1- reactive ketone sites are more, and oxidation process is exothermic reaction, so
Oxygen content and control reaction speed are controlled in reaction, it is ensured that reaction activation process matches with oxygen molecule cohesive process reacts
The key that yield is promoted.The inventors discovered that reaction speed is too fast, it is the main reason for by-product generates that it is relatively low, which to activate oxygen concentration,
Control reaction temperature and oxygen pressure are affected to reaction.
Preferably, carrying out cooling processing, cooling extent 10- to the liquid phase isolated using external tubular heat exchanger
30 DEG C, preferably 15-20 DEG C；Liquidus temperature after cooling is 25~50 DEG C, preferably 30~45 DEG C.
Preferably, cooling jacket is arranged in the surface of injection reactor, at this point, external heat exchanger is added by collet, so that
The hot fast transfer that oxidation reaction generates, guarantees that reaction temperature is precisely controlled, reduces the generation of side reaction.
Preferably, being equipped with oxygen content tester in injection reactor；
Oxygen content (oxygen content herein refers to volume content) in injection reactor is 3-16%, preferably 6-
12%.
Preferably, the reaction is compressive reaction, reactor pressure 0.3-1.5MPa, preferably 0.6-1.2MPa.
Preferably, the catalyst is metal complex, wherein metal cation is iron, in cobalt, nickel, copper, zinc, manganese
One or two, ligand are one of acetylacetone,2,4-pentanedione, schiff bases, porphyrin；
The solvent is ethylenediamine, triethylamine, tripropyl amine (TPA), one or both of pyridine.
Preferably, liquid holdup is 30-80%, preferably 40%-60% in reactor.
Compared with the existing technology, the beneficial effects of the present invention are embodied in:
(1) present invention is using injection circulation reactive mode, and gas-liquid mass transfer efficiency is substantially compared to traditional stirring reactor
Degree is promoted, and the reaction time is greatly reduced, and reaction efficiency is obviously improved.
(2) present invention adds external exothermic mode that can be accurately controlled reacting liquid temperature using collet, while by adding
Pressure promotes oxygen concentration, it is ensured that the matching of reaction temperature and concentration can limit the generation of side reaction, be conducive to improve reaction choosing
Selecting property.
(3) big for velocity contrast under the different concentration of substrate of this reaction, the present invention passes through two sets of injection circulation reactor strings
Connection controls reaction condition different in two reactors in conjunction with different reactivenesses, compared to 2,6,6- trimethyl -2- hexamethylenes
Alkene-Isosorbide-5-Nitrae-diketone synthesis realizes successive reaction using other reactor types.Overall reaction shorter residence time was by 10 hours
Within, reaction conversion ratio reaches 99.5% or more, and reaction selectivity reaches 96% or more, significantly improves reaction efficiency and receipts
Rate, and by being recycled inside oxygen, the mode of external complement realizes tail gas zero-emission, is environmentally protective technique, has
The prospect of industrial applications.
Detailed description of the invention
Fig. 1 is of the invention 2,6,6- trimethyl -2- cyclohexene-Isosorbide-5-Nitrae-diketone reaction unit schematic diagram, in figure: 1: spray
Penetrate reactor, 2: circulating pump, 3: heat exchanger, 4: thermometer, 5: injector, 6: gas circulating tube, 7: oxygen content instrument, 8: pressure
Table, 9:Y type filter, the valve of V-1~21 (different type), I-1~2: flowmeter.
Specific embodiment
Reaction unit schematic diagram as shown in Figure 1 is it is found that reaction unit of the invention includes two sets and is connected in a series arrangement
The injection circulation reactor system connect.Each injection circulation reactor system includes sequentially connected injection reactor 1, circulating pump
2 and tubular heat exchanger 3, reaction solution can be circulated in injection circulation reactor internal system, can also by first spray
It penetrates circulation flow reactor system and is flowed into second injection circulation reactor system, specifically controlled by corresponding valve.
Injection reactor includes feed inlet, the injector being connected with feed inlet 5 and discharge port.Feed inlet is by reactant
Material is passed through injector, and reaction mass includes the reaction solution and circulation of fresh material liquid, fresh oxygen-containing gas and circulation
Oxygen-containing gas, fresh material liquid are made of reaction raw materials, catalysts and solvents；Fresh oxygen-containing gas is mixed by oxygen and nitrogen
It closes, specific ratio is configured as needed.Reaction mass is ejected into inside reactor by injector, is sent out in course of injection
Raw reaction, into injection reactor inside after material occur gas-liquid separation, liquid is from lower part discharge port output.The output liquid according to
The difference of the extent of reaction, the reaction solution that can be used as circulation is reacted back to the same level injection reactor, or is output to down
Level-one injection reactor discharges as product liquid.
