CN103214393B - Oximation method of ketone - Google Patents
Oximation method of ketone Download PDFInfo
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- CN103214393B CN103214393B CN201310150573.8A CN201310150573A CN103214393B CN 103214393 B CN103214393 B CN 103214393B CN 201310150573 A CN201310150573 A CN 201310150573A CN 103214393 B CN103214393 B CN 103214393B
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Abstract
The invention discloses an oximation method of ketone. The method is to carry out an oximation reaction on ketone, ammonia and hydrogen peroxide in the presence of catalysts and solvents. The method is characterized in that a reactor 1 comprises a reaction area and a separation area, wherein most of catalyst particles in a reaction liquid are settled in the separation area and return to the reaction area; the reaction liquid containing a small amount of catalyst grains at the upper part of the separation area flows into an external filter 4 to be subjected to liquid-solid separation; a filtered clear liquid enters a next procedure; after being pressurized by a circulation pump 5 and is cooled by a circulation cooler 6, the filtered reaction liquid containing the catalyst is sufficiently mixed with external materials in a static mixer 7 and is fed back to the reactor 1. By utilizing the oximation method, the external liquid amount and the content of the catalyst in the circulation liquid are reduced to a large extent, the consumption of the catalyst and the operation cost of the device are effectively reduced, and the investment on the external filter, the circulation pump and the circulation cooler is saved.
Description
Technical field
The present invention relates to a kind of oximation process of ketone.Especially pimelinketone, acetone, the butanone method that oximate is produced cyclohexanone-oxime, acetoxime, Diacetylmonoxime respectively.
Background technology
Hexanolactam is the main raw material of producing nylon fibre and engineering plastics, and the preparation of cyclohexanone-oxime is the committed step of producing hexanolactam.At present, the method for preparing cyclohexanone-oxime mainly contains Raschig process, NO catalytic reduction method, phosphatic hydroxylamine method, amidoxime method.Wherein, amidoxime method with its preparation method simply, the advantage of by-product sulphur ammonium not, become the main flow of Caprolactam unit development in recent years, the improvement of relevant cyclohexanone oxamidinating process is studied still and to be carried out continuing.
Acetoxime and Diacetylmonoxime are mainly used in oxygen scavenging chemical etc.Industrial traditional processing technology mainly contains hydroxyamine hydrochloride, oxammonium sulfate method and sodium nitrite method at present.These three kinds of techniques not only complex process, Production Flow Chart is long, facility investment is high, have more serious corrosion and pollution problem, and the hydrochloride of a large amount of low values of association or vitriol byproduct.In the novel process that acetoxime and Diacetylmonoxime are produced, the most representative is that the direct oximate of acetone or butanone is prepared acetoxime or Diacetylmonoxime, have that transformation efficiency and selectivity are high, by product is few, the environmentally friendly and simple feature of technique, have the trend that replaces traditional technology.
Chinese patent ZL02100227.4 discloses the separation method of HTS in a kind of ketone oxamidinating reaction system.The continuous separate of realizing HTS and reaction product ketoxime with external settling vessel in this technical scheme from.
Chinese patent ZL02100228.2 discloses a kind of method of preparing cyclohexanone oxime by ammoximation of cyclohexanone.The continuous separate of realizing HTS and reaction product ketoxime with external settling vessel in this technical scheme from.
Chinese patent ZL200510133880.0 discloses a kind of preparation method of cyclohexanone-oxime.The claim of this technical scheme is mainly that reaction mixture forms cycling stream, and pimelinketone on reactor, ammonia, hydrogen peroxide add location schemes, do not relate to the separation scheme of reaction mass and catalyzer.
Chinese patent application CN200810227656.1 has announced the Ammoximation reaction of a kind of ketone or aldehyde.Adopt to be reacting slurry carry out multistage liquid-solid separation through wet cyclone and mineral membrane or metal sintering pipe, in this patent, wet cyclone and mineral membrane or metal sintering pipe etc. are reactor outer filter, and are all arranged on after recycle pump.
Chinese patent ZL201020046146.7 discloses a kind of cyclohexanone oxamidinating reactor.The core of this patent is the film filter by being installed in Ammoximation reaction device inside, completes separating of filtrate and catalyzer.
Chinese patent ZL201120054873.2 discloses a kind of cyclohexanone oxamidinating catalysts tripping device.The principal feature of this technical scheme is that the built-in and external filter of reactor series connection secondary substep filters, and the filtrate of built-in filter is directly sent into external filter and further filtered, and the film pore footpath of external filter film pipe aperture ratio built-in filter is little.
Chinese patent application CN201110209393.3 discloses the Ammoximation reaction device of producing cyclohexanone-oxime, and claim is mainly the structure of inside reactor, comprises inner filtering system, liquefied ammonia vaporizing coil, ring distributor, column drainage tube etc.
Chinese patent application CN201210016278.9 discloses a kind of method of preparing cyclohexanone oxime by ammoximation of cyclohexanone, it is characterized in that: by reactant outer circulation heat-obtaining mode control temperature of reaction, reaction product separates in strainer with HTS.This scheme is also by external filter is set after recycle pump, completes separating of filtrate and catalyzer.
Chinese patent ZL201220142109.5 discloses a kind of external mineral membrane amidoxime catalyzed reaction tripping device, reaction mass carries out systemic circulation between retort, charging pump, external mineral membrane cross-flow filter, mixing tank, and wherein a part of material carries out partial circulating in the formations such as feeding pipeline, recycle pump, external mineral membrane cross-flow filter, partial circulating pipeline closed circuit.This scheme is also by external filter is set after recycle pump, completes separating of filtrate and catalyzer, and does not relate to the scheme that removes reaction heat.
Chinese patent ZL201220294588.2 relates to a kind of cyclohexanone oxamidinating catalyzer dynamic separation device.This technical scheme realizes separating of catalyzer and feed liquid by the video disc film filtering element in dynamic separator tank body, and this scheme is also by dynamic separator is set after recycle pump, completes separating of filtrate and catalyzer, and does not relate to the scheme that removes reaction heat.
Chinese patent application CN201210328123.9 relates to a kind of method of the reactive system catalyzer filtering separation of preparing cyclohexanone-oxime, and the core of the method is that reactive system catalyzer filtering separation is to adopt catalyzer preseparator and two steps of catalyzer accurate filter to combine to complete continuously whole sepn processes.This scheme is arranged on catalyzer preseparator after recycle pump, and does not relate to the scheme that removes reaction heat.
Chinese patent application CN200410018607.9 relates to the technique of a kind of acetone or butanone oxidation production acetoxime or Diacetylmonoxime.Mainly lay particular emphasis on the description to reaction parameter, do not comprise concrete technique and describe.
Chinese patent application CN201110374542.1 relates to a kind of device of preparing acetoxime, comprises condenser, integral reactor, outer circulation pump.Wherein integral reactor is turriform reactor.
Chinese patent application CN201010229701.4 relates to a kind of method of preparing acetoxime, it is characterized in that acetone contacts under solvent, oxygenant, tensio-active agent and catalyzer exist with ammonia.Claim is mainly the selection to solvent, oxygenant, tensio-active agent and catalyzer.
In full scale plant, generally all adopt membrane filtration to reach the object of reaction solution and catalyst separating at present.Due to catalyst concn in reactive system higher (4%wt left and right), and due to impact and the abrasion of agitator paddle, circulating pump impeller, duct wall and appts wall in reactive system, catalyzer is compared with cracky, easily cause filter element to stop up, so strainer needs regularly to switch, so that back flushing or regenerated offline.
In above document, some schemes adopt built-in filter, are arranged in reactor, this scheme existence cleaning inconvenience and the more shortcoming of renew cartridge difficulty; Some schemes adopt external filter, are arranged on circulation pump outlet, and in reaction solution, catalyst content is high, and the time that this scheme strainer regularly switches is shorter.
Summary of the invention
The present invention is directed to the deficiency that prior art exists, a kind of oximation process of good ketone is provided.
The present invention has announced a kind of oximation process of ketone, is under the existence of catalysts and solvents, and ketone, ammonia and hydrogen peroxide carry out oximation reaction.Described ketone is selected from pimelinketone or acetone or butanone, and oximate product is respectively cyclohexanone-oxime or acetoxime or Diacetylmonoxime.The method comprises reactor 1, external filter 4, recycle pump 5, recirculation cooler 6, static mixer 7 and attached pipe fitting.