The liquid for needing to carry out circular response can be carried out primary cooling operation by circulating pump and tubular heat exchanger, to keep away
Exempt from the generation of side reaction caused by high temperature, cooling extent is generally 10~30 DEG C, is equipped with temperature in the exit of tubular heat exchanger
Degree meter 4.
Meanwhile on injection reactor top, there are also gas circulating tubes 6, connect upper space and the charging of injection reactor
Mouthful, the oxygen-containing gas (from gas-liquid separation) of upper space is delivered to feed inlet again and is reacted, is recycled in the gas
Oxygen content instrument 7 is provided on pipe, for monitor recycled oxygen-containing gas oxygen content.
In order to further control the temperature of reaction, injection reactor is equipped with cooling jacket, for being passed through cooling water；Meanwhile
In order to monitor the pressure of reactor, pressure gauge is equipped on injection reactor.
The present invention will be further described combined with specific embodiments below.
Embodiment 1:
According to signal workflow graph, under conditions of continuous steady state operation, catalyst (ferric acetyl acetonade) will be contained, solvent
The mixed liquor (mass ratio 0.02:2:1) of (triethylamine) and reaction raw materials (3,5,5- trimethyl -3- cyclohexene -1- ketone) enters
Two kettle tandem reaction systems, control condition and residence time react until completing, and oxidation liquid is continuously arranged from discharge port
Out, sampling is detected.Wherein specific response parameter is as follows:
Reactor 1: oxygen content: 8%；Pressure: 0.5MPA；Fluid temperature in reactor: 45 DEG C；Pump discharge temperature: 30 DEG C；
Flow rate pump: 1m/s (being equivalent to jet velocity is 10m/s)；Residence time: 5h.
Reactor 2: oxygen content 6%, pressure are as follows: 0.4MPA, liquid reactor temperature: 60 DEG C；Pump discharge temperature: 45
℃；Flow rate pump are as follows: 1.2m/s (being equivalent to jet velocity is 12m/s) residence time: 4h.
Testing result: 1 conversion ratio of kettle: 86.5%；Selectivity: 97.3%；
2 conversion ratio of kettle: 99.8%；Selectivity: 96.4%
Claims (10)
1. a kind of continuous high-efficient oxidation preparation 2,6,6- trimethyl -2- cyclohexene-Isosorbide-5-Nitrae-diketone method, which is characterized in that packet
It includes:
(1) material liquid is reacted in a manner of spraying mixing with oxygen-containing gas, obtains reaction solution；
(2) reaction solution is subjected to gas-liquid separation, then adjust liquid phase temperature, then with oxygen-containing gas in a manner of spraying and mix into
Row reaction obtains reaction solution；
Oxygen-containing gas in step (2) is the obtained gas phase of gas-liquid separation or the gas newly prepared；
(3) process of step (2) is repeated to fully reacting, obtains 2,6,6- trimethyl -2- cyclohexene-Isosorbide-5-Nitrae-diketone product liquid；
The material liquid includes catalyst, reaction raw materials and solvent.
2. the side that continuous high-efficient oxidation according to claim 1 prepares 2,6,6- trimethyl -2- cyclohexene -1,4- diketone
Method, which is characterized in that injection, which is blended in the injection reactor of two-stage series connection, to be carried out, and the conversion ratio in the first stage reactor reaches
When to 85%-90%, it is transferred to the second stage reactor and continues to react.
3. the side that continuous high-efficient oxidation according to claim 2 prepares 2,6,6- trimethyl -2- cyclohexene -1,4- diketone
Method, which is characterized in that reaction carries out under conditions of continuous steady state operation；
Gas-liquid separation is carried out after the feed inlet continuous supplementation material liquid and oxygen-containing gas of the first stage reactor, reaction, gas phase is returned
The feed inlet for returning the first stage reactor is recycled, and the feed inlet that liquid phase a part returns to the first stage reactor after cooling follows
Ring enters the feed inlet of second level reactor after another part cooling；
In the second level, the feed inlet of reaction solution supplements oxygen-containing gas, and gas-liquid separation is carried out after reaction, and gas phase returns to the second order reaction
The feed inlet of device is recycled, and liquid phase a part returns to the feed inlet circulation of the second stage reactor, another part after cooling
It is continuously exported as product liquid.