Reactor 1 is made up of reaction zone and disengaging zone.Reaction zone is positioned at reactor 1 bottom, inner with guide shell 9 and agitator 10, reaction solution in the inside and outside interregional pump circulation of guide shell 9 to react fully.Disengaging zone is positioned at reactor 1 top, inner with weir 2 and catalyzer backward channel 3, and reaction solution is in certain residence time of the interior maintenance in weir 2, allows most of granules of catalyst in reaction solution settle down, and returns to reaction zone by catalyzer backward channel 3.
Reaction zone outer wall is with chuck 8, internal guide cylinder 9 can be selected from double-layered cylinder, cylinder shape coil pipe or their combination of internal solid cylinder, interlayer hollow, if select double-layered cylinder or the cylinder shape coil pipe of interlayer hollow, while leading to water coolant in interlayer or coil pipe, guide shell 9, with the function of cooling reaction solution, can remove reactive system by part or all of reaction heat; In interlayer or coil pipe when logical steam, can heating use when driving.The heat interchanging area that increases chuck 8 and guide shell 9, can partly or entirely remove reactive system by reaction heat, can reduce or cancel recirculation cooler 6.
Weir, disengaging zone 2 includes the reaction solution of a small amount of granules of catalyst, flows into external filter 4 carry out liquid-solid separation from reaction solution outlet 11, and after filter, clear liquid enters next step operation; After filter containing the reaction solution of catalyzer through recycle pump 5 superchargings and recirculation cooler 6 cooling after, after static mixer 7 fully mixes, send reactor 1 back to additional material.
The catalyst grain size that reaction is used is at 1-200 μ m.External filter 4 is arranged between reactor 1 and recycle pump 5, and it is a kind of candle filter, and separate unit or many series/parallel combinations can be set.Filter core 4 is metal powder sintering membrane pipe, and the rejection that its percolation filters is 100%, and material is selected from 300 series stainless steels, Inconel(nickel alloys), nickel, Monel 400, Hastelloy C alloys 276, iron aluminium or other nickelic/Chrome metal powder.
Solvent, ammonia, ketone, hydrogen peroxide can add on the circulation line between recirculation cooler 6 and static mixer 7, and multiple reserved opening 12 that also can arrange on reactor 1 add respectively.Described recycle pump 5 can be separate unit or many parallel connections, and separate unit flow is at 200-1200m
3/ h, in loop slurry, solids content is at 0.5-16%wt.
The present invention adopts the method that disengaging zone is set at inside reactor, most of catalyzer is rested in reactor to be participated in reacting, reduce the catalytic amount of bringing external circulating system into, alleviated the working load of external filter, extended the switching time of Filter Back Washing and regenerated offline; Also reduced the damaged probability in catalyzer working cycle outside, when shortening reactive system operates non-cutting time, reduced the loss of catalyzer, reduced device running cost simultaneously.
The present invention, when reaction zone arranges chuck, is also provided with the guide shell that can have cooling effect concurrently, has strengthened reactor and remove the ability of reaction heat, can effectively reduce and even cancels external circulation heat exchanging device; In outer circulation, remove thermal load when reducing, because catalyst content in outer circulation reaction solution reduces, can suitably reduce external filter and recycle pump, can reduce significantly the investment of external filter, pump and recirculation cooler, be also conducive to save energy and reduce the cost.
Brief description of the drawings
Fig. 1 is process flow diagram of the present invention.
In figure: 1, reactor; 2, weir; 3, catalyzer backward channel; 4, external filter; 5, recycle pump; 6, recirculation cooler; 7, static mixer; 8, chuck; 9, guide shell; 10 agitators; 11, reaction solution outlet; 12, reserved opening.
Embodiment
Following examples are intended to illustrate the present invention instead of limitation of the invention.The present invention can implement by the either type described in summary of the invention.
Taking 100,000 tons/year of pimelinketone oximate reaction process flow processs as example, as shown in Figure 1, under concentration 4%wt catalyzer exists, solvent, ammonia, circulation fluid and the hydrogen peroxide respectively mouth of pipe from reactor 1 add, participate in the pump circulation in reaction zone, pimelinketone adds on circulation fluid pipeline.Pimelinketone, ammonia and hydrogen peroxide carry out oximation reaction in reactor 1.Reaction solution self-separation district flows into external filter 4 and carries out liquid-solid separation, and after filter, clear liquid enters next step operation; After filter containing the reaction solution of catalyzer through recycle pump 5 superchargings and recirculation cooler 6 cooling after, send back in reactor 1 after static mixer 7 fully mixes with additional pimelinketone.
External filter 4 filter cores adopt the powder sintered film pipe of 316 low carbon stainless steel, and the rejection that its percolation filters is 100%.Through detecting, approximately there is the granules of catalyst of 60%wt left and right to stay in reactor, in loop slurry, solids content is in 1.4%wt left and right; Recycle pump 5 flows can tune to 500m
3/ h; Recirculation cooler heat interchanging area can tune to 100m
2.In industrialized unit, in circulation fluid, solids content is about 4%wt at present; Pump flow is about 1000m
3/ h; The about 250m of recirculation cooler heat interchanging area
2.The present invention by comparison, has obvious advantage.
Claims (6)
1. an oximation process for ketone, is under the existence of catalysts and solvents, and ketone, ammonia and hydrogen peroxide carry out the method for oximation reaction, it comprises reactor (1), external filter (4), recycle pump (5), recirculation cooler (6), static mixer (7) and attached pipe fitting, is characterized in that:
A, reactor (1) are made up of reaction zone and disengaging zone, and reaction zone is positioned at reactor (1) bottom, and inner with guide shell (9) and agitator (10), outer wall is with chuck (8); Disengaging zone is positioned at reactor (1) top, inner with weir (2) and catalyzer backward channel (3), with reaction solution outlet (11), in reaction solution, most of granules of catalyst settles down in disengaging zone, returns to reaction zone by catalyzer backward channel (3);
B, certainly flow to further liquid-solid separation of external filter (4) containing the reaction solution autoreaction liquid outlet (11) of a small amount of granules of catalyst, after filter, clear liquid enters next step operation; After filter containing the reaction solution of catalyzer through recycle pump (5) supercharging and recirculation cooler (6) cooling after, after static mixer (7) fully mixes, send reactor (1) back to additional material;
C, under agitator (10) effect, reaction solution is in the inside and outside interregional pump circulation of guide shell (9).
2. the oximation process of ketone according to claim 1, is characterized in that: the catalyst grain size using is at 1-200 μ m.
3. the oximation process of ketone according to claim 1, is characterized in that: guide shell (9) can be double-layered cylinder or cylinder shape coil pipe or their combination of internal solid cylinder or interlayer hollow.
4. the oximation process of ketone according to claim 1, is characterized in that: external filter (4) is a kind of candle filter, and separate unit or many series/parallel combinations can be set.
5. according to the oximation process of the ketone described in claim 1,4, it is characterized in that: the filter core of external filter (4) is metal powder sintering membrane pipe, material is selected from 300 series stainless steels or Inconel(nickel alloys) or nickel or Monel 400 or Hastelloy C alloys 276 or iron aluminium.
6. the oximation process of ketone according to claim 1, is characterized in that: described ketone is pimelinketone or acetone or butanone, and oximate product is respectively cyclohexanone-oxime or acetoxime or Diacetylmonoxime.
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103551087B (en) * | 2013-11-08 | 2015-11-18 | 神马实业股份有限公司 | A kind of Ammoximation reaction system for the preparation of cyclohexanone oxime |
| CN104001461A (en) * | 2014-04-24 | 2014-08-27 | 金华精锐制药机械有限公司 | Detachable multifunctional kettle internal jacket easy to clean |
| CN103949191B (en) * | 2014-05-13 | 2016-04-20 | 湖北三宁化工股份有限公司 | A kind of cyclohexanone oximation reaction adds the device and method of catalyst continuously |
| CN107362765A (en) * | 2017-09-04 | 2017-11-21 | 阳煤集团太原化工新材料有限公司 | Oximation reaction feeding regulating device and adjusting method |
| CN109382071A (en) * | 2018-12-13 | 2019-02-26 | 上海释颉化工技术合伙企业(有限合伙) | A kind of combined type generation reactor being used to prepare hexamethylene diamine |
| CN110394134B (en) * | 2019-08-28 | 2024-04-19 | 沧州旭阳化工有限公司 | Cooling system |
| CN112174850B (en) * | 2019-10-11 | 2022-11-22 | 福建天辰耀隆新材料有限公司 | Preparation method of cyclohexanone oxime |
| CN112759530B (en) * | 2020-12-30 | 2022-11-11 | 河北美邦工程科技股份有限公司 | Large-scale cyclohexanone-oxime production device and method |
| CN115069184A (en) * | 2022-05-31 | 2022-09-20 | 南通联升电力科技有限公司 | Continuous saponification control system based on distributed IO |
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