4. the side that continuous high-efficient oxidation according to claim 3 prepares 2,6,6- trimethyl -2- cyclohexene -1,4- diketone
Method, which is characterized in that the flow rate of liquid of the reactor injector outlet is 5-15m/s, preferably 8-12m/s.
5. described in any item continuous high-efficient oxidation preparation 2,6,6- trimethyl -2- cyclohexene -1,4- according to claim 1~3
The method of diketone, which is characterized in that cooling processing, cooling extent are carried out to the liquid phase isolated using external tubular heat exchanger
It is 10-30 DEG C, preferably 15-20 DEG C.
6. described in any item continuous high-efficient oxidation preparation 2,6,6- trimethyl -2- cyclohexene -1,4- according to claim 1~3
The method of diketone, which is characterized in that cooling jacket is arranged in the surface of injection reactor.
7. described in any item continuous high-efficient oxidation preparation 2,6,6- trimethyl -2- cyclohexene -1,4- according to claim 1~3
The method of diketone, which is characterized in that oxygen content tester is equipped in injection reactor；
Oxygen content in injection reactor is 3-16%, preferably 6-12%.
8. described in any item continuous high-efficient oxidation preparation 2,6,6- trimethyl -2- cyclohexene -1,4- according to claim 1~3
The method of diketone, which is characterized in that the reaction is compressive reaction, reactor pressure 0.3-1.5MPa, preferably 0.6-
1.2MPa。
9. the side that continuous high-efficient oxidation according to claim 1 prepares 2,6,6- trimethyl -2- cyclohexene -1,4- diketone
Method, which is characterized in that the catalyst is metal complex, and wherein metal cation is iron, cobalt, nickel, copper, zinc, one in manganese
Kind or two kinds, ligand be one of acetylacetone,2,4-pentanedione, schiff bases, porphyrin；
The solvent is one or both of ethylenediamine, triethylamine, tripropyl amine (TPA), pyridine.
10. described in any item continuous high-efficient oxidation preparation 2,6,6- trimethyl -2- cyclohexene -1,4- according to claim 1~3
The method of diketone, which is characterized in that liquid holdup is 30-80%, preferably 40%-60% in reactor.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811100511.5A CN109438199B (en) | 2018-09-20 | 2018-09-20 | Method for preparing 2,6, 6-trimethyl-2-cyclohexene-1, 4-diketone by continuous and efficient oxidation |
| PCT/CN2019/095187 WO2020057235A1 (en) | 2018-09-20 | 2019-07-09 | Method for continuously and efficiently preparing 2,6,6-trimethyl-2-cyclohexene-1,4-dione by oxidation |
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| CN201811100511.5A CN109438199B (en) | 2018-09-20 | 2018-09-20 | Method for preparing 2,6, 6-trimethyl-2-cyclohexene-1, 4-diketone by continuous and efficient oxidation |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2020057235A1 (en) * | 2018-09-20 | 2020-03-26 | 浙江新和成股份有限公司 | Method for continuously and efficiently preparing 2,6,6-trimethyl-2-cyclohexene-1,4-dione by oxidation |
| EP3766570A1 (en) * | 2019-07-16 | 2021-01-20 | thyssenkrupp Industrial Solutions AG | Process for the production of alkoxylates |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2020057235A1 (en) * | 2018-09-20 | 2020-03-26 | 浙江新和成股份有限公司 | Method for continuously and efficiently preparing 2,6,6-trimethyl-2-cyclohexene-1,4-dione by oxidation |
| EP3766570A1 (en) * | 2019-07-16 | 2021-01-20 | thyssenkrupp Industrial Solutions AG | Process for the production of alkoxylates |
| WO2021009269A1 (en) * | 2019-07-16 | 2021-01-21 | Thyssenkrupp Industrial Solutions Ag | Process for the production of alkoxylates |
| CN114127155A (en) * | 2019-07-16 | 2022-03-01 | 蒂森克虏伯工业解决方案股份公司 | Process for producing alkoxylates |
| CN114127155B (en) * | 2019-07-16 | 2024-06-28 | 蒂森克虏伯伍德有限公司 | Method for producing alkoxylates |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109438199B (en) | 2020-04-07 |
| WO2020057235A1 (en) | 2020-03-26 |
